JP3240981B2 - Electrolytic ozone generator - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to the deodorization of air and water,
Mildew, sterilization, relates to an electrolytic ozone generator for generating ozone for use as a purpose of sterilization.

[0002]

2. Description of the Related Art The basic structure and principle of a water electrolysis-type ozonizer were developed in the late 1970's and are disclosed in U.S. Pat. No. 4,316,782 (1982) and U.S. Pat. No. 4,541,989. (1985) The specification includes a solid polymer electrolyte membrane (Nafion: DuPont) and HBF ₄
Using solution as electrolyte, lead dioxide (PbO ₂ ) for anode
A basic water electrolysis system that supplies water using oxygen or platinum electrodes to generate ozone with oxygen, and uses a gas diffusion electrode as the cathode to generate hydrogen or supplies air to generate water. The configuration of the ozonizer is described.

Japanese Patent Application Laid-Open No. 5-109418 discloses a cell configuration in which air is supplied to a cathode side and water is supplied to an anode side to generate ozone. Further, JP-A-3-2
No. 71385 describes a structure in which a plurality of electrolytic cells are stacked, water is circulated through an anode and a cathode, and ozone is generated from the anode.

FIG. 10 is a flow chart showing the structure of a typical conventional water electrolysis type ozonizer. In the figure, 61 is the anode of the water electrolysis type ozonizer, 62 is the anode side plate,
63 is an anode water flow path, 64 is a cathode of a water electrolysis type ozonizer, 65 is a cathode side plate, 66 is a cathode water flow path, and 67 is an electrolyte membrane. In addition, the anode 61, the anode-side plate 62, the anode water channel 63, the cathode 64, the cathode-side plate 65, the cathode water channel 66, and the electrolyte membrane 67 of the water electrolysis type ozonizer for the water electrolysis type ozonizer for easy understanding of the structure. It is shown in a cross-sectional view in a cross section in the flow direction of water.

Reference numeral 68 denotes a water circulation pump, 69 denotes a deionized filter, 70 denotes an anode water discharge pump, 71 denotes a cathode water discharge pump, 72 denotes an anode water outlet pipe, 73 denotes an ozone-containing oxygen discharge pipe, and 74 denotes gas-liquid separation. Anode water tank, 75 is a cathode water outlet pipe, 76 is a hydrogen discharge pipe, 77 is a hydrogen catalytic combustor, 78 is an exhaust pipe, 79 is a cathode water tank for gas-liquid separation, 80 is a water circulation pipe, and 81 is an anode. Water supply piping, 8
2 is a water supply pipe to the cathode, 83 is a water storage tank, 83a
Is a water supply pipe for supplying water from the outside to the water storage tank 83, 84 is an external DC power supply, and 85 is a power supply plate.

The anode 61 of the water electrolysis type ozonizer is, for example, a titanium mesh plated with platinum and electrodeposited with lead dioxide. The electrolyte membrane 67 is made of Nafion (DuPont) and the water electrolysis type ozonizer. Cathode 6
No. 4 generally employs a titanium mesh or carbon paper coated with platinum fine particle powder or carbon powder carrying platinum fine particles.

In the water electrolysis type ozonizer, water is directly supplied to the anode 61 and the cathode 64, a DC voltage of several volts is applied, ozone and oxygen are generated on the anode side, and hydrogen is generated on the cathode side. Therefore, water containing oxygen and ozone is discharged from the anode water outlet 72, and oxygen and ozone are separated as gas in the gas-liquid separation tank 74, and used for ozone treatment.

On the other hand, water containing hydrogen is discharged to the cathode water outlet 75, hydrogen is separated as a gas in the gas-liquid separation tank 79, and oxidized by the air in the catalytic combustor 77 and discharged. In the catalytic combustor 77, catalytic oxidation is performed at a low temperature in the presence of air using an oxidation catalyst in which platinum particles are supported on an alumina carrier, and converted into water. A method of providing a hydrogen separation tower and circulating a gas-liquid mixture to separate hydrogen is described in JP-A-4-119903.

The water from which oxygen or ozone has been separated is moved to a water storage tank 83 using a pump 70. Similarly, water from which hydrogen has been separated is moved to a water storage tank 83 using a pump 71. Since water is constantly consumed by the water electrolysis, water is supplied from outside using the water supply port 83a.

The water circulated by the water circulating pump 68 is mixed with ions from a pipe or the like, so that it is necessary to remove the ions using a deionizing filter 69.
This is because if ions are mixed, the ion conduction resistance of the electrolyte membrane 67 may be increased, or the reaction of the anode 61 or the cathode 64 may be inhibited, thereby significantly reducing the ozone generation performance. When water is replenished from the outside, for example, tap water contains a large amount of ions such as calcium, and thus needs to be removed by the deionizing filter 69. In addition, the deionization filter 69 needs to be periodically replaced because ions are constantly accumulated and the ion exchange capacity is reduced.

On the other hand, in such a water electrolysis ozonizer, heat generated by water electrolysis can be easily removed by directly circulating water to the anode and the cathode.
In addition, the gas generated at the anode is occupied only by oxygen and ozone, and does not contain nitrogen or the like in the air, so that the ozone generation efficiency can be kept high, and a high concentration of ozone can be obtained. it can.

However, since the anode side is placed in an atmosphere almost close to pure oxygen, there is a potential danger inherent to oxygen, such as the danger of burning if oil-like substances are present. In addition, since a large amount of hydrogen is generated from the cathode side and hydrogen is often retained therein, thorough facilities for safety such as measures against hydrogen explosion are required. For this reason, the water electrolysis type ozonizer has a drawback that the device becomes complicated.

In addition to the method described above, hydrogen generated at the cathode is guided to the fuel electrode side of the fuel cell having an external short circuit, and air is sent to the air electrode side to perform the electrochemical reaction. Japanese Patent Laid-Open No. Hei 2
-101184. However, even if such a method is used, a large amount of pure hydrogen is always generated, and there is also a space in which hydrogen stays. Therefore, there is a problem of safety.

The water electrolysis type ozonizer is mainly used for water treatment or air treatment utilizing the oxidizing power of ozone, and is used for sterilization, deodorization, mold prevention and the like. Therefore, a method is used in which ozone generated by an ozone generator is dissolved or mixed in water or air for ozone treatment. The ozone concentration required for the ozone treatment at this time is water,
Both air require a very dilute concentration of ozone, at most on the order of 100 ppm. However, the gas generated from the anode is a mixture of oxygen and ozone, and the concentration of ozone is as high as several percent.

On the other hand, water or air subjected to ozone treatment may contain flammable substances such as oil and alcohol and organic substances. Since pure oxygen has extremely high flammability, and high concentration of ozone may cause explosion, it must be mixed with water and air for ozonation with great care.

[0016]

Since the conventional electrolytic ozonizer is configured so that water is directly supplied to the anode and the cathode as described above, the purity of the water is always kept high, and Also, it was necessary to remove ions in advance with a deionizing filter. In addition, there is a space in which a large amount of pure oxygen and pure hydrogen are generated and stay, and there is a problem in safety. Further, there is a safety problem when mixing a mixture of high concentration oxygen and ozone with water or air for ozone treatment.

[0017]

The present invention has been made in order to solve the above-described problems. Instead of directly supplying water to the anode and the cathode, water is supplied by supplying humidified air to the anode and the cathode. It is an object of the present invention to provide an electrolytic ozone generator that does not need to keep high purity. It is another object of the present invention to provide a highly safe electrolytic ozone generator by eliminating a space in which pure oxygen and pure hydrogen stay. Furthermore, in order to eliminate the danger of safety when mixing pure oxygen or high-concentration ozone with water or air subjected to ozone treatment, electrolysis that generates relatively low-concentration ozone with the same oxygen concentration as air as much as possible. It is an object of the present invention to provide an ozone generator.

[0019]

[0020]

An electrolytic ozone generator according to the present invention supplies a pair of electrodes comprising an anode and a cathode provided to face each other with an electrolyte membrane interposed therebetween, and supplies humidified air to the anode. A first humidified air supply means, a second humidified air supply means for supplying humidified air to the cathode, and a voltage application means for applying a voltage between the anode and the cathode, and supply to the electrodes by applying a voltage between the electrodes It electrolyzes the moisture in the humidified air.

A first humidified air flow passage provided near the anode and supplied with humidified air by the first humidified air supply means, and humidified air supplied near the cathode by a second humidified air supply means. And a second humidified air flow passage.

[0022] Further, there is provided an outlet exhaust pipe connected to the humidified air outlet of the first humidified air flow passage and the humidified air outlet of the second humidified air flow passage.

Further, humidified air generating means for humidifying the air to generate humidified air is provided, and the humidified air generated by the humidified air generating means is supplied to the humidified air flow passage by the humidified air supply means.

Further, a flowing water passage for flowing water is provided near the humidified air flowing passage. Further, the humidified air generating means generates humidified air using water flowing through the flowing water passage. Furthermore, a water-permeable membrane is provided so as to be in contact with the flowing water passage, and the air is humidified by the water passing through the water-permeable membrane.

The first humidified air flow path is a flow path without branch. Further, the first humidified air flow passage is a bellows type flow passage.

Further, the apparatus includes a plurality of stacked electrolytic ozone generators and a cooler provided between the electrolytic ozone generators. Further, the second humidified air supply means supplies humidified air in parallel to the second humidified air flow passage of each electrolytic ozone generator.

Further, the outflow side of the first humidified air flow passage of the electrolytic ozone generator and the inflow side of the first humidified air flow path of another electrolytic ozone generator are connected to each other to generate electrolytic ozone. The humidified air is supplied in series to the first humidified air flow passage of the vessel.

[0028]

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 FIG. 1 is a flowchart showing the configuration of the electrolytic ozone generator according to the first embodiment. In the figure, 1 is an anode-side plate of an electrolytic ozone generator, 2 is a cathode-side plate of an electrolytic ozone generator, 3
Is an electrode / membrane assembly in which an anode and a cathode are opposed to each other with an electrolyte membrane interposed therebetween, 4 is a current-carrying plate opposed to each other across an anode-side plate 1, a cathode-side plate 2, and an electrode / membrane assembly 3; 4
Is an external DC power supply that applies a voltage to the power supply. Reference numeral 6 denotes an air blower for supplying air, 7 denotes an external humidifier for humidifying the air supplied from the air blower 6, a water supply port 7a for supplying water to the external humidifier 7, and an external humidifier 7 A water discharge port 7b for discharging water from is provided.

8 is an air pipe for supplying air supplied from the air blower 6 to the external humidifier 7, 9 is a pipe for supplying air humidified by the external humidifier 7 to humidified air supply pipes 10 and 11, and 10 is a pipe. A humidified air supply pipe connected to the pipe 9 to supply humidified air to the anode-side plate 1, 11 is a humidified air supply pipe connected to the pipe 9 to supply humidified air to the cathode-side plate 2, and 12 is a humidified air supply pipe from the anode-side plate 1. An outlet pipe for discharging an anode outlet gas containing air with increased ozone and oxygen concentration, an outlet pipe 13 for discharging a cathode outlet gas containing air with reduced oxygen concentration from the cathode side plate 2, 14 an outlet pipe 12 and The outlet pipe is connected to the outlet pipe 13 and discharges air containing ozone.

FIG. 2 shows the anode-side plate 1 shown in FIG.
FIG. 2 is a cross-sectional side view showing the structure of a cathode-side plate 2 and an electrode / membrane assembly 3. FIG. 3 is a plan view of the AA cross section shown in FIG. 2 as viewed from the electrolyte membrane side. In the figure, reference numeral 3 denotes an electrode / membrane assembly, which comprises an anode 3a of an electrolytic ozone generator, a cathode 3b of an electrolytic ozone generator, and an electrolyte membrane 3c.
Reference numeral 15 denotes a humidified air flow passage of the anode-side plate 1, which comprises an air supply groove 15a of the anode-side plate 1 and an anode-side internal manifold 15b. Reference numeral 16 denotes a humidified air flow passage of the cathode plate 2, and an air supply groove 16 of the cathode plate 2.
a, the cathode-side internal manifold 16b.
17 is an anode side gasket, 18 is a cathode side gasket.

The other reference numerals are the same as those described with reference to FIG. Although the shape of the anode-side plate 1 has been described with reference to FIG. 3, in the present embodiment, it is assumed that the cathode-side plate 2 has the same shape as the anode-side plate 1.

Since the anode side plate 1 is required to have corrosion resistance at a high potential, the humidified air flow passage 15 including the air supply groove 15a and the internal manifold 15b is formed by plating a machined titanium plate with platinum plating. However, a stainless steel plate plated with platinum or gold can also be used. The air supply groove 15a and the internal manifold 15b can also be formed by pressing a titanium plate.

On the other hand, since the cathode side plate 2 does not require corrosion resistance because the potential on the cathode side is low, a plate provided with an air supply groove 16a and an internal manifold 16b by machining a carbon plate was used. However, a titanium plate may be used similarly to the anode side plate 1.

Although a proton conductive solid polymer electrolyte membrane is used as the electrolyte membrane 3c, a porous electronic insulating material impregnated with an acidic electrolyte or an alkaline electrolyte can also be used. For the anode 3a, a sheet of fine powder of β-PbO ₂ was used, and a mesh made of titanium was used as a current collector. The cathode 3b was formed by coating a carbon paper with a catalyst powder having platinum particles supported on a carbon carrier.

On the other hand, the anode side gasket 17 and the cathode side gasket 18 were formed by piercing a sheet made of a fluorine resin. In addition, the anode 3a, the cathode 3b, and the electrolyte membrane 3c were joined to the electrolyte membrane 3c by hot pressing together with the gaskets 17 and 18 to form the electrode / membrane assembly 3. However, the electrodes 3a, 3b and the electrolyte membrane 3c
Does not need to be adhered, but only needs to be physically adhered.

Next, the operation will be described. The air in the atmosphere is guided by the air blower 6 to the external humidifier 7 through the pipe 8 and bubbling is performed underwater to humidify the air. And
The humidified air is supplied to the anode side plate 1 by a pipe 9 and a humidified air supply pipe 10, and the pipe 9, a humidified air supply pipe 11
To the plate 2 on the cathode side.

The humidified air supplied to the anode-side plate 1 passes through the humidified air flow passage 15 (air supply groove 15a, internal manifold 15b).
The moisture of the air passing through 5 is taken into the electrolyte membrane 3c, and when the electrolyte membrane 3c is acidic, the moisture is electrolyzed at the anode 3a to generate ozone and oxygen. Then, the generated ozone and oxygen are discharged from the outlet discharge pipe 12 together with the air.

On the other hand, the humidified air supplied to the cathode-side plate 2 passes through the humidified air flow passage 16 (the air supply groove 16a, the internal manifold 16b). Protons generated at the time of electrolysis on the anode side 3a are converted into the cathode 3 via the electrolyte membrane 3c.
Water that is combined with the one that has reached b is generated. The generated water is discharged together with air from the outlet pipe 13 through the humidified air flow passage 16, but a part of the water is again absorbed by the electrolyte membrane 3c, returns to the anode side 3a by diffusion, and is used for electrolysis. .

The details of the electrolysis will be described. In addition, electricity flows from the external DC power supply 5 to the anode 3a and the cathode 3b through the conducting plate 4, and electrolysis occurs. The moisture in the humidified air permeates the electrolyte membrane 3c from both the anode side and the cathode side via the electrode, and the anode 3a uses this moisture as a reactant.
Oxygen and ozone are generated by the following (Equation 1) and (Equation 2). 2H ₂ O → O ₂ + 4H ⁺ + 4e ⁻ (Formula 1) 3H ₂ O → O ₃ + 6H ⁺ + 6e ⁻ (Formula 2)

Therefore, at the outlet side of the anode 3a (the outlet side of the humidified air flow passage 15), air containing ozone, having an increased oxygen concentration and reduced humidity comes out. Protons reach the cathode 3b through the electrolyte membrane 3c, and electrons reach the cathode 3b through the external circuit and the DC power supply 5.

On the other hand, since sufficient air is supplied on the cathode side, water is generated by the reaction of the following (formula 3). The water is discharged to the cathode side together with the air, but part of the water is diffused to the anode side via the electrolyte membrane 3c and used as a reactant of the anodic reaction. O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O (formula 3)

Therefore, the cathode outlet side (humidified air flow passage 1)
At the outlet side (6), air with a reduced oxygen concentration comes out. Further, by combining the gas of the outlet pipe 12 of the anode outlet gas and the gas of the outlet pipe 13 of the cathode outlet gas, the air having the same oxygen concentration as the atmosphere and the ozone added from the outlet pipe 14 can be obtained. can get.

Here, the reason why the oxygen concentration becomes almost the same as that in the atmosphere is that oxygen is generated by the reaction of (Equation 1) at the anode, but almost the same amount of oxygen is consumed by the reaction of (Equation 3) at the cathode. That is because Thus, as long as the ozone-containing gas has an oxygen concentration almost the same as that in the atmosphere, there is no problem in using the oxygen concentration gas at any place and there is no effect on the human body.

In a conventional water electrolysis-type ozonizer, since water is circulated and supplied directly to the anode side, water supplied from the outside is always required to have high purity, and is provided with an expensive deionization filter. It was necessary to remove all the contained ions. Also, if tap water is used directly, calcium will be taken in on the anode side, penetrate into the electrolyte membrane and increase the resistance significantly, deteriorating the performance, or deteriorating on the cathode side to inhibit the reaction. There was fear. Further, the deionization filter had to be replaced frequently.

However, in this embodiment, since the water evaporated in the humidifier is supplied to the anode side, ordinary water such as tap water can be used as it is for the humidifier. In addition, impurities such as calcium contained in tap water are accumulated, but when supplying water to the humidifier, the remaining water is discharged from the water outlet, and new water is supplied from the water supply port. If this is the case, it is easier and more economical than to provide a deionization filter because the concentrated impurities can be easily removed.

Further, since the amount of ozone generation can be controlled by adjusting the flow rate of the humidified air, the amount of ozone generation can be freely adjusted as necessary.

In this embodiment, by sending humidified air to the anode and the cathode, the concentration of oxygen generated at the anode can be diluted to reduce the danger of high-concentration oxygen with respect to combustion. Even if hydrogen is generated at the cathode, the danger of hydrogen can be greatly reduced by oxidizing the hydrogen generated at the cathode with oxygen in the air, so safety is maintained without taking special safety measures be able to.

Further, since the water used for the reaction is replenished with the humidified air, even if the water in the water tank is slightly contaminated, there is little possibility that the contaminated water directly reaches the anode or the cathode.
Therefore, there is no need to provide an ion exchanger. Further, since the amount of ozone generation can be controlled by adjusting the flow rate of the humidified air, the amount of ozone generation can be freely controlled as required.

With the area of the anode and the cathode set to 25 cm ² , a DC voltage of 3.5 V was applied to the electrolytic ozone generator having the structure shown in FIG. When the operation was performed by supplying air at a rate of 40%, the outlet gas temperature was 40 ° C and the oxygen concentration was
As a result, an ozone-containing gas having an average ozone concentration of 900 ppm was obtained stably.

Embodiment 2 FIG. 4 is a flowchart showing the configuration of the electrolytic ozone generator according to the second embodiment. In the figure, 19 is a carbon cooler having a flow path shape as shown in FIG. 3, 20 is a cooling water circulation pump, 21 is a cooling water pipe, and 22 is a pipe for supplying water to the cooler 19. . Other configurations are the same as those in the first embodiment, and a description thereof is omitted. In the cooler 19, water is directly supplied to the carbon plate having the same flow path shape as in FIG. 3, but a metal pipe or the like may be provided.

Next, the operation will be described. Except for cooling by the cooler 19, the operation is the same as that described in the first embodiment, and therefore the other description is omitted. The water stored in the external humidifier 7 is supplied to the cooler 19 via the pipe 22 by the cooling water circulation pump 20, and the water from the cooler 19 is circulated to the external humidifier 7 via the pipe 21. . At this time, water passes through the inside of the cooler 19, and the anode-side plate 1 can be cooled.

The anode generates a large amount of heat, and if the temperature increases, the generation efficiency of ozone may decrease. However, in the present embodiment, since the cooler is provided, the anode-side plate 1 is cooled and generated by electrolysis. By removing heat, the reaction temperature for generating ozone can be kept low.

The warmed cooling water is supplied to the humidifier to heat the humidifying water, so that the air can be sufficiently humidified. Therefore, an electrolytic ozone generator having a larger electrode area than in the first embodiment can be used.

In this embodiment, the cooler 19 is arranged on the anode side plate side, but this is not particularly limited. The cooler 19 may be arranged on the cathode side plate side or both plate sides. What is necessary is just to arrange so that the generated heat can be removed.

In this embodiment, since the cooling water flows near the anode and the cathode, the cooling can be performed effectively, and the operation can be performed while keeping the temperature constant even when the current increases. Also,
By using the warmed cooling water for humidifying the air, it is possible to give sufficient moisture to the air, and to take away the heat of evaporation when the water evaporates, so that the cooling water can be cooled effectively.

The area of the anode and the cathode was 100 cm.
As an example ² , the electrolytic ozone generator having the configuration shown in FIG. 4 was operated by applying a DC voltage of 3.5 V and supplying air at a rate of 8 liters per minute in accordance with the anode and the cathode. Outlet gas temperature 35 ° C, oxygen concentration 20
%, An ozone-containing gas having an ozone concentration of 1100 ppm on average was obtained stably.

In this embodiment, the water in the external humidifier is used for cooling. However, the water stored in another water tank may be circulated, or new water may be supplied. Such a structure may be adopted.

Embodiment 3 FIG. 5 is a flowchart showing the configuration of the electrolytic ozone generator according to the third embodiment. In the figure, reference numeral 23 denotes a humidifying / cooling water plate made of carbon having a flow path shape as shown in FIG. 3, 24 denotes a water-permeable membrane provided in contact with the humidifying / cooling water plate 23, 25
Is an air humidification plate provided on the opposite side of the humidification and cooling water plate 23 via the water permeable film 24. Reference numeral 26 denotes a water tank having a water supply port 26a for supplying water and a discharge port 26b for discharging water. Other reference numerals are the same as those in the second embodiment, and a description thereof will be omitted.

As the air humidifying plate 25 and the humidifying / cooling water plate 23, a carbon plate having the same flow path as in FIG. 3 is used, and the air humidifying plate 25 and the humidifying / cooling water plate 23 Are configured to face each other. As the water permeable film 24, carbon felt was used. Other suitable materials include a solid polymer electrolyte membrane and a porous membrane made of carbon, fluorine or polypropylene.

Next, the operation will be described. Except for cooling by the humidifying and cooling water plate 23 and humidification of the air by the air humidifying plate 25, the operation is the same as that described in the first embodiment, and the other description is omitted.

The cooling water circulation pump 20 controls the water tank 2
The water stored in 6 is supplied to the humidifying / cooling water plate 23 via the pipe 22, and the water from the humidifying / cooling water plate 23 is circulated to the water tank 26 via the pipe 21. At this time, the water in the humidification and cooling water plate 23 heated by the heat transfer from the electrolytic cell is supplied to the air humidification plate 25 via the water permeable film 24, and the humidified air is supplied to the pipe 9.

As described above, the humidification and cooling water plate 2
3, the electrolytic cell composed of the anode-side plate 1, the cathode-side plate 2, and the electrode / membrane assembly 3 is cooled, and the air is humidified via the water-permeable membrane 24. The air humidification plate 25 is warmed by heat transfer from the electrolytic cell via the humidification / cooling water plate 23, so that sufficient humidification of air is performed.

In the present embodiment, sufficient humidification is performed only by passing air through the surface of the wet membrane, and it is not necessary to bubble the air in water. Driving is possible.

The area of the anode and the cathode was 100 cm.
^{As a second} example, the electrolytic ozone generator having the configuration shown in FIG. 5 was operated by applying a DC voltage of 3.5 V and supplying air at a rate of 8 liters per minute in accordance with the anode and the cathode. Outlet gas temperature 35 ° C, oxygen concentration 20
%, An ozone-containing gas having an average ozone concentration of 1000 ppm was stably obtained.

Embodiment 4 FIG. 6 is a plan view of the electrolytic ozone generator according to Embodiment 4 as viewed from the air supply groove side of the anode-side plate. In the figure, reference numeral 15 denotes a bellows type flow path which is a humidified air flow path of the anode side plate, 15c denotes an anode air inlet side area in the bellows type flow path 15, and 15d denotes an anode air outlet side area in the bellows type flow path 15. In addition,
As in the case of the first embodiment, a plate formed by machining a titanium plate to form a groove and performing platinum plating was used as the anode-side plate 1.

In this embodiment, since the air flow path is of a bellows type (also known as serpentine type), ozone hardly contained in the air inlet area 15c is supplied to the air outlet area 15d of the bellows type flow path 15. The density gradually increases as approaching, and becomes the highest concentration in the air outlet region 15d.

In the case of the flow path of the type shown in FIG. 3 of the first embodiment, a reaction distribution occurs in the plane, and the amount of ozone generated differs depending on the location. Although a high concentration of ozone cannot be obtained, a high concentration ozone can be obtained without being influenced by the reaction distribution in the case of the flow path of the type shown in FIG.

It is known that the higher the oxygen concentration, the higher the efficiency of ozone generation. However, in the configuration shown in FIG. 6, the oxygen concentration gradually increases with the generation of oxygen from the air inlet region to the air outlet region. As a result, the current efficiency of ozone generation is gradually increased, and a higher concentration of ozone can be obtained.

In the present embodiment, the humidified air flow passage of the anode side plate 1 is of a bellows type, but this is not particularly limited, and the humidified air flow passage is always branched without being branched. What is necessary is just a thing which becomes one path.

In the present embodiment, since the air supply groove on the anode side is a bellows type flow path, the oxygen concentration increases as approaching the outlet side, and it is possible to increase the current efficiency of ozone generation and operate efficiently. it can.

The area of the anode and the cathode was 25 cm ²
The plate of the electrolytic ozone generator having the structure shown in FIG. 1 was constructed as shown in FIG. 6, a DC voltage of 3.5 V was applied, and air was supplied at a rate of 2 liters per minute for the anode and the cathode. Was supplied, and an ozone-containing gas having an outlet gas temperature of 35 ° C., an oxygen concentration of 20%, and an ozone concentration of 1500 ppm on average was obtained stably.

Embodiment 5 FIG. 7 is a diagram showing a configuration of an electrolytic ozone generator according to the fifth embodiment. FIG. 7A is a plan view of the electrolytic ozone generator, and FIG. 7B is a front view of the electrolytic ozone generator. It is.

In the drawing, reference numeral 10 denotes an inlet port for supplying humidified air to the anode plate 1, and reference numeral 11 denotes a cathode plate 2.
An inlet port for supplying humidified air to the anode, an outlet port for discharging an anode outlet gas containing air having an increased ozone and oxygen concentration from the anode side plate, and an air having a reduced oxygen concentration from the cathode side plate. An outlet port for discharging a cathode outlet gas containing

Reference numeral 19 denotes a cooler inserted between every two electrolytic cells, reference numeral 27 denotes a holding plate, and reference numeral 28 denotes a fastening jig. The cooler 19 is inserted between a plurality of stacked electrolytic cells and between the electrolytic cells. Is held down by the holding plates 27 on both sides, and the fastening jig 28 is fixed by tightening. 29 is a terminal mounting portion of the power supply plate 4, 30 is a cooling water inlet port for supplying cooling water to the cooler 19, and 31 is a cooling water outlet port for discharging cooling water from the cooler 19. Here, the electrolytic cell means an electrode-membrane assembly,
Hereinafter, the same meaning is used.

The electrolytic ozone generator according to the present embodiment is a laminated electrolytic ozone generator having an effective area of 100 cm ^2.
Electrode / membrane assembly 3 is stacked in four cells. In addition, the coolers 19 are inserted every two cells, and the cooling water of each cooler 19 flows from the cooling water inlet port 30 through the common internal manifold (not shown) and is taken out from the cooling water outlet port 31. It has become.

Next, the operation will be described. An internal manifold through which the humidified air penetrates a laminated body including the anode-side plate 1, the cathode-side plate 2, the electrode / membrane assembly 3, the cooler 19, etc. using the inlet ports 9 and 10 and the outlet ports 11 and 12. (Not shown) to each plate
Discharge. Here, it is assumed that the internal manifold is connected to the inlet side or the outlet side of each plate in a cylindrical space.

FIG. 7 does not show the humidification tank, the cooling water circulation loop, the air piping, and the like, but the same configuration as that of the first embodiment shown in FIG. 1 can be used.
Note that a humidifying portion may be provided in contact with the laminate as in Embodiment 3.

In the present embodiment, cooling can be performed effectively by using a cooler inserted every several cells for a plurality of electrolysis cells, and the operation can be performed while keeping the temperature constant.

The area of the anode and the cathode was 100 cm ²
In a four-cell stacked electrolytic ozone generator having the structure shown in FIG. 7, a DC voltage of 14 V is applied, and air is supplied at a rate of 30 liters per minute for both the anode and cathode sides. As a result, an ozone-containing gas having an outlet gas temperature of 35 ° C., an oxygen concentration of 20% and an average ozone concentration of 900 ppm was obtained stably.

Embodiment 6 FIG. FIG. 8 is a gas flow diagram of the laminate showing the configuration of the electrolytic ozone generator of the sixth embodiment. In the figure, reference numeral 32 denotes an electrolysis cell, which is a first cell 32a, a second cell 32b, a third cell 32c, and a fourth cell 32d in the order in which they are stacked. 33 is an air pipe from the anode outlet of the first cell 32a to the anode inlet of the second cell 32b, and 34 is a third air pipe from the anode outlet of the second cell 32b.
Is an air pipe from the anode outlet of the third cell 32d to the anode inlet of the fourth cell 32d.

The anode gas pipes 33, 34, 35 and the cathode gas pipe were formed using a cylindrical internal manifold provided in common to each plate. For example,
In the air pipe 33 from the anode outlet of the first cell 32a to the anode inlet of the second cell, a cylindrical manifold provided in the peripheral gas seal portion is connected to the anode outlet of the first cell 32a and the second manifold.
In the air pipe 34 from the anode outlet of the second cell 32b to the anode inlet of the third cell 32c, a cylindrical manifold provided in the peripheral gas seal portion is provided so as to communicate only between the anode inlets of the cells 32b. The communication was established only between the anode outlet of the second cell 32b and the anode inlet of the third cell 32c.

Such a structure is disclosed in, for example,
An internal manifold type laminate structure used in a polymer electrolyte fuel cell described in Japanese Patent No. 215781 can be applied.

In the present embodiment, the humidification air flow passages of the plurality of anode side plates stacked in series are connected in series, that is, the outlet of the immediately preceding humidification air flow passage is connected to the entrance of the next humidification air flow passage. Therefore, the humidified air flows in series to the plurality of anodes, and the oxygen concentration increases toward the downstream anode, so that the current efficiency of ozone generation can be increased.

In this embodiment, since the humidified air flow passages of the plurality of cathode side plates stacked in parallel are arranged in parallel, air having a constant oxygen concentration is supplied to the humidified air flow passages of each cathode side. Hydrogen generation at each cathode can be reliably prevented.

The area of the anode and the cathode was 100 cm ²
A four-cell laminated electrolytic ozone generator having the structure shown in FIG. 8 was constructed as shown in FIG. 4, a DC voltage of 14 V was applied, and the anode and cathode sides were combined at a rate of 30 liters per minute. As a result, an ozone-containing gas having an ozone concentration of 35 ° C. at an outlet gas temperature and an average of 1300 ppm of oxygen was obtained stably.

Reference example . Figure 9 is a diagram showing no residual hydrotreater. In the figure,
51 is a residual hydrogen-treated anode plate, 52 is an anode-side electrode, 53 is an electrolyte membrane, 54 is a residual hydrogen-treated cathode plate, 55 is a cathode-side electrode, 56 is a resistor, 57 is an external wiring, 58 is a current collector plate, and 59 is a current collector plate. Anode side flow path, 60
Is a cathode-side flow path, 61 is an anode gas inlet, 62 is an anode gas outlet, 63 is a cathode gas inlet, and 64 is a cathode gas outlet.

The structure of the flow path is substantially the same as that of FIG.
The material of No. 4 is carbon. Also, the anode-side electrode 52
For the cathode 55, a catalyst obtained by applying a catalyst in which platinum particles are supported on carbon powder to carbon paper and heat-treated was used. A solid polymer electrolyte membrane was used as the electrolyte membrane. As for the channels 59 and 60, channels having substantially the same shape as that of FIG. 3 were provided by machining a carbon plate.

Next, the operation will be described. Hydrogen to be processed is supplied to the anode gas inlet 61, and air is supplied to the cathode gas inlet 63. The hydrogen supplied from the anode gas inlet 61 passes through the anode-side flow path (air supply groove, internal manifold) 59, so that the hydrogen passing through the anode-side flow path 59 is taken into the electrolyte membrane 53, and
In 2, the hydrogen is electrolyzed as shown below using this hydrogen as a reactant. 2H ₂ → 4H ^{+ +} 2e ^-

On the other hand, the air supplied from the cathode gas inlet 63 passes through the cathode side flow path (air supply groove, internal manifold) 60, so that oxygen in the air passing through the cathode side flow path 60 is transferred to the electrolyte membrane 53. Water is generated by the following reaction because the oxygen is supplied and sufficient oxygen is supplied on the cathode side. O ₂ + 4H ⁺ + 2e ⁻ → 2H ₂ O In this case, most of the energy generated at the anode and the cathode is converted into electric energy. The electric energy generated by the above reaction is consumed by the resistor 56 connected between the current collecting plates 58 via the external wiring 57.

Here, a resistor is connected as the load, but this is not particularly limited, and any resistor that consumes electric energy may be used.

In the residual hydrogen treatment device shown in FIG . 9, since the electric energy generated during the reaction at the anode and the cathode is consumed by the load connected between the electrodes, the heat generated at the anode and the cathode is reduced. Can be reduced.

In the first to sixth embodiments, the absolute amount of water required for electrolysis of water for generating ozone can be increased by humidifying air having a low relative humidity. Since the absolute humidity greatly varies depending on the temperature and rapidly increases as the temperature rises, the absolute humidity, that is, the supply amount of water can be greatly increased by using the heated cooling water for humidification. Also, by heating the heater etc.
The absolute humidity may be increased by increasing the temperature of the humidifying water.

Although the degree of humidification varies depending on the flow rate of the flowing air, it is desirable that the relative humidity is 70% or more, and preferably about 100%. As a method of increasing the relative humidity of the humidified air, the structure of a conventional humidifier or gas cleaning bottle is sufficient, but humidification through a water-permeable membrane is
It was the most effective of the above embodiments.

[0095]

In the air supply type electrolytic ozone generator according to the present invention, a pair of electrodes comprising an anode and a cathode provided to face each other with an electrolyte membrane interposed therebetween, and humidified air is supplied to the anode. A first humidified air supply means, a second humidified air supply means for supplying humidified air to the cathode, and a voltage application means for applying a voltage between the anode and the cathode, wherein a voltage is applied between the electrodes. Since the water in the humidified air supplied to the electrode is electrolyzed, even if the water supplied to the anode and the cathode is dirty, there is little possibility that the contaminated water directly reaches the anode or the cathode. No need to prepare.

The first humidified air flow passage provided near the anode and supplied with humidified air by the first humidified air supply means, and the humidified air supplied near the cathode and supplied by the second humidified air supply means. The provision of the second humidified air flow passage makes it possible to determine a route through which the humidified air flows in the vicinity of the anode and the cathode.

[0097] Since there is an outlet exhaust pipe connected to the humidified air outlet of the first humidified air flow passage and the humidified air outlet of the second humidified air flow passage, the danger of oxygen at the anode and The danger when hydrogen is generated at the cathode can be greatly reduced, and safety can be maintained.

[0098] Humidified air generating means for humidifying air to generate humidified air is provided, and the humidified air generated by the humidified air generating means is supplied to the humidified air flow passage by the humidified air supply means. The humidity of the supplied humidified air can be adjusted.

Since the flowing water passage is provided near the humidified air flowing passage, the electrodes and the electrolyte membrane can be efficiently cooled. Therefore, even when the current increases, the operation can be performed while keeping the temperature constant.

Since the humidified air generating means generates the humidified air using the water flowing through the flowing water passage, the cooling water in the flowing water passage heated by the heat generated by the electrode / membrane assembly is used as the humidifying water for air humidification. Can be used. Further, by using the warmed cooling water for humidifying the air, sufficient air can be given to the air, and the heat of evaporation of the water is taken away, so that the cooling water can be cooled efficiently.

Since the flowing water passage and the air are opposed to each other via the water-permeable membrane, and the air is humidified by the water permeating the water-permeable membrane, sufficient humidification can be achieved only by passing the air through the surface of the squeezed membrane. In this case, the air does not need to be bubbled in the water, and the power of the pump for sending the air can be kept low and the pump can be operated efficiently.

Since the first humidified air flow passage is a flow passage without branching, the oxygen concentration increases as approaching the outlet side, and the current efficiency of ozone generation can be increased to operate efficiently.

Since the first humidified air flow passage is a bellows-type flow passage, the first humidified air flow passage can pass evenly in the vicinity of the anode, and the oxygen concentration increases as it approaches the outlet side. In addition, the current efficiency of ozone generation can be increased to operate efficiently.

A plurality of stacked electrolytic ozone generators;
Since it is equipped with a cooler provided between electrolytic ozone generators, it cools efficiently using coolers inserted every few cells for a plurality of electrolytic cells, and operates while keeping the temperature constant. can do.

Since the second humidified air supply means supplies humidified air in parallel to the second humidified air flow passage of each electrolytic ozone generator, it is necessary to supply air having a constant oxygen concentration to each cathode. And the generation of hydrogen at each cathode can be reliably prevented.

The outflow side of the first humidified air flow path of the electrolytic ozone generator is connected to the inflow side of the first humidified air flow path of another electrolytic ozone generator, and 1
Since the humidified air is supplied to the humidified air flow passage in series, the anode concentration on the downstream side is higher, the current efficiency of ozone generation can be increased, and the operation can be performed efficiently.

[0107]

[Brief description of the drawings]

FIG. 1 is a diagram showing an electrolytic ozone generator according to Embodiment 1 of the present invention.

FIG. 2 is a side sectional view of the anode-side plate shown in FIG.

FIG. 3 is a plan view of the anode-side plate shown in FIG.

FIG. 4 is a diagram showing an electrolytic ozone generator according to Embodiment 2 of the present invention.

FIG. 5 is a view showing an electrolytic ozone generator according to Embodiment 3 of the present invention.

FIG. 6 is a plan view of an anode-side plate of the electrolytic ozone generator according to Embodiment 4 of the present invention.

FIG. 7 is a diagram showing an electrolytic ozone generator according to Embodiment 5 of the present invention.

FIG. 8 is a diagram showing an electrolytic ozone generator according to Embodiment 6 of the present invention.

9 is a side sectional view showing a hydrogen treatment apparatus.

FIG. 10 is a schematic cross-sectional view of a conventional water electrolysis ozonizer.

[Explanation of symbols]

Reference Signs List 1 anode side plate 2 cathode side plate 3 electrode / membrane assembly 3a anode of electrolytic ozonizer 3b cathode of electrolytic ozonizer 3c electrolyte membrane 4 conducting plate 5 external DC power supply 6 air blower 7 external humidifier 7a water supply port 7b water drain Outlet 8 air pipe 9 pipe 10 humidified air supply pipe 11 humidified air supply pipe 12 anode outlet gas outlet pipe 13 cathode outlet gas outlet pipe 14 outlet pipe 15 humidified air flow path 15a air supply groove 15b anode internal manifold 15c anode air Inlet side area 15d Anode air outlet side area 16 Humidifying air flow passage 16a Air supply groove 16b Cathode side internal manifold 17 Anode side gasket 18 Cathode side gasket 19 Cooler 20 Cooling water circulation pump 21 Cooling water pipe 22 Pipe 23 Humidification and cooling water Plate 24 Water permeable membrane 25 Air supply Plate 26 Water tank 26a Water supply port 26b Water discharge port 27 Holding plate 28 Tightening jig 29 Terminal mounting part of current supply plate 30 Cooling water inlet port 31 Cooling water outlet port 32 Electrolytic cell 33-35 Air piping 51 Residual hydrogen treatment anode plate 52 Anode side electrode 53 Electrolyte membrane 54 Residual hydrogen treatment cathode plate 55 Cathode side electrode 56 Resistance 57 External wiring 58 Current collector plate 59 Anode side flow path 60 Cathode side flow path 61 Anode gas inlet 62 Anode gas outlet 63 Cathode gas inlet 64 Cathode Gas outlet 65 Cathode side plate 66 Cathode water flow path 67 Electrolyte membrane 68 Water circulation pump 69 Deionization filter 70 Anode water discharge pump 71 Cathode water discharge pump 72 Anode water outlet pipe 73 Discharge pipe 74 Anode water tank for gas-liquid separation 75 Cathode water Outlet pipe 76 Hydrogen discharge pipe 77 Hydrogen catalytic combustor 78 Exhaust pipe 79 Cathodic water tank for gas-liquid separation 80 Water circulation pipe 81 Water supply pipe to anode 82 Water supply pipe to cathode 83 Water storage tank 83a Water supply pipe 84 External DC power supply 85

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI H01M 8/02 H01M 8/10 8/10 A01N 59/00 Z // A01N 59/00 C25B 1/00 F (72) Inventor Yasushi Hatanaka Hyogo Hyogo (6-1) Inventor Takeshi Aizawa 2-14-10 Kugahara, Ota-ku, Tokyo Inside Optec Didi Melco Laboratory Co., Ltd. (72) Inventor Sorimachi Makoto Makoto 2-6-4 Kita-Ueno, Taito-ku, Tokyo Toyotaka Sand Dry Battery Co., Ltd. (72) Inventor Tetsuya Abe 8-1-1, Tsukaguchi Honcho, Amagasaki City, Hyogo Pref. JP-A-2-101184 (JP, A) JP-A-7-240220 (JP, A) JP-A-8-106914 (JP, A) JP-A-61-216714 (JP, A) JP-A-4-289664 (JP) JP-A-9-161819 (JP, A) JP-A-9-50819 (JP, A) JP-A-61-216714 (JP, A) JP-B-6-33494 (JP, A) 2) (58) investigated the field (Int.Cl. ^7, DB name) C25B 1/00 - 15/08 H01M 8/10 H01M 8/02 A61L 2/20 A61L 9/015 C01B 13/10 A01N 59/00

Claims (12)

(57) [Claims] 1. A pair of electrodes comprising an anode and a cathode provided so as to face each other with an electrolyte membrane interposed therebetween, first humidified air supply means for supplying humidified air to the anode, and humidified air supplied to the cathode. A second humidified air supply unit for supplying a voltage, and a voltage application unit for applying a voltage between the anode and the cathode, and electrolyzes moisture in the humidified air supplied to the electrodes by applying a voltage between the electrodes. An electrolytic ozone generator characterized in that: 2. A humidified air flow passage provided near the anode and supplied with humidified air by the first humidified air supply means, and humidified air supplied by the second humidified air supply means provided near the cathode. The electrolytic ozone generator according to claim 1, further comprising a second humidified air flow passage formed. 3. The humidified air outlet of the first humidified air passage and the humidified air outlet of the second humidified air passage are provided with an outlet exhaust pipe. Electrolytic ozone generator. 4. Humidifying air generating means for generating humidified air by humidifying air is provided, and the humidified air generated by said humidified air generating means is supplied to a humidified air flow passage by humidified air supply means. The electrolytic ozone generator according to claim 2 or 3, wherein: 5. The electrolytic ozone generator according to claim 2, further comprising a flowing water passage for flowing water near the humidifying air flowing passage. 6. The electrolytic ozone generator according to claim 5, wherein the humidified air generating means generates the humidified air using water flowing through the flowing water passage. 7. The electrolytic ozone generator according to claim 6, wherein a water-permeable membrane is provided so as to be in contact with the flowing water passage, and the air is humidified by water permeating the water-permeable membrane. 8. The electrolytic ozone generator according to claim 2, wherein the first humidified air flow passage is a flow passage without branch. 9. The electrolytic ozone generator according to claim 8, wherein the first humidified air flow passage is a bellows type flow passage. 10. An electrolytic ozone generator according to claim 2, wherein the electrolytic ozone generator is provided with a plurality of stacked electrolytic ozone generators, and a cooler provided between the electrolytic ozone generators. Electrolytic ozone generator. 11. The electrolytic ozone generation according to claim 10, wherein the second humidified air supply means supplies humidified air in parallel to the second humidified air flow passage of each electrolytic ozone generator. vessel. 12. An electrolytic ozone generator comprising: an outlet of a first humidified air flow passage of an electrolytic ozone generator and an inflow side of a first humidified air flow passage of another electrolytic ozone generator; The humidified air is supplied to the first humidified air flow passage in series.
The electrolytic ozone generator according to the description.