WO2019193776A1

WO2019193776A1 - Apparatus for producing hydrogen water

Info

Publication number: WO2019193776A1
Application number: PCT/JP2018/033649
Authority: WO
Inventors: 総橋本; 西　善一
Original assignee: 株式会社ドクターズ・マン
Priority date: 2018-04-03
Filing date: 2018-09-11
Publication date: 2019-10-10
Also published as: JP6371489B1; JP2019181316A

Abstract

Provided is an apparatus for producing hydrogen water comprising an anode layer which has a catalyst necessary for electrolysis and through which water and gas can pass, a cathode layer which has a catalyst necessary for electrolysis and through which water and gas can pass, a solid polymer membrane sandwiched between the anode layer and the cathode layer while being in close contact therewith, an anode chamber in contact with the anode layer, and a cathode chamber in contact with the cathode layer. In the first state in which drinking water at a predetermined pressure or higher is supplied to the cathode chamber, electrolysis is performed by controlling the pressure of water or gas alone or the mixing pressure of water and gas below the pressure of the cathode chamber, thereby dissolving the hydrogen gas generated in the cathode layer in the drinking water to produce hydrogen water, and in the second state in which the drinking water is not supplied to the cathode chamber, the mixing pressure of water and gas in the cathode chamber is controlled to be less than the pressure of water or gas alone or the mixing pressure of water and gas in the anode chamber.

Description

Hydrogen water production equipment

The present invention relates to an apparatus for producing hydrogen water that generates hydrogen water for beverages.

As a method for producing hydrogen water using hydrogen gas generated by electrolysis of water, a method in which hydrogen gas generated by electrolysis in advance is dissolved in water under pressure, or hydrogen gas generated by electrolysis in an electrolysis apparatus is used. There are methods for directly dissolving in water. In the former method in which hydrogen gas generated by electrolysis in advance is dissolved in water under pressure, hydrogen gas is produced by utilizing the reaction in solid polymer electrolysis shown in FIG. In this method, hydrogen gas generated by electrolyzing RO water or pure water in a solid polymer electrolytic cell is dissolved in water outside the electrolyzer. In this electrolysis, the electrolyte membrane is sandwiched between two electrode layers having an electrocatalyst such as platinum, and water is pressurized and adhered, and the anode side is filled with RO water or pure water to generate hydrogen gas from the cathode side. Let On the anode side, a reaction of H ₂ O → 1 / 2O ₂ ↑ + 2H ⁺ + 2e ⁻ occurs, and on the cathode side, a reaction of 2H ⁺ + 2e ⁻ → H ₂ ↑ occurs.

However, according to this method, equipment such as a deionized water device is required to obtain hydrogen gas, and since deionized water has poor conductivity, there is a disadvantage that it is expensive to make the solid polymer membrane thin and efficient. there were. In addition, since the conductivity of pure water is low, heat builds up in the electrolytic cell due to charging, so it was also necessary to study a cooling method. Furthermore, in order to dissolve hydrogen gas in water, a dissolving device is required separately from the electrolytic device.

As a method for directly dissolving hydrogen gas generated by electrolysis in the latter electrolysis apparatus in water, there is a method utilizing a reaction in alkaline water electrolysis as shown in FIG. In this alkaline water electrolysis, a reaction of 2OH ⁻ → 1 / 2O ₂ ↑ + H ₂ O + 2e ⁻ occurs on the anode side, and a reaction of 2H ₂ O + 2e ⁻ → H ₂ ↑ + 2OH ⁻ occurs on the cathode side. That is, the hydrogen water obtained by this method shows alkalinity because OH ⁻ ions remain on the cathode side (hydrogen water side), and the hydrogen concentration must be kept low in order to make the drinking standard pH 8.6 or lower. did not become.

In order to neutralize alkalinity in alkaline water electrolysis, a hydrogen water production apparatus has been proposed in which the anode side has the same configuration as in the case of solid polymer electrolysis and the cathode side has the same configuration as in alkaline water electrolysis ( Patent Documents 1 and 2). This apparatus is intended to lower the pH by neutralizing the hydrogen water that has become alkaline with the acidic water produced at the anode.

Japanese Patent No. 3349710 Japanese Patent Laying-Open No. 2015-221397

However, since the hydrogen water production apparatus described in Patent Document 1 neutralizes hydrogen ions and hydroxyl ions under a large amount of saturated gas, there is a disadvantage that it takes several minutes for pH neutralization. In the gap between the solid polymer membrane and the cathode catalyst, water becomes somewhat alkaline, and dissolved cationic substances such as calcium and magnesium in the water concentrate as the water decreases by electrolysis, and some alkaline and dissolved cations There was a phenomenon that calcium scale (sediment) and magnesium scale (sediment) were generated and adhered due to high concentration. As a result, an energization failure between the negative and positive electrodes occurs, the current value decreases, and the amount of hydrogen gas generated also decreases, causing a problem that a desired dissolved hydrogen water concentration cannot be obtained.

In Patent Document 2, as an anti-scale measure, the conductivity of the water to be treated is desirably 10 mS / m (100 μS / cm) or less in the structure of the electrolytic cell as shown in FIG. The raw water is desalted with an ion exchange resin or a reverse osmosis membrane, and the water to be treated of about 1 mS / m or less is supplied to the cathode chamber. However, since general tap water has a conductivity of about 15 mS / m, pretreatment is necessary.

The present invention solves such problems of the prior art, and the purpose of the present invention is to reduce the amount of general Japanese tap water directly to the cathode chamber as treated water as it is. An object of the present invention is to provide an apparatus for producing hydrogen water that can generate hydrogen water in a time and can prevent a phenomenon in which calcium scale and magnesium scale are generated and adhered between the gaps between the solid polymer membrane and the cathode catalyst.

Another object of the present invention is that the production cost is low, the hydrogen gas generation amount does not decrease even when used for a long time, stable hydrogen water is obtained, and an efficient hydrogen gas generation function is maintained for a long time. An object of the present invention is to provide an apparatus for producing hydrogen water that can be used.

According to the present invention, an apparatus for producing hydrogen water includes an anode layer having a catalyst necessary for electrolysis and capable of passing water and gas, and a cathode having a catalyst necessary for electrolysis and capable of passing water and gas. A solid polymer film sandwiched between the anode layer and the cathode layer, an anode chamber in contact with the anode layer, and a cathode chamber in contact with the cathode layer. In the first state in which drinking water of a predetermined pressure or higher is supplied to the cathode chamber, electrolysis is performed by controlling the water or gas single pressure in the anode chamber or the mixed pressure of water and gas below the pressure in the cathode chamber. The hydrogen gas generated in the cathode layer is dissolved in the drinking water to generate hydrogen water. In the second state in which the drinking water is not supplied to the cathode chamber, the water and gas in the cathode chamber are The mixing pressure is controlled to be less than the water or gas single pressure of the anode chamber or the water and gas mixing pressure.

Thus, in the present invention, in the first state (during water intake, during electrolysis) in which drinking water of a predetermined pressure or higher is supplied to the cathode chamber where the solid polymer membrane that is the diaphragm contacts via the cathode layer, Water is supplied into the solid polymer membrane and the gap between the solid polymer membrane and the cathode layer by drinking water (pressurized water) having a higher pressure than the anode chamber, and this water is electrolyzed to cause the surface of the cathode layer to be electrolyzed. The generated hydrogen gas is dissolved in the drinking water to generate hydrogen water. At this time, the dissolved solid matter such as calcium and magnesium accumulated in the gap between the solid polymer film and the cathode layer is concentrated, but the drinking water is not supplied to the cathode layer side. The solid polymer film is pressed against the cathode layer by making the pressure in the anode chamber higher than the pressure in the cathode chamber (when water intake is stopped and electrolysis is stopped), and the solid polymer film accumulates in the gap between the solid polymer film and the cathode layer. In addition, water in which dissolved solids such as calcium and magnesium are concentrated results in being pushed out to the cathode chamber. Next, when drinking water having a higher pressure than the anode chamber is supplied to the cathode chamber and electrolyzed, Water with reduced concentration is supplied in the molecular film and in the gap between the solid polymer film and the cathode layer. That is, by changing the pressure in the cathode chamber and the pressure in the anode chamber, the solid polymer film is moved between the cathode layer and the anode layer by piston movement, so that the gap exists between the solid polymer film and the cathode layer. The water is replaced to remove scales such as calcium and magnesium.

Further, the present invention utilizes solid polymer electrolysis, pressurizes and supplies drinking water having conductivity due to inorganic substance dissolution to the cathode chamber, and dissolves hydrogen gas generated on the cathode surface in the drinking water. Is generated. In the polymer electrolyte, as described above, the reaction of H ₂ O → 1 / 2O ₂ ↑ + 2H ⁺ + 2e ⁻ occurs on the anode side, and the reaction of 2H ⁺ + 2e ⁻ → H ₂ ↑ occurs on the cathode side. Since such solid polymer electrolysis is used, it does not become alkaline with a pH of 9 or more unlike alkaline water electrolysis while directly electrolyzing drinking water, and mixing of hypochlorite ions is limited. Hydrogen water can be produced. Furthermore, since drinking water is used, there is no need for a device to make RO water or pure water from raw water. In addition, this drinking water contains inorganic solids and has electrical conductivity. Since there is little heat generation at the time of decomposition and drinking water is supplied from the outside, a cooling device for the electrolytic cell becomes unnecessary, and the manufacturing cost of the device can be reduced.

In the first state, it is also preferable that the single pressure of water or gas in the anode chamber or the mixed pressure of water and gas is a pressure in the range of 0.03 MPa to 0.1 MPa. In the present specification, the pressure is expressed on the basis of atmospheric pressure (gauge pressure) where the atmospheric pressure is 0 MPa.

In the first state, it is also preferable that the pressure of the drinking water supplied to the cathode chamber is a pressure in the range of 0.1 MPa to 0.3 MPa.

In the second state, it is also preferable that the pressure in the cathode chamber is atmospheric pressure.

It is also preferable that a relief valve is connected between the anode chamber and the atmosphere.

It is also preferable that a pressure gauge is connected to the anode chamber and a solenoid valve is connected between the anode chamber and the atmosphere so that the solenoid valve is controlled based on the measured value of the pressure gauge. .

It is also preferable that the water content of the solid polymer membrane is a cation exchange membrane having a water content of 27.6% or more (38.2% or more with respect to the dry solid polymer film) as a water content with respect to the saturated water film. If the water content of the solid polymer membrane is within this range, the solid matter remaining in the solid polymer membrane is inhibited to some extent from dilution with water. In other words, the solid concentration in the solid polymer membrane is maintained at the same level as the solid concentration of the drinking water in the cathode chamber, so the oxidation reaction / reduction reaction of the solid matter in the solid polymer membrane performed in the solid polymer membrane. Does not react drastically in a high concentration state, the redox electron offset due to the 2e ^- ion content does not increase, and a decrease in the amount of hydrogen gas generated is suppressed. Further, in-film substances such as chloride ions that undergo oxidation and reduction are oxidized in the anode layer, and when they are about to flow out of the film into the cathode chamber, they are reduced in the cathode layer and released into the cathode chamber. There is almost no mixing of oxides in water.

The catalyst for the anode layer and the cathode layer is also preferably a platinum catalyst. By making the anode layer and the cathode layer contain a platinum catalyst, electrolysis is promoted and the generation of hydrogen gas is made more efficient. Further, the reaction of NaClO + 2H ⁺ + 2e ⁻ → NaCl + H ₂ O occurs in the cathode layer, Chlorate ions can be neutralized.

The anode layer and / or the cathode layer is preferably a titanium platinum electrode formed of a lath net of titanium or punch metal.

Because it uses solid polymer electrolysis, it does not become alkaline more than pH 9 as in alkaline water electrolysis, while it is direct electrolysis of drinking water, and the mixing of hypochlorite ions is limited. Water can be produced. Furthermore, since drinking water is used, there is no need for a device to make RO water or pure water from raw water. This drinking water contains inorganic solids and has electrical conductivity, and the voltage value decreases. Therefore, since the drinking water is supplied from the outside, a cooling device for the electrolytic cell becomes unnecessary, and the manufacturing cost of the device can be reduced.

In particular, according to the present invention, by changing the pressure in the cathode chamber and the pressure in the anode chamber, the solid polymer film is moved in a piston motion between the cathode layer and the anode layer. Since the scales such as calcium and magnesium are removed by replacing the water present in the gap between them, the amount of solids remaining in the solid polymer membrane does not increase, and the solids concentration is the drinking water in the cathode chamber It is maintained at the same level as the solid concentration. As a result, the oxidation reaction / reduction reaction of the solid matter in the solid polymer film in the solid polymer film does not react drastically in the high concentration state, and the redox electron cancellation due to the 2e ^- ion component does not increase. In addition, a decrease in the amount of hydrogen gas generated is suppressed. Further, in-film substances such as chloride ions that undergo oxidation and reduction are oxidized in the anode layer, and when they are about to flow out of the film into the cathode chamber, they are reduced in the cathode layer and released into the cathode chamber. There is almost no oxide mixed into the water. In addition, even if pressurized drinking water is supplied to the cathode chamber, the drinking water does not leak into the anode chamber, eliminating the need for water treatment on the anode chamber side, and providing an efficient hydrogen gas generation function. Can be maintained over time.

It is a figure explaining the reaction of the anode side and cathode side in the method of generating hydrogen gas by electrolysis, (A) is a case of solid polymer electrolysis, (B) is a case of alkaline water electrolysis. It is a disassembled perspective view which shows roughly the whole structure of the electrolytic vessel in the manufacturing apparatus of hydrogen water as one Embodiment of this invention. It is a decomposition | disassembly side view which shows roughly the whole structure of the electrolytic vessel in the manufacturing apparatus of the hydrogenous water of FIG. FIG. 3A is a plan view schematically showing a configuration of an anode side casing of an electrolytic cell in the hydrogen water production apparatus of FIG. 2, and FIG. FIG. 3A is a plan view schematically showing a configuration of a cathode side casing of an electrolytic cell in the hydrogen water production apparatus of FIG. 2, and FIG. FIG. 3 is a block diagram schematically showing an electrical configuration of the hydrogen water production apparatus of FIG. 2. It is a schematic diagram which shows the structure of the electrolytic vessel in the manufacturing apparatus of the hydrogenous water of FIG. It is a block diagram which shows roughly the system configuration | structure of the manufacturing apparatus of the hydrogenous water of FIG. It is a flowchart which shows roughly the flow of control of the control apparatus in the manufacturing apparatus of the hydrogenous water of FIG. It is a block diagram which shows roughly the system configuration | structure of the manufacturing apparatus of hydrogenous water as other embodiment of this invention. It is a flowchart which shows roughly the flow of control of the control apparatus in the manufacturing apparatus of the hydrogenous water of FIG. It is a block diagram which shows roughly the system configuration | structure of the manufacturing apparatus of the hydrogenous water used in Comparative Examples 1 and 2. It is a block diagram which shows roughly the system configuration | structure of the manufacturing apparatus of the hydrogenous water used in Example 1 and 2. FIG. It is a characteristic view of the electrolysis current value and the electrolysis voltage value with respect to the water intake amount in Comparative Example 1. It is a figure which shows the result of having observed the scale adhering to the surface by the side of the diaphragm of a cathode layer in the comparative examples 1 and 2 and Examples 1 and 2. FIG. It is a characteristic view of the electrolysis current value and the electrolysis voltage value with respect to the water intake amount in Comparative Example 2. It is a characteristic view of the electrolysis current value and the electrolysis voltage value with respect to the amount of water intake in Example 1. It is a characteristic view of the electrolysis current value and the electrolysis voltage value with respect to the amount of intake water in Example 2. It is the characteristic view which showed the electrolysis current value and the electrolysis voltage value with respect to the amount of water intake in Comparative Examples 1 and 2 and Example 1 on the same figure.

2 and 3 schematically show the overall configuration of the electrolytic cell in the hydrogen water production apparatus as one embodiment of the present invention, and FIG. 4 shows the electrolytic cell anode in the hydrogen water production apparatus of the present embodiment. The structure of the side housing is schematically shown in plan and cross section, and FIG. 5 schematically shows the structure of the cathode side housing of the electrolytic cell in the hydrogen water production apparatus of this embodiment in plan and cross section. .

The difference in configuration between the anode-side casing in FIG. 4 and the cathode-side casing in FIG. 5 in this embodiment is the difference in the presence or absence of the O-ring groove, and FIG. 4 shows the configuration of the cathode-side casing. However, the anode side housing may be configured. The configuration of the cathode side casing and the configuration of the anode side casing are not limited by the presence or absence of the O-ring groove.

2 and 3, reference numeral 10 denotes a solid polymer electrolytic cell. The electrolytic cell 10 is in a state in which the contact surfaces of the anode-side casing 11 and the cathode-side casing 12 are in contact with each other. By bolting with, an integrated housing is formed. Inside the casing are an anode layer 13, a cathode layer 14, a diaphragm 15 which is a solid polymer film sandwiched between the anode layer 13 and the cathode layer 14 in pressure contact with each other, and a packing for sealing the casing 16 is housed. A lead wire connection terminal 17 is connected to the anode layer 13 and is electrically connected to the anode of the power supply device via a lead wire (not shown), and a lead wire connection terminal 18 is connected to the cathode layer 14. It is electrically connected to the cathode of the power supply device via a lead wire (not shown).

The outer dimension of the casing of the electrolytic cell 10 is merely an example, but is about 146 mm (vertical) × about 96 mm (horizontal) × about 60 mm (height). In this embodiment, a transparent acrylic resin is molded. Have been made. Needless to say, the casing may be manufactured using opaque resin of various colors, or may be manufactured using other types of resins or other materials.

As shown in FIG. 4, the anode-side casing 11 has two gas (gas) outlets 11b penetrating through the casing 11, and two gas outlets 11b are connected to the inside of the casing. A gas passage (anode chamber) 11c is formed. The gas passage (anode chamber) 11c is configured to meander by ribs 11d formed in a comb shape so as to alternately mesh with each other. A circumferential groove 11e that accommodates the packing 16 is further provided inside the housing.

As shown in FIG. 5, the cathode-side casing 12 has a water inlet 12a and a water outlet 12b penetrating the casing 12, and the water inlet 12a and the water outlet 12b are connected to the inside of the casing. A water channel (cathode chamber) 12c is formed. The water channel (cathode chamber) 12c is configured to meander by ribs 12d formed in a comb shape so as to alternately mesh with each other. As a result, the hydrogen gas is quickly and efficiently dissolved in the pressurized water flowing meandering.

The anode layer 13 is composed of a titanium platinum electrode formed of a titanium lath net or punch metal, or a catalyst-carrying carbon electrode layer in which platinum-based nanoparticles are supported on conductive carbon so that gas can pass through. Yes.

The anode layer 13 needs to be provided with a large number of through holes for opening the gas to the anode chamber 11 c and further to the atmosphere, and one surface needs to be in contact with the diaphragm 15. Therefore, carbon materials such as carbon cloth, carbon non-woven fabric, or carbon porous film, or a lath net or punching metal of titanium is used as the electrode material. Platinum or iridium can be used as the catalyst, but platinum is used in this embodiment. By using a platinum catalyst for the anode layer 13, a reaction of NaCl + H ₂ O → NaClO + 2H ⁺ + 2e ⁻ also occurs. There are methods such as coating, sintering, or plating for bonding the catalyst and the electrode material, and any method may be adopted. The dimension of the anode layer 13 is merely an example, but is about 100 mm (vertical) × about 50 mm (horizontal).

The cathode layer 14 is composed of a titanium platinum electrode formed of a lath net of titanium or punch metal so that gas and water can pass, or a catalyst-supported carbon electrode layer in which platinum-based nanoparticles are supported on conductive carbon. Has been.

The cathode layer 14 needs to be provided with a large number of through holes for opening gas and water to the cathode chamber 12 c, and one surface needs to be in contact with the diaphragm 15. Therefore, carbon materials such as carbon cloth, carbon non-woven fabric, and carbon porous film, titanium lath net, and punching metal are used as electrode materials. Platinum or iridium can be used as the catalyst, but platinum is used in this embodiment. By using a platinum catalyst for the cathode layer 14, a reaction of NaClO + 2H ⁺ + 2e ⁻ → NaCl + H ₂ O can be caused to neutralize hypochlorite ions. There are methods such as coating, sintering, and plating for bonding the catalyst and the electrode material, and any method may be adopted. The dimensions of the cathode layer 14 are merely an example, but are about 100 mm (vertical) × about 50 mm (horizontal).

The diaphragm 15, which is a solid polymer membrane, is a cation exchange membrane made of an organic polymer porous material. In this embodiment, a styrene polymerization type cation exchange membrane is used. This cation exchange membrane contains 40 to 60 wt% of sulfonic acid sodium salt of a styrene / divinylbenzene polymer as a resin material having an exchange function, and 40 to 60 wt% of a polyolefin mixture as a reinforcing material. The dimension of the diaphragm 15 is only an example, but is about 119 mm (length) × about 69 mm (width).

In particular, the diaphragm 15 has a water content capable of diluting water-soluble solids in the film by pressurized water in contact with the cathode surface on the cathode layer side. The moisture content of the diaphragm 15 is 27.6% or more (38.2% or more with respect to the dry diaphragm) in terms of the moisture content with respect to the saturated water-containing diaphragm, as will be described in Examples described later. As a result, the solid matter remaining in the diaphragm 15 is diluted with water, so that an increase in the amount is suppressed to some extent, and the solids concentration in water contained in the diaphragm 15 is equal to the solids concentration of drinking water in the cathode chamber 12c. It is held at the same level. As a result, the oxidation / reduction reaction of the solid matter in the diaphragm performed in the diaphragm 15 does not react drastically in a high concentration state, and the redox electron cancellation due to 2e ⁻ ions does not increase, and the amount of hydrogen gas generated The decline is suppressed. Further, substances in the diaphragm 15 such as chloride ions that undergo oxidation / reduction are oxidized by the anode layer 13 and are reduced by the cathode layer 14 and released to the cathode chamber 12c when they flow out of the diaphragm 15 into the cathode chamber 12c. As a result, there is almost no contamination of drinking water with oxides.

The diaphragm 15 further has water permeability so that pressurized water does not flow out into the anode chamber 11c on the anode layer side. Specifically, when the pressure of pressurized water passed through the cathode chamber 12c is in the range of 0.1 to 0.3 MPa, the diaphragm 15 enters the diaphragm 15 in a state where water does not leak into the anode chamber 11c. It has water permeability to retain water. Thereby, even if pressurized drinking water is supplied to the cathode chamber 12c, the drinking water does not leak into the anode chamber 11c, and an efficient hydrogen gas generation function can be maintained for a long time. Moreover, the diaphragm 15 naturally has pressure resistance performance against pressures up to 0.3 MPa. As described above, in the present specification, the pressure is expressed not based on the absolute pressure but based on the atmospheric pressure (gauge pressure) where the atmospheric pressure is 0 MPa.

In order to pressure-bond the anode layer 13, the diaphragm 15, and the cathode layer 14, it is most preferable to use the anode layer 13 and the cathode layer 14 in which platinum is supported on a titanium steel plate. When the anode side casing 11 and the cathode side casing 12 are bolted, the diaphragm 15 is pressed and adhered to the anode layer 13 and the cathode layer 14 by pressing the anode layer 13 and the cathode layer 14. It will be. When a carbon material is selected as the material for the anode layer 13 and the cathode layer 14, it is desirable to prepare an electrode pressing plate such as a lath net of titanium or a punching metal.

Although not shown in the figure, the diaphragm 15 of the electrolytic cell 10 can be damaged by installing a water level indicator that allows visual confirmation that water is not discharged from the anode chamber 11c in communication with the anode chamber 11c. This can be confirmed, and this is also a guideline for replacing the electrolytic cell 10. The water level display unit may display the water level with a transparent cylindrical tube or a bar display with LEDs using an electric water level meter as long as the user can easily confirm water leakage.

FIG. 6 schematically shows the electrical configuration of the hydrogen water production apparatus of this embodiment.

As shown in the figure, the anode layer 13 of the electrolytic cell 10 is electrically connected to the positive output terminal of the constant current power supply 61 via the ammeter 60, and the cathode layer 14 is negatively connected to the negative electrode of the power supply 61. Is electrically connected to the output terminal. By supplying a direct current from the power supply device 61, electrolysis is performed in the electrolytic cell 10, hydrogen is generated in the cathode chamber 12c, dissolved in drinking water, and hydrogen water is obtained. On the other hand, oxygen is vaporized in the anode chamber 11c and diffused into the atmosphere.

If the current flowing from the power supply device 61 to the electrolytic cell 10 is measured by the ammeter 60, only the electrolytic current value used for hydrogen gas generation can be measured, and the amount of hydrogen gas generated can be grasped. The hydrogen gas concentration can be easily known from the hydrogen gas generation amount and the flow rate of drinking water (a constant value can be set as a constant). The reason why the amount of hydrogen gas generated can be grasped from the measured electrolysis current value is that, even if hydrogen generation of 4H ⁺ + 4e ⁻ → 2H ₂ ↑ is initially performed by charging, H ₂ O → 1 / 2O _{2 in the} anode layer 13. If a reaction of ↑ + 2H ⁺ + 2e ^{− and} a reaction of NaCl + H ₂ O → NaClO + 2H ⁺ + 2e ⁻ occur, and if a reaction of NaClO + 2H ⁺ + 2e ⁻ → NaCl + H ₂ O occurs on the cathode side in the diaphragm 15, in fact, H ₂ As a result, only the reaction of O → 1 / 2O ₂ ↑ + 2H ⁺ + 2e ^{− and} the reaction of 2H ⁺ + 2e ⁻ → H ₂ ↑ occur. In other words, the ammeter 60 does not measure the 2e ⁻ offset electrolysis current value due to hypochlorite ions, so that the electrolysis current value actually used only for hydrogen generation can be known.

The display of the hydrogen gas concentration may be an analog display such as an analog ammeter, a digital numerical display, or a bar display with LEDs as long as the user can easily understand the concentration. There may be. If the user can easily recognize the hydrogen gas concentration, the user can search for drinking source water with a higher hydrogen gas concentration, select low salt and low solids water, and use safer drinking water It can be performed. Moreover, in order to further ensure the safety as drinking water, by limiting the electrolysis current value and the electrolysis voltage value in the power supply device 61, it becomes possible to electrolyze only water suitable for drinking. The numerical value to be limited varies depending on the specifications of the electrolytic cell 10.

FIG. 7 schematically shows the configuration of the electrolytic cell 10 in the hydrogen water production apparatus of the present embodiment. Hereinafter, the hydrogen water generating operation in the electrolytic cell 10 will be described in detail.

Pressurized drinking water is supplied into the cathode chamber 12c through the water inlet 12a. In this case, the water pressure is set in a range of 0.1 to 0.3 MPa suitable for dissolving hydrogen gas generated by electrolysis. Hydrogen gas should be dissolved in water under pressure, which follows Henry's law. That is, the dissolved oxygen concentration in water at 25 ° C. open to the atmosphere is 8.09 mg / L, the partial pressure ratio of dissolved oxygen is 8.09 / 40.44 × 100 = 20%, and nitrogen is 80%. . When this water becomes 2 atm (0.1 MPa), the partial pressure ratio of oxygen is 10%, the partial pressure ratio of nitrogen is 40%, and a partial pressure frame is formed in which hydrogen dissolves, and a maximum of 50% can be dissolved. It becomes. In other words, 1.57 mg / L × (1/2) × 2 atm = 1.57 mg / L is the maximum solubility, which is close to the maximum solubility of 1.6 mg / L at atmospheric pressure. Since the reaction consumption of NaClO + 2H ⁺ + 2e ⁻ → NaCl + H ₂ O is covered and the solution concentration does not reach a saturated hydrogen concentration of 1.6 mg / L at atmospheric pressure, 1 at 3 atm (0.2 MPa) It is desirable to obtain a dissolution amount that provides a maximum dissolution concentration of twice the atmospheric pressure of .57 mg / L × (2/3) × 3 atmospheric pressure = 3.14 mg / L, and the pressure is 0.1 MPa or more and the pressure resistance of the diaphragm Considering the strength (about 0.4 MPa), it is desirable to be performed within the range of 0.1 to 0.3 MPa centered around 0.2 MPa, and more preferably within the range of 0.2 to 0.3 MPa. To become.

The diaphragm 15 has a pressure resistance that does not break even when subjected to the cell permeation water pressure by the pressurized drinking water as described above. Moreover, the diaphragm 15 has water permeability that prevents pressurized water from flowing out into the anode chamber on the anode layer 13 side. For this reason, even if pressurized drinking water is supplied to the cathode chamber 12c, the drinking water does not leak into the anode chamber 11c, water treatment on the anode chamber 11c side is unnecessary, and efficient hydrogen gas. The generating function can be maintained for a long time.

Furthermore, the diaphragm 15 is a thin film in which the salt content does not accumulate in the film as much as possible. That is, the diaphragm 15 has a water content that can dilute the water-soluble solid matter in the film by pressurized water that is in contact with the cathode surface on the cathode layer 14 side. As a result, the oxidation / reduction reaction of the solid matter in the diaphragm performed in the diaphragm 15 does not react drastically in a high concentration state, and the redox electron cancellation due to 2e ⁻ ions does not increase, and the amount of hydrogen gas generated The decline is suppressed.

In solid polymer electrolysis, when water is supplied from the cathode chamber 12c to the anode side through the water content of the diaphragm 15 which is a solid polymer film, H ₂ O → 1 / 2O ₂ ↑ + 2H in the vicinity of b in FIG. ^{A +} + 2e ⁻ reaction occurs, oxygen gas is released from the vicinity of a, hydrogen ions are attracted from the vicinity of b through the diaphragm 15 to the cathode side, and a reaction of 2H ⁺ + 2e ⁻ → H ₂ ↑ occurs near c. , D is dissolved in water in the cathode chamber 12c in the vicinity of d to generate hydrogen water.

The drinking water supplied to the cathode chamber 12c is typically tap water, which contains metal ions such as calcium ions and magnesium ions. If tap water is decomposed into hydrogen gas or oxygen gas by electrolysis, the concentration of dissolved metal ions such as calcium ions and magnesium ions is concentrated and increased. Thus, between the diaphragm 15 and the cathode layer 14 and the vicinity thereof becomes alkaline, and when the dissolved concentration of calcium ions and magnesium ions is increased, calcium scale and magnesium scale are generated between the diaphragm 15 and the cathode layer 14 and in the vicinity thereof. Even if it is an inevitable phenomenon and it is going to prevent such scale generation | occurrence | production by flowing drinking water, the diaphragm 15 and the cathode layer are under the pressurized water flow in which the cathode chamber 12c was constantly pressurized to about 0.2 MPa. It is difficult to prevent the generation of scale up to the gap between 14, and as a result, in the long-term use, calcium scale and magnesium scale are attached to the surface of the cathode layer 14 at an early stage. The concentration will decrease.

Further, since the diaphragm 15 is constantly pressed against the anode layer 13 and the diaphragm 15 is pressed into the depression of the electrode plate, the diaphragm 15 is cracked at the corners of the electrode plate, or the stress of the diaphragm 15 is increased. Deterioration will occur. As a result, water leakage into the anode chamber 11c increases, and there is a risk that impurities in the water leakage will be mixed due to oxidation into drinking water, so this water leakage cannot be taken.

Therefore, in the present invention, in the first state in which electrolysis is performed (during hydrogen water intake and electrolysis), the pressure in the anode chamber 11c (single pressure of water or gas in the anode chamber 11c or water and gas in the anode chamber 11c) The pressure of the pressure is higher than a predetermined pressure (for example, 0.1 to 0.3 MPa) higher than the mixing pressure (for example, 0.03 to 0.1 MPa). Is weakened to prevent the diaphragm 15 from cracking at the corners of the electrode plate and the stress deterioration of the diaphragm 15 from occurring. Further, new pressurized water is supplied into the diaphragm 15 and the gap between the diaphragm 15 and the cathode layer 14. On the other hand, in the second state in which no drinking water is supplied to the cathode chamber 12c (when hydrogen water intake is suspended, when electrolysis is suspended), the pressure in the anode chamber 11c (single pressure of water or gas in the anode chamber 11c or water and water) By configuring the gas mixture pressure to be higher than the pressure in the cathode chamber 12c (water and gas mixture pressure in the cathode chamber 12c), the diaphragm 15 is pressed against the cathode layer 12c, and the diaphragm 15 and the cathode layer The concentrated water accumulated in the gap between 12c is pushed back into the cathode chamber 12c. Next, when pressurized water having a pressure higher than the pressure in the anode chamber 11C is supplied to the cathode chamber 12c in the first state, new pressurized water whose concentration is diluted is supplied to the gap between the diaphragm 15 and the cathode layer 14. The In the first state and the second state, the diaphragm 15 repeats the piston movement, that is, the water pumping phenomenon due to minute pulsations. By configuring in this way, according to the present invention, it is not necessary to carry out a desalting treatment in advance even for water with a large amount of dissolved solids such as tap water, and a large amount of scale may adhere to the electrode layer. It can be used over a long period of time.

In the first state (during hydrogen water intake and electrolysis), the water pressure of the drinking water supplied under pressure to the cathode chamber 12c is 0.2 to 0 suitable for dissolving the hydrogen gas generated by electrolysis. The reason for setting in the range of 3 MPa is as described above.

In the first state (at the time of hydrogen water intake and electrolysis) and the second state (at the time of hydrogen water intake stop and electrolysis stop), the pressure in the anode chamber 11c is desirably in the range of 0.03 to 0.1 MPa. It is good to set by pressure. The lower limit pressure of 0.03 MPa is such that when the pressurized water supplied to the cathode chamber 12c in the second state is stopped and the cathode chamber 12c is opened to the atmosphere, the pressure in the cathode chamber 12c becomes 0 MPa. It is desirable that the pressure in the chamber 11c be higher than that, that is, 0.01 MPa, and further, a pressure decrease due to the movement of the piston of the diaphragm 15 is expected to be 0.02 MPa. Therefore, the pressure in the anode chamber 11c is set to 0.01 MPa + 0. 02 MPa = 0.03 MPa or more is desirable. The upper limit pressure of 0.1 MPa is adjusted by adjusting the gap between the cathode layer 14 and the anode layer 13 to a thickness of 93.7% of the thickness of the diaphragm 15, and applying 0.2 MPa of pressurized water to the cathode chamber 12c for electrolysis. When the pressure in the anode chamber 11c is greater than 0.1 MPa, the diaphragm 15 is pressed and thinned at a pressure of 0.3 MPa, the contact with the electrode layer is weakened, and a voltage (( In order to suppress unnecessary power consumption, 0.1 MPa or less is desirable.

FIG. 8 schematically shows the system configuration of the hydrogen water production apparatus of this embodiment.

In the figure, 10 is the above-described electrolytic cell, 80 is a tank storing drinking water, 81 is a pump connected to the

tank

80, 82 is connected to the pump 81 and the cathode chamber 12c of the electrolytic cell 10. The pressure reducing valve 83 is a relief valve connected to the outlet of the anode chamber 11 c of the

electrolytic cell

10, 84 is a flow rate adjusting valve connected to the cathode chamber 12 c of the

electrolytic cell

10, and 85 is connected to the flow rate adjusting valve 84. The electromagnetic valve 86 is a control device for controlling the electrolysis of the electrolytic cell 10 and controlling the operation of the pump 81 and the electromagnetic valve 85, respectively.

Drinking water is stored in the tank 80, and pumped from the tank 80 and sent from the pressure reducing valve 82 to the cathode chamber 12c of the electrolytic cell 10 to generate hydrogen water. The generated hydrogen water is the cathode chamber 12c of the electrolytic cell 10. Then, the flow rate adjusting valve 84 and the electromagnetic valve 85 are fed in this order to take out hydrogen water (withdrawal).

The control device 86 has a computer that can be programmed, and the operation of the pump 81, the electrolysis of the electrolytic cell 10, and the operation of the electromagnetic valve 85 are controlled by the computer so that hydrogen water is generated. It is configured. The pressure reducing valve 82 is configured to adjust the pressure of drinking water pressurized by the pump 81 in the range of 0.2 to 0.3 MPa. The relief valve 83 is configured such that the discharge pressure is in the range of 0.03 to 0.1 MPa. Thereby, the pressure in the anode chamber 11 c of the electrolytic cell 10 is maintained below the pressure adjusted by the relief valve 83. The water intake speed is adjusted by the flow rate adjusting valve 84.

FIG. 9 schematically shows a control flow of the control device 86 in the hydrogen water production apparatus of the present embodiment.

As shown in the figure, when water is taken in, first, the solenoid valve 85 is opened (step S1). Next, the operation of the pump 81 is started, and power is supplied to the electrolytic cell 10 to start electrolysis (step S2). Note that electrolysis may be started by supplying power to the electrolytic cell 10 simultaneously with the start of operation of the pump 81 (step S2). The pressure of drinking water during this electrolysis, in other words, the pressure of drinking water in the cathode chamber 12c of the electrolytic cell 10 is adjusted to a pressure in the range of 0.2 to 0.3 MPa by the pressure reducing valve 82. On the other hand, the pressure in the anode chamber 11 c of the electrolytic cell 10 is increased by storing oxygen gas generated by electrolysis, and adjusted to a pressure of 0.03 to 0.1 MPa by the relief valve 83. With such a configuration, when the pump 81 is in operation (in the first state), the pressure in the anode chamber 11c of the electrolytic cell 10 is controlled to be less than the pressure in the cathode chamber 12c of the electrolytic cell 10.

Thereafter, it is continuously determined whether or not the intake of hydrogen water has been completed (step S3). If the intake of hydrogen water has been completed, the operation of the pump 81 is stopped (step S4). Next, the electrolysis of the electrolytic cell 10 is finished (step S5). Thereafter, the electromagnetic valve 85 is closed (step S6). The operation of the pump 81 is stopped first because the solenoid valve 85 needs to be closed after the pressure in the cathode chamber 12c of the electrolytic cell 10 is made equal to the atmospheric pressure (0 MPa). Thus, the pressure in the cathode chamber 12c of the electrolytic cell 10 is controlled to atmospheric pressure (0 MPa), while the pressure in the anode chamber 11c of the electrolytic cell 10 is adjusted to a pressure of 0.03 to 0.1 MPa by the relief valve 83. Adjusted. With such a configuration, the pressure in the cathode chamber 12c of the electrolytic cell 10 is controlled to be lower than the pressure in the anode chamber 11c of the electrolytic cell 10 when the water intake is stopped (in the second state). In this case, the high-pressure gas in the anode chamber 11c does not escape through the diaphragm 15 and into the cathode chamber 12c. This is because a water film is stretched between the diaphragm 15 and the anode layer 14 and this water film effectively prevents gas permeation.

FIG. 10 schematically shows a system configuration of an apparatus for producing hydrogen water as another embodiment of the present invention.

tank

80, 82 is connected to the pump 81 and the cathode chamber 12c of the electrolytic cell 10. The pressure reducing valve 84 is a flow rate adjusting valve connected to the cathode chamber 12c of the

electrolytic cell

10, 85 is an electromagnetic valve connected to the flow

rate adjusting valve

84, and 87 is connected to the outlet of the anode chamber 11c of the electrolytic cell 10. 88 is a flow rate adjusting valve connected to the

electromagnetic valve

87, 89 is a pressure gauge connected to the outlet of the anode chamber 11c of the

electrolytic cell

10, 90 is electrolysis of the electrolytic cell 10, and a pump 81 And a control device for controlling the operation of the electromagnetic valve 85, receiving the detection value of the pressure gauge 89, and controlling the operation of the electromagnetic valve 87.

The control device 90 has a computer that can be controlled by a program. The operation of the pump 81, the electrolysis of the electrolytic cell 10, the detected value of the pressure gauge 89, and the operation of the

solenoid valves

85 and 87 are controlled by the computer. Thus, the hydrogen water is generated. The pressure reducing valve 82 is configured to adjust the pressure of drinking water pressurized by the pump 81 in the range of 0.2 to 0.3 MPa. Further, the electromagnetic valve 87 is controlled in accordance with the detection value of the pressure gauge 89, so that the pressure of the generated oxygen gas in the anode chamber 11c of the electrolytic cell 10 is in the range of 0.03 to 0.1 MPa. ing. The water intake speed is adjusted by the flow rate adjusting valve 84.

FIG. 11 schematically shows a control flow of the control device 90 in the hydrogen water production apparatus of the present embodiment.

As shown in the figure, when water is taken in, first, the solenoid valve 85 is opened (step S11). Next, the operation of the pump 81 is started, and power is supplied to the electrolytic cell 10 to start electrolysis (step S12). The electrolysis may be started by supplying power to the electrolytic cell 10 simultaneously with the start of operation of the pump 81 (step S12). The pressure of drinking water during this electrolysis, in other words, the pressure of drinking water in the cathode chamber 12c of the electrolytic cell 10 is adjusted to a pressure in the range of 0.2 to 0.3 MPa by the pressure reducing valve 82. On the other hand, the pressure of the generated oxygen gas in the anode chamber 11 c of the electrolytic cell 10 is adjusted to a pressure of 0.03 to 0.1 MPa by the operation of the pressure gauge 89 and the electromagnetic valve and the control of the control device 90. The pressure adjustment in the cathode chamber 12c receives the detection value of the pressure gauge 89 (step S13), and the received detection value, that is, the pressure value measured in the anode chamber 11c of the electrolytic cell 10 is a predetermined pressure (0.03 to 0.03). It is determined whether or not the pressure range is within 0.1 MPa (including the boundary) (step S14), and it is determined that the measured pressure value is within a predetermined pressure (pressure range of 0.03 to 0.1 MPa). In the case (in the case of YES), the electromagnetic valve 87 is closed or kept closed (step S16). When it is determined in step S14 that the measured pressure value is not within the predetermined pressure (pressure range of 0.03 to 0.1 MPa) (in the case of NO), the electromagnetic valve 87 is opened (step S15), and step S13 is performed. In step S14, the detection value of the pressure gauge 89 is received, and the determination in step S14 is performed again. When the electromagnetic valve 87 is opened and closed, the pressure is reduced by opening and closing the valve so that the pressure is reduced by the action of the flow rate adjusting valve 88, and the pressure value of the anode chamber 11c is adjusted within a desired range. As a result, the pressure in the anode chamber 11c of the electrolytic cell 10 is controlled to a pressure of 0.03 to 0.1 MPa. With such a configuration, the pressure in the anode chamber 11c of the electrolytic cell 10 is controlled to be less than the pressure in the cathode chamber 12c of the electrolytic cell 10 during electrolysis (in the first state).

Thereafter, it is continuously determined whether or not the intake of hydrogen water has ended (step S17). If the intake of hydrogen water has ended, the operation of the pump 81 is stopped (step S18). Next, the electrolysis of the electrolytic cell 10 is finished (step S19). Thereafter, the electromagnetic valve 85 is closed (step S20). The operation of the pump 81 is stopped first because the solenoid valve 85 needs to be closed after the pressure in the cathode chamber 12c of the electrolytic cell 10 is made equal to the atmospheric pressure (about 0.1 MPa). Thus, the pressure in the cathode chamber 12c of the electrolytic cell 10 is controlled to atmospheric pressure (0 MPa) by opening to the atmosphere. With such a configuration, the pressure in the cathode chamber 12c of the electrolytic cell 10 is controlled to be lower than the pressure in the anode chamber 11c of the electrolytic cell 10 when the water intake is stopped (in the second state). Instead of the flow rate adjusting valve 88, a fixed flow rate orifice may be used. In this case, the high-pressure gas in the anode chamber 11c does not escape through the diaphragm 15 and into the cathode chamber 12c. This is because a water film is stretched between the diaphragm 15 and the anode layer 14 and this water film effectively prevents gas permeation.

As described above, according to the present embodiment, at the time of water intake (electrolysis) in which drinking water having a predetermined pressure or higher is supplied to the cathode chamber 12c with which the diaphragm 15 contacts via the cathode layer 14, it is higher than the anode chamber 11c. Water is supplied to the inside of the diaphragm 15 and the gap between the diaphragm 15 and the cathode layer 14 by drinking water (pressurized water) having pressure, and the hydrogen gas generated on the surface of the cathode layer 14 is electrolyzed. Hydrogen water is generated by dissolving in drinking water. At that time, dissolved solids such as calcium and magnesium accumulated in the gap between the diaphragm 15 and the cathode layer 14 are concentrated, but the water intake pause (electrolysis pause) in which drinking water is not supplied to the cathode chamber 12c. ) In some cases, the diaphragm 15 is pressed against the cathode layer 14 by making the pressure in the anode chamber 11c higher than the pressure in the cathode chamber 12c, and dissolution of calcium, magnesium, etc. accumulated in the gap between the diaphragm 15 and the cathode layer 14 The water in which the solid matter is concentrated is pushed into the cathode chamber 12c, and when drinking water having a higher pressure than the anode chamber 11c is supplied to the cathode chamber 12c at the next water intake (electrolysis), the inside of the diaphragm 15 In addition, water having a reduced concentration is supplied to the gap between the diaphragm 15 and the cathode layer 14, and the dissolved solid matter is pushed out. That is, by alternately changing the pressure in the cathode chamber 12c and the pressure in the anode chamber 11c, the diaphragm 15 is moved between the cathode layer 14 and the anode layer 13 by piston movement, so that the gap between the cathode layer 14 and the diaphragm 15 is obtained. The existing water is replaced to remove scales such as calcium and magnesium.

In addition, according to the present embodiment, solid polymer electrolysis is utilized, and drinking water having conductivity due to inorganic dissolution is supplied to the cathode chamber 12c under pressure, and hydrogen gas generated on the cathode surface is supplied to the drinking water. To produce hydrogen water. In solid polymer electrolysis, the reaction of H ₂ O → 1 / 2O ₂ ↑ + 2H ⁺ + 2e ⁻ occurs on the anode side, and the reaction of 2H ⁺ + 2e ⁻ → H ₂ ↑ occurs on the cathode side. Although it is electrolysis, it does not become alkalinity of pH 9 or more unlike alkaline water electrolysis, and it is possible to produce hydrogen water in which mixing of hypochlorite ions is restricted. Furthermore, since drinking water is used, a device for making RO water or pure water from raw water is unnecessary, and this drinking water contains inorganic solids and has conductivity, and the electrolysis voltage value is lowered. Since there is little heat generation at the time of electrolysis and drinking water is supplied from the outside, a cooling device for the electrolytic cell becomes unnecessary, and the manufacturing cost of the device can be reduced.

Hereinafter, test results will be described for Comparative Examples 1 and 2 and Examples 1 and 2 using a certain amount of test water, respectively.

Comparative Examples 1 and 2 were performed with a hydrogen water production apparatus having the system configuration shown in FIG. In the figure, the electrolytic cell 10, the tank 80 ', the pump 81, the pressure reducing valve 82, the relief valve 83, the flow rate adjusting valve 84, the electromagnetic valve 85, and the control device 86 are substantially the same as the elements in the embodiment shown in FIG. It has the same configuration. However, the test water is stored in the tank 80 ′, no relief valve is connected to the anode chamber 11 c of the electrolytic cell 10, and the anode chamber 11 c is open to the atmosphere. In FIG. 12, 91 is a power supply device for electrolysis, 92 is an electrolysis current selector switch from the

power supply device

91, 93 is an ammeter that measures the electrolysis current, and 94 is a flow rate counter that measures the test water flow rate. Each is shown. The electrolytic voltage was measured with a voltmeter attached to the power supply device 91.

The test water is stored in the tank 80 ', and is sent from the tank 80' by the pump 81 through the pressure reducing valve 82 and the flow rate counter 94 to the cathode chamber 12c of the electrolytic cell 10 in this order to generate hydrogen water. Water was fed from the cathode chamber 12c of the electrolytic cell 10 through the flow rate adjustment valve 84 and the electromagnetic valve 85, and hydrogen water was taken.

The control device 86 has a computer that can be programmed, and the operation of the pump 81, the electrolysis of the electrolytic cell 10, and the operation of the electromagnetic valve 85 are controlled by the computer so that hydrogen water is generated. Configured. The measured value of the flow rate counter 94 was taken into the control device. The pressure reducing valve 82 was configured to adjust the pressure of drinking water pressurized by the pump 81 in the range of 0.2 to 0.3 MPa. The pressure in the anode chamber 11c of the electrolytic cell 10 was maintained at atmospheric pressure.

Examples 1 and 2 were performed with a hydrogen water production apparatus having the system configuration shown in FIG. In the drawing, the electrolytic cell 10, the tank 80 ', the pump 81, the pressure reducing valve 82, the flow rate adjusting valve 84, the electromagnetic valve 85, and the control device 86 have substantially the same configuration as each element in the embodiment shown in FIG. is doing. However, test water is stored in the tank 80 '. In FIG. 12, 91 is a power supply device for electrolysis, 92 is an electrolysis current selector switch from the

power supply device

91, 93 is an ammeter that measures the electrolysis current, and 94 is a flow rate counter that measures the test water flow rate. Each is shown.

The control device 86 has a computer that can be programmed, and the operation of the pump 81, the electrolysis of the electrolytic cell 10, and the operation of the electromagnetic valve 85 are controlled by the computer so that hydrogen water is generated. Configured. The measured value of the flow rate counter 94 was taken into the control device. The pressure reducing valve 82 was configured to adjust the pressure of drinking water pressurized by the pump 81 in the range of 0.2 to 0.3 MPa. The relief valve 83 was configured such that the discharge pressure was in the range of 0.03 to 0.1 MPa.

That is, in Comparative Examples 1 and 2, the anode chamber 11c of the electrolytic cell 10 is maintained at atmospheric pressure (0 MPa). In Examples 1 and 2, the anode chamber 11c of the electrolytic cell 10 is provided with a relief valve 83. The pressure was maintained in the range of 0.03 to 0.1 MPa.

In both Comparative Examples 1 and 2 and Examples 1 and 2, Ryuo-cho tap water was directly used as test water (dechlorination treatment was not performed). The water temperature was adjusted to 15 ° C. The test water quality was as shown in Table 1.

The operating conditions for Comparative Examples 1 and 2 and Examples 1 and 2 were as follows.
a) Cathode chamber water pressure: 0.2 MPa
b) Water intake amount: 1,200 mL / min
c) Electrode plate: 50 × 99 × 5t titanium lath plate with platinum coating (expanded specification: LW6 SW3 W1)
d) Membrane (solid polymer membrane): 78 × 113 Cation exchange membrane Composition: Sulfonate sodium salt of styrene copolymer Polyolefin mixture Film thickness: 0.16 mm
Burst strength: 0.53 MPa
e) Gap between Yin and Yang electrode plates: 0.15 mm (excluding Example 2)
f) Water intake / cleaning cycle:
[Intake cycle]
Intake operation: 30 seconds (600 mL hydrogen water intake)
Rest (stationary): 30 seconds [Charge reverse cleaning cycle]
Cycle: Water intake 40 times Once every cycle Washing operation: 20 seconds (400 mL acidic water drainage)
Rest (stationary): 40 seconds g) Electrolytic power source: Use constant current / constant voltage device. When the electrolysis voltage value was 17.8V or less, the constant current was given priority at 3.5A, and the current was supplied at 3.5A. From the time when the electrolysis voltage value reached 17.8V, the electrolysis current value was decreased and maintained at 17.8V. The amount of hydrogen generated when energized at 3.5 A was 30 NmL / min, and the dissolved hydrogen concentration of hydrogen water obtained at 15 ° C. was 1.1 mg / L.
h) Target water intake: The final target hydrogen water intake was 12,000 L (12 tons). The reason is “Assuming water intake of 3L / day at home, it is 1,095L in one year, 10,950L can be used for 10 years as a device, and the target is 12 tons.

(Comparative Example 1)
This is a method that is generally performed from the past, and is a method of closing the solenoid valve 85 simultaneously with the stop of the pump 81. The system configuration is as shown in FIG. 12, and the control flow is the flow shown in FIG. 9 in which the processes of steps S4 to S6 are performed simultaneously. Table 2 shows the pressures in the cathode chamber 12c and the anode chamber 11c during water intake and when water intake was stopped.

As shown in Table 2, in Comparative Example 1, since the anode chamber 11c is open to the atmosphere, the pressure is maintained at the atmospheric pressure during both water intake (electrolysis) and water intake stop (electrolysis stop). Therefore, the pressure in the anode chamber 11c is maintained below the pressure in the cathode chamber 12c. In such Comparative Example 1, the electrolysis current value (A) and the electrolysis voltage value (V) with respect to the water intake amount (L) were measured. The result is shown in FIG. In the figure, the horizontal axis represents the amount of hydrogen water taken in by the flow rate counter 94 (L), and the vertical axis represents the electrolysis current value (A) and the electrolysis voltage value (V).

As can be seen from the figure, in the test of Comparative Example 1, a current decrease started when 1 ton (1000 L) of hydrogen water was taken from the start of electrolysis. It is considered that the scale adhesion suddenly progressed to the cathode layer 14 from the point where the electrolytic current value fell below 3A.

In fact, when the scale attached to the surface of the cathode layer 14 on the side of the diaphragm 15 after the test was observed, a large amount of scale was accumulated as shown in FIG. Is shown). Although not shown, not much scale was collected on the surface of the cathode layer 14 opposite to the diaphragm 15.

(Comparative Example 2)
In this method, the electromagnetic valve 85 is closed after the pump 81 is stopped. The system configuration is as shown in FIG. 12, and the control flow is the same as that shown in FIG. Table 3 shows the pressures in the cathode chamber 12c and the anode chamber 11c at the time of water intake and when water intake was stopped.

As shown in Table 3, in this comparative example 2, since the anode chamber 11c is open to the atmosphere, the pressure is maintained at atmospheric pressure both during water intake (electrolysis) and during water intake stop (electrolysis stop). . On the other hand, the cathode chamber 12c is pressurized at the time of water intake (electrolysis), but the electromagnetic valve 85 is closed after the stop of the pump 81 (after 1 second) when the water intake is stopped. The chamber 12c is opened in the meantime, and is maintained at atmospheric pressure when the water intake is stopped (electrolytic stop). In such Comparative Example 2, the electrolysis current value (A) and the electrolysis voltage value (V) with respect to the water intake amount (L) were measured. The result is shown in FIG. In the figure, the horizontal axis represents the amount of hydrogen water taken in by the flow rate counter 94 (L), and the vertical axis represents the electrolysis current value (A) and the electrolysis voltage value (V).

As can be seen from the figure, in the test of Comparative Example 2, a current drop started when 8 tons (8000 L) of hydrogen water was taken from the start of electrolysis. Compared with the test of Comparative Example 1, the deposition of scale on the cathode layer 14 starts later, but it is considered that it also occurred.

Actually, when the scale attached to the surface of the cathode layer 14 on the side of the diaphragm 15 after the test was observed, a considerable amount of scale was accumulated as shown in FIG. 15B (the white portion in the figure was accumulated). Shows the scale). Although not shown, not much scale was collected on the surface of the cathode layer 14 opposite to the diaphragm 15.

Example 1
Similar to the case of Comparative Example 2, the electromagnetic valve 85 is closed after the pump 81 is stopped. The system configuration is as shown in FIG. 13, and the control flow is the same as that shown in FIG. The film thickness of the diaphragm 15 was 0.16 mm, and the gap between the cathode layer 14 and the anode layer 13 was set to 0.15 mm. Therefore, the diaphragm 15 is pressed by the cathode layer 14 and the anode layer 13 until the film thickness becomes 0.15 mm. Table 4 shows the pressures in the cathode chamber 12c and the anode chamber 11c at the time of water intake and when the water intake was stopped.

As shown in Table 4, in Example 1, since the relief valve 83 is connected to the anode chamber 11c, the pressure of the relief valve 83 is low during water intake (electrolysis) and when water intake is stopped (electrolysis stop). It is maintained below a predetermined pressure to be set (in this case, 0.04 MPa). The cathode chamber 12c is maintained at a pressure of pressurized water (in this case, 0.2 MPa) during water intake (electrolysis). Therefore, at the time of water intake, the pressure in the anode chamber 11c is maintained below the pressure in the cathode chamber 12c. On the other hand, when the water intake is stopped, the solenoid valve 85 is closed behind the stop of the pump 81 (after one second), so the cathode chamber 12c is opened during that time, so that when the water intake is stopped (electrolysis stop) Maintained at atmospheric pressure (0 MPa). Accordingly, when the water intake is stopped (electrolysis is stopped), the pressure in the anode chamber 11c is higher than the pressure in the cathode chamber 12c. Therefore, when the diaphragm 15 is pressed against the cathode layer 14 and moved, a pressure decrease of 0.02 MPa occurs. As a result, as shown in Table 4, the pressure in the anode chamber 11c when the water intake is stopped is 0.02 MPa. Since the diaphragm 15 is pressed against the cathode layer 14 when the water intake is stopped (electrolytic stop), the moisture in the diaphragm 15 and the cathode layer 14 is pushed out into the cathode chamber 12c.

The relationship between the pressure in the anode chamber 11c, the electrolysis current value, and the electrolysis voltage value during water intake (electrolysis) was examined. That is, as described above, the thickness of the diaphragm 15 is set to 0.16 mm, the gap between the cathode layer 14 and the anode layer 13 is set to 0.15 mm, the pressure in the cathode chamber 12c is set to a constant pressure of 0.2 MPa, and the anode chamber 11c. The electrolysis current value and electrolysis voltage value when the pressure was changed were examined. The results are shown in Table 5.

At the time of water intake, the diaphragm 15 is pressed from both sides of the cathode chamber 12c and the anode chamber 11c, and the film thickness becomes 0.14 mm or less. In this case, since the pressure in the cathode chamber 12c is higher than the pressure in the anode chamber 12c, the diaphragm 15 and the cathode layer 14 are not in close contact with each other and are slightly separated from each other. For this reason, the electrolytic voltage value for maintaining the H ⁺ ion movement and obtaining the same electrolytic current value becomes high. From Table 5, when the pressure of the anode chamber 11c was 0.10 MPa, the electrolytic current value was the same, but the electrolytic voltage value was high. Moreover, when the pressure of the anode chamber 11c became larger than 0.10 MPa, the electrolysis current value decreased. Accordingly, the pressure in the anode chamber 11c is desirably 0.10 MPa or less.

In such Example 1, the electrolysis current value (A) and the electrolysis voltage value (V) with respect to the water intake amount (L) were measured. The result is shown in FIG. In the figure, the horizontal axis represents the amount of hydrogen water taken in by the flow rate counter 94 (L), and the vertical axis represents the electrolysis current value (A) and the electrolysis voltage value (V).

As can be seen from the figure, in the test of Example 1, even when 12 tons (12000 L) of hydrogen water was taken from the start of electrolysis, the electrolysis current value could be maintained at a constant value of 3.5A. That is, it was found that the scale failure can be prevented by making the pressure in the anode chamber 11c larger than the pressure in the cathode chamber 12c when the water intake is stopped. In the figure, although there is a variation in the electrolytic voltage value, it is considered that this variation is caused by the intensity of pulsation and the difference in cleaning efficiency.

Actually, when the scale attached to the surface of the cathode layer on the diaphragm side after the test was observed, only a small amount of scale was accumulated as shown in FIG. 15C (the white portion in the figure was accumulated). Scale). Although not shown, almost no scale was collected on the surface of the cathode layer opposite to the diaphragm.

(Example 2)
Similar to the first embodiment, the electromagnetic valve 85 is closed after the pump 81 is stopped. The system configuration is as shown in FIG. 13, and the control flow is the same as that shown in FIG. The film thickness of the diaphragm 15 was 0.16 mm, and the gap between the cathode layer 14 and the anode layer 13 was set to 0.10 mm. Therefore, the diaphragm 15 is considerably pressed by the cathode layer 14 and the anode layer 13 until the film thickness becomes 0.10 mm. In Example 2, the gap between the cathode layer 14 and the anode layer 13 was set to be considerably narrower than that in Example 1. Table 6 shows the pressures in the cathode chamber 12c and the anode chamber 11c at the time of water intake and when the water intake was stopped.

As shown in Table 6, in Example 1, since the relief valve 83 is connected to the anode chamber 11c, the pressure of the relief valve 83 is low during water intake (electrolysis) and when water intake is stopped (electrolysis stop). It is maintained below a predetermined pressure to be set (in this case, 0.05 MPa). The cathode chamber 12c is maintained at a pressure of pressurized water (in this case, 0.2 MPa) during water intake (electrolysis). Therefore, at the time of water intake, the pressure in the anode chamber 11c is maintained below the pressure in the cathode chamber 12c. On the other hand, when the water intake is stopped, the solenoid valve 85 is closed after a stop of the pump 81 (after one second), so the cathode chamber 12c is opened during that time, so that when the water intake is stopped (electrolysis stop) Maintained at atmospheric pressure (0 MPa). Accordingly, when the water intake is stopped (electrolysis is stopped), the pressure in the anode chamber 11c is higher than the pressure in the cathode chamber 12c. Therefore, when the diaphragm 15 is pressed against the cathode layer 14 and moved, a pressure decrease of 0.02 MPa occurs. As a result, as shown in Table 6, the pressure in the anode chamber 11c when the water intake is stopped is 0.03 MPa. Since the diaphragm 15 is pressed against the cathode layer 14 when the water intake is stopped (electrolytic stop), the moisture in the diaphragm 15 and the cathode layer 14 is pushed into the cathode chamber 12c.

The relationship between the pressure in the anode chamber 11c, the electrolysis current value, and the electrolysis voltage value during water intake (electrolysis) was examined. That is, as described above, the thickness of the diaphragm 15 is set to 0.16 mm, the gap between the cathode layer 14 and the anode layer 13 is set to 0.10 mm, the pressure in the cathode chamber 12c is set to a constant pressure of 0.2 MPa, and the anode chamber 11c. The electrolysis current value and electrolysis voltage value when the pressure was changed were examined. The results are shown in Table 7.

At the time of water intake, the diaphragm 15 is considerably pressed from both sides of the cathode chamber 12c and the anode chamber 11c to increase the adhesion, and the film thickness becomes 0.10 mm or less. In this case, the pressure in the cathode chamber 12c is higher than the pressure in the anode chamber 12c, but because the degree of adhesion is high, the diaphragm 15 and the cathode layer 14 are kept in close contact with each other. From Table 7, even when the pressure in the anode chamber 11c was 0.10 MPa or more, the electrolysis current value was maintained at the same value, and the electrolysis voltage value was also maintained at the same value.

In such Example 2, the electrolysis current value (A) and the electrolysis voltage value (V) with respect to the water intake amount (L) were measured. The result is shown in FIG. In the figure, the horizontal axis represents the amount of hydrogen water taken in by the flow rate counter 94 (L), and the vertical axis represents the electrolysis current value (A) and the electrolysis voltage value (V).

As can be seen from the figure, in the test of Example 2, even when 12 tons (12000 L) of hydrogen water was taken from the start of electrolysis, the electrolysis current value could be maintained at a constant value of 3.5A. Further, even if the gap between the diaphragm 15 and the cathode layer 14 and the gap between the diaphragm 15 and the anode layer 13 are extremely narrow, in other words, even if the diaphragm 15 is pressed tightly with the cathode layer 14 and the anode layer 13. The electrolytic current value did not change. Conversely, the same electrolysis current value as in Example 1 could be obtained with a lower electrolysis voltage value. That is, when the water intake is stopped, the pressure in the anode chamber 11c is made larger than the pressure in the cathode chamber 12c, so that the scale failure can be achieved regardless of the gap amount between the diaphragm 15 and the cathode layer 14 and the gap amount between the diaphragm 15 and the anode layer 13. It was found that can be prevented.

In fact, when the scale adhered to the surface of the cathode layer on the diaphragm side after the test was observed, only a small amount of scale was accumulated as shown in FIG. 15D (the white portion in the figure was accumulated). Scale). Although not shown, almost no scale was collected on the surface of the cathode layer opposite to the diaphragm.

FIG. 19 shows the electrolysis current value and electrolysis voltage value with respect to the amount of water taken in Comparative Examples 1 and 2 and Example 1 described above on the same diagram. However, the film thickness of the diaphragm 15 is 0.16 mm, and the test data in which the gap between the cathode layer 14 and the anode layer 13 is set to 0.15 mm is compared.

As can be seen from FIG. 15 and FIG. 15, a relief valve 83 is attached to the anode chamber 11c, and the compression state of the diaphragm 15 is moved like a piston by utilizing pressure fluctuations in the anode chamber 11c, so that the diaphragm 15 and the cathode can be moved. Water was able to be sucked and discharged between the layers 14, and in particular, scale adhesion to the cathode layer 14 could be prevented.

The embodiments and examples described above are all illustrative and do not limit the present invention, and the present invention can be implemented in various other modifications and changes. Therefore, the scope of the present invention is defined only by the claims and their equivalents.

In the field of producing hydrogen water for beverages or other purposes, tap water can be used and can be applied to a hydrogen water production apparatus that is used for a long time.

DESCRIPTION OF SYMBOLS 10 Electrolysis cell 11 Case on anode side

11b Gas outlet

11c Anode chamber

11d, 12d Rib 11e Circumferential groove 12 Case on cathode side

12a Water inlet

12b Water outlet 12c Cathode chamber 13 Anode layer 14 Cathode layer 15 Diaphragm 16

Packing

17, 18 Connection terminal for lead wire 60

Ammeter

61, 91

Power supply device

80, 80 ′ Tank 81 Pump 82 Pressure reducing valve 83

Relief valve

84, 88

Flow control valve

85, 87

Solenoid valve

86, 90 Control device 89 Pressure gauge 91 Power supply (voltage) (With meter)
92 selector switch 93 ammeter 94 flow counter

Claims

An anode layer having a catalyst necessary for electrolysis and allowing water and gas to pass therethrough, a cathode layer having a catalyst necessary for electrolysis and allowing water and gas to pass therethrough, and the anode layer and the cathode layer being in close contact with each other And a cathode chamber in contact with the cathode layer, and drinking water having a predetermined pressure or higher is supplied to the cathode chamber. In the state 1, the hydrogen gas generated in the cathode layer is electrolyzed by controlling the water or gas single pressure of the anode chamber or the mixed pressure of water and gas to be less than the pressure of the cathode chamber, and the drinking water In the second state in which no drinking water is supplied to the cathode chamber, the mixing pressure of water in the cathode chamber and gas is the water in the anode chamber or Single pressure of gas or water and gas Apparatus for producing hydrogen water, characterized in that it is configured to control the under combined pressure.
The water or gas single pressure or the water and gas mixing pressure in the anode chamber in the first state is a pressure in the range of 0.03 MPa to 0.1 MPa. Hydrogen water production equipment.
2. The apparatus for producing hydrogen water according to claim 1, wherein in the first state, the pressure of drinking water supplied to the cathode chamber is a pressure in the range of 0.1 MPa to 0.3 MPa.
The apparatus for producing hydrogen water according to claim 1, wherein, in the second state, the pressure in the cathode chamber is atmospheric pressure.
5. A hydrogen water production apparatus according to claim 1, wherein a relief valve is connected between the anode chamber and the atmosphere.
A pressure gauge is connected to the anode chamber and a solenoid valve is connected between the anode chamber and the atmosphere, and the solenoid valve is controlled based on a measured value of the pressure gauge. The apparatus for producing hydrogen water according to any one of claims 1 to 4, wherein:
The apparatus for producing hydrogen water according to claim 1, wherein the moisture content of the solid polymer membrane is a cation exchange membrane having a moisture content of 27.6% or more with respect to a saturated moisture-containing membrane.
The apparatus for producing hydrogen water according to claim 1, wherein the catalyst of the anode layer and the cathode layer is a platinum catalyst.
The apparatus for producing hydrogen water according to claim 1, wherein the anode layer and / or the cathode layer is a titanium platinum electrode formed of a lath net or punch metal of titanium.