JP2003342773A - High-pressure hydrogen manufacturing method and device for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and a device for manufacturing high-pressure hydrogen for stably, efficiently and safely generating hydrogen only by water electrolysis by the power generated by a considerably changing natural energy such as solar beam without using any gas compressor. <P>SOLUTION: High-pressure hydrogen is manufactured by electrolysis of pure water using a hydro-electrolysis cell 1 formed of a solid polymer electrolytic film while regulating the differential pressure between the pressure in a high- pressure hydrogen vessel 2 to store generated hydrogen and the pressure in a high-pressure oxygen vessel 62 to store oxygen by the movement of pure water in the vessels 2 and 62. A differential pressure detector 53 or a pressure regulator is provided, and the pressure is regulated by the movement of pure water thereby. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a solid polymer electrolyte membrane (PEM) without using a gas compressor, and produces high-pressure hydrogen by simply electrolyzing pure water, that is, high-pressure hydrogen. The present invention relates to a hydrogen production device and belongs to hydrogen clean energy related technology.

[0002]

2. Description of the Prior Art Fossil fuels such as coal and petroleum, which are the mainstream of energy at present, are caused by global warming due to the carbon dioxide emitted by their use. Nitrogen oxides and sulfur oxides are harmful to human health and cause acid rain, and their reserves are not infinite and there are many problems such as depletion sooner or later. is doing.

In order to solve these problems, it is required to develop a technology for replacing fossil fuel with renewable and clean natural energy. Among them, solar energy is equivalent to one hour of energy that the earth receives for more than a year's energy consumed by humanity today, and solar energy alone can cover humanity's energy demand. It is not a dream.

As well known as a method for utilizing natural energy, such as solar power generation and wind power generation, natural energy is generally extracted and used as electric power, but the electric power is not used as it is. Since it cannot be stored or carried, there is a method of charging and storing the battery for use, but the battery is extremely heavy and self-discharges, so it is consumed even if it is not used. Have a problem.

Therefore, the shift to a hydrogen economic society in which electric power obtained from natural energy is efficiently converted into clean hydrogen energy by water electrolysis and hydrogen is used as energy is under study. Furthermore, the development of a fuel cell (PEFC) that uses hydrogen as fuel has been actively promoted, and its widespread use in private power generation for automobiles and households is under consideration. However, it is required to efficiently produce hydrogen with natural energy.

In response to such a demand, a solid polymer electrolyte membrane having proton (hydrogen ion) conductivity (hereinafter referred to as P
It is called EM. ), PEM water electrolysis that directly electrolyzes pure water into hydrogen and oxygen attracts attention as a method for efficiently producing hydrogen. This PEM water electrolysis lacks the ability to follow fluctuations, and unlike alkaline water electrolysis, which cannot be started and stopped freely, it has the feature that it can be started and stopped freely. This is the most suitable method for converting the obtained electric power that fluctuates into hydrogen.

The biggest problem in using the thus obtained hydrogen as energy is how to safely and compactly carry hydrogen as a gas (transportation).
Since it is either stored or stored, a method of making gaseous hydrogen into liquid hydrogen and storing it in a storage alloy has been studied, but recently, the safety of high pressure hydrogen has been reviewed, As the compressed hydrogen obtained by compressing hydrogen to a high pressure of 350 atm or higher, the method of filling and storing in a cylinder or the like is increasingly adopted, and it has been widely used as a technology that constitutes a hydrogen economic society. Is coming.

[0008] The electrolysis of water has a pressurizing ability to generate high-pressure hydrogen and oxygen by itself, and in principle, electrolysis can be performed without using a booster such as a compressor. It is not a dream to generate high-pressure hydrogen above atmospheric pressure, and since there is no moving part compared to when mechanically boosting pressure, there is no need for maintenance work such as regular inspection and replacement of consumable parts. It has many advantages such as low boosting efficiency and low power cost.

However, in electrolysis using a PEM-based water electrolysis cell, since the current water electrolysis cell has a low withstand voltage, hydrogen or oxygen of several atmospheres to several tens of atmospheres is generated at most, which is necessary for energy utilization. It is not possible to generate high pressure hydrogen of 350 atm or higher, and such a high pressure booster is a development theme of its own as of today. The advent of high-pressure hydrogen production equipment that can generate high-pressure hydrogen has been awaited.

Patent No. 3,22 which first solves this problem
No. 0,607 (US Pat. No. 5,690,797) discloses a pressure applied to a water electrolysis cell when a water electrolysis cell is placed in pure water in a high-pressure container for storing pure water and oxygen and water electrolysis is performed. Pays attention to the fact that only the differential pressure between hydrogen and oxygen is generated, and by controlling the pressures of hydrogen and oxygen to be equal, even if a water electrolysis cell with a low pressure resistance is used, It is capable of generating high pressure hydrogen and oxygen far exceeding the above.

However, according to the present invention, since the water electrolysis cell is soaked in pure water, if the water quality of the pure water deteriorates and the specific resistance decreases, leakage or electrolysis occurs between the electrodes of the water electrolysis cell. Since the problem of corrosion occurs, it cannot be said that it is easy to generate high-pressure hydrogen of several hundred atmospheric pressure or more, which is required for energy utilization.

In particular, the specific resistance of pure water decreases as the temperature rises, but in addition to that, the elution of the container wall and the like into the pure water becomes faster, so it is necessary to constantly regenerate the pure water with an ion exchange resin. However, if the pure water to be treated has a high pressure, the ion-exchange resin particles will be destroyed, so the pressure that can be generated is limited, and it is difficult to generate high-pressure hydrogen that is necessary for the use of hydrogen energy. It was

In order to prevent such a problem, a proposal (Japanese Patent Laid-Open No. 2001-130901) to store the water electrolysis cell in a high-pressure container filled with an insulating liquid has been made, but it is practical as an insulating liquid. It was found that there is no such thing in the present situation, and it is poor in practicality.

For example, PCB as an insulating liquid is flame-retardant and excellent in performance, but its production and use are prohibited due to problems such as pollution. Currently, all insulating oils that can be used are
After all, pure water is excellent as an insulating liquid because it is flammable and may explode if oxygen leaks, but pure water has problems such as a change in resistivity over time as described above. Yes, its use is difficult.

In order to solve these problems, the inventor previously disclosed in Japanese Patent Application No. 2002-019713 that a water electrolysis cell is arranged in a high-pressure container which also serves as a storage portion for the generated hydrogen, that is, water. While placing the electrolysis cell in high-pressure hydrogen, the pressure difference between the pressure of the high-pressure vessel in which the water electrolysis cell is placed and the pressure of the high-pressure vessel that also functions as a reservoir of pure water for electrolysis and generated oxygen is equal to or lower than the pressure resistance of the water electrolysis cell. Adjust to the pressure of
I made a proposal.

This proposal is based on the above-mentioned patent No. 3,220,60.
Not only did it solve the problems of electrolytic corrosion and reduction in the specific resistance of pure water, which were problems with No. 7, etc., but it also served to separate pure water from oxygen even if the water electrolysis cell was damaged. This is a breakthrough in safety such as the prevention of explosions.

[0017]

However, in this proposal, in order to keep the force acting on the water electrolysis cell within the pressure resistance of the water electrolysis cell, the generated differential pressure of hydrogen and oxygen is within the pressure resistance of the water electrolysis cell. However, since the pressure resistance of the water electrolysis cell is constant, the higher the pressure of the generated hydrogen and oxygen, the higher the control accuracy is required. Will be a limiting factor for the hydrogen pressure generated.

That is, when the allowable withstand pressure of the water electrolysis cell is 4 atm and the generated pressure of hydrogen and oxygen is 10 atm, the pressure control accuracy is 4/10, in other words, within 40%. Although it is possible to deal with the water electrolysis cell without damaging the water electrolysis cell, considering the case of generating hydrogen and oxygen of 400 atm using this water electrolysis cell, 4/400, that is, 1% The above precise and highly accurate pressure control is required, and it is difficult to achieve it with a normal pressure control method. Moreover, since the required pressure will be higher in the future, further strict pressure control precision is required.
A new method is required because the conventional pressure control method is almost impossible.

Further, in the method proposed in this proposal, there is a problem in the water level gauge for measuring the liquid level of pure water. That is,
Pure water, which is a raw material for electrolysis, is stored in a high-pressure container together with oxygen generated by water electrolysis.
(Atmospheric pressure) oxygen density is 1.429 × 10 ⁻³ g / cc
It is very light, and it is common sense that water is below and oxygen is above in the container.
From /1.429×10 ⁻³ = 700, oxygen at 700 atm has the same density as water. This means that at 700 atmospheric pressure or higher, water floats on oxygen, and the normal rule of thumb that gas is lighter than water does not hold.

Fortunately, such a density reversal is
Considering the size and intermolecular force of oxygen molecules, it does not occur unless the atmospheric pressure is 1000 atm or more. However, in the float type water level meter that has been widely used in the past, when the difference in density between water and oxygen becomes small, the operation is caused by water flow. It becomes unstable and cannot detect the water surface accurately. In addition to this, the float used in the float type water level gauge has to be manufactured to have an apparent specific gravity of 1 or less, so that there is a problem in pressure resistance, and pressure such as that required for energy use of hydrogen is required. Since it is difficult to manufacture a float that can withstand the above conditions, it is possible to solve such problems and to develop a water level gauge that operates stably under high pressure in order to carry out the proposed method widely and stably. , Is strongly demanded.

Unless the above problems, especially the problem of pressure control accuracy, are solved, hydrogen of 350 atm or higher, which is required for energy utilization of hydrogen, can be stably produced only by electrolysis of water. It can be said that it is impossible, and the inventor has solved the problems as described above, and is required to use as energy without using mechanical means such as a compressor. The purpose of this study was to provide a high-pressure hydrogen production device that can safely and safely generate high-pressure hydrogen simply by electrolyzing water.

As a result, the inventor has paid attention to the fact that pure water exists in both the hydrogen high-pressure container and the oxygen high-pressure container for storing the generated hydrogen and oxygen, and the pure water having a higher pressure is used. By the method of eliminating the differential pressure by moving from the lower to the above, the problem of the pressure control can be solved, and by utilizing the fact that the electric conductivity characteristics of the gas such as oxygen and pure water are greatly different, The inventors have found that the problem of the water level gauge can be solved by detecting the water level, and have completed the present invention.

[0023]

That is, the method for producing high-pressure hydrogen according to claim 1 of the present invention is to produce hydrogen by electrolyzing pure water with a water electrolysis cell comprising a solid polymer electrolyte membrane. , The pressure difference between the hydrogen high pressure container that stores the generated hydrogen and the oxygen high pressure container that stores oxygen,
The pure water existing in each container is adjusted by moving it to one side.

Further, in the high-pressure hydrogen production method according to the second aspect of the present invention, when the pure water is electrolyzed to generate hydrogen by the water electrolysis cell composed of the solid polymer electrolyte membrane, the generated hydrogen is generated. The pressure difference between the hydrogen high-pressure container for storing oxygen and the oxygen high-pressure container for storing oxygen is adjusted so that the hydrogen pressure of each container, the adjustment of the oxygen pressure, and the pure water present in each container are moved to either side. It is characterized by being controlled by.

The invention according to claim 3 of the present invention is characterized in that, in the high-pressure hydrogen production method according to claim 1 or 2, the pressure difference is suppressed to a value equal to or lower than the withstand voltage of the water electrolysis cell. Is.

The invention according to claim 4 of the present invention is the method for producing high-pressure hydrogen according to claim 1 or 2, wherein the pure water is moved by pure water connecting a hydrogen high-pressure container and an oxygen high-pressure container. It is characterized in that it is performed by operating an opening valve connected to a pipe and provided in each container.

The invention according to claim 5 of the present invention is the method for producing high-pressure hydrogen according to claim 4, wherein the operation of the opening valve is a state in which the opening valve is immersed in pure water in a container. It is characterized by doing in.

The invention according to claim 6 of the present invention is the method for producing high-pressure hydrogen according to claim 1 or 2, wherein the pure water is moved by pure water connecting a hydrogen high-pressure container and an oxygen high-pressure container. It is characterized in that it is automatically performed by a pressure regulator provided in the pipe.

The invention according to claim 7 of the present invention is the method for producing high-pressure hydrogen according to claim 1 or 2, wherein the movement of the pure water is pure water connecting a hydrogen high-pressure vessel and an oxygen high-pressure vessel. It is characterized in that the operation is performed by opening and closing a valve provided in the pipe.

The invention according to claim 8 of the present invention is the method for producing high-pressure hydrogen according to claim 1 or 2, wherein the pure water volume stored in the hydrogen high-pressure container is stored in the oxygen high-pressure container. And a volume of pure water stored in the oxygen high pressure container is controlled to be equal to or larger than the volume of hydrogen stored in the hydrogen high pressure container.

According to a ninth aspect of the present invention, in the high-pressure hydrogen production method according to the first or second aspect, the amount of oxygen stored in the oxygen high-pressure container is stored in the hydrogen high-pressure container. The high-pressure hydrogen production method is characterized in that the hydrogen is produced while being controlled within 4% of the amount of hydrogen.

Further, the invention according to claim 10 of the present invention is a water electrolysis cell comprising a solid polymer electrolyte membrane, a hydrogen high-pressure container for storing generated hydrogen and pure water accompanying hydrogen,
An oxygen high-pressure container for storing raw materials and returned pure water and generated oxygen, a pure water pipe connecting the pure water in the hydrogen high-pressure container with the pure water in the oxygen high-pressure container, and a hydrogen high-pressure container and hydrogen in the oxygen high-pressure container. A high-pressure hydrogen production apparatus comprising a differential pressure detector for detecting a pressure difference of oxygen and controlling the pressure difference.

The invention according to claim 11 of the present invention is a water electrolysis cell comprising a solid polymer electrolyte membrane, a hydrogen high-pressure container for storing generated hydrogen and pure water accompanying hydrogen, and pure water as a raw material. Oxygen high pressure container for storing oxygen, pure water pipe for communicating pure water in the hydrogen high pressure container with pure water in the oxygen high pressure container, and pure water of the hydrogen high pressure container and oxygen high pressure container provided in the pure water pipe The high-pressure hydrogen production apparatus is provided with a pressure regulator having a slider inside which slides according to the pressure difference from the pure water.

According to a twelfth aspect of the present invention, in the high-pressure hydrogen production apparatus according to the tenth or eleventh aspect, the water electrolysis cell is installed in a hydrogen high-pressure vessel or a pure water oxygen high-pressure vessel. It is characterized by being.

According to a thirteenth aspect of the present invention, in the high-pressure hydrogen production apparatus according to the tenth or eleventh aspect, a high-pressure pure water supply tank and a pure water supply tank are provided above the oxygen high-pressure vessel. , A water pump connecting their bottoms, an ion-exchange resin cylinder, a pure water circulation feed pipe having a filter, a pure water circulation return pipe connecting the upper part of the high-pressure pure water supply tank and the upper part of the pure water supply tank, oxygen high pressure An oxygen supply pipe connecting the upper part of the container to the upper part of the high-pressure pure water supply tank, and a pure water production / supply system in which a pure water injection pipe connecting the bottom of the high-pressure pure water supply tank to the inside of the oxygen high-pressure container are arranged. Is a high-pressure hydrogen production apparatus characterized by.

According to a fourteenth aspect of the present invention, in the high-pressure hydrogen producing apparatus according to the tenth aspect, pure water in the hydrogen high-pressure container communicates with pure water in the oxygen high-pressure container. The pipe is characterized in that it is composed of two pipes, one having an opening valve provided in the hydrogen high-pressure container and the other having an opening valve provided in the oxygen high-pressure container.

According to a fifteenth aspect of the present invention, in the high-pressure hydrogen production apparatus according to the fourteenth aspect, the release valve has a discharge port having a triangular shape in a front view. It is what

According to a sixteenth aspect of the present invention, in the high pressure hydrogen production apparatus according to the tenth aspect, the differential pressure detector is the pressure of the hydrogen high pressure container or the oxygen high pressure container in the axial direction. A cylinder made of a non-magnetic material whose both ends are sealed by a bellows that expands and contracts, and the inside of which is filled with an inert fluid, an inner magnetic body which is movably provided in close contact with the inner surface of the cylinder, and in close contact with the outer surface. It is characterized by comprising a device main body composed of an movably provided external magnetic body and a detector for detecting a differential pressure based on the position of the external magnetic body changed by expansion and contraction of a bellows. Is.

According to a seventeenth aspect of the present invention, in the high-pressure hydrogen producing apparatus according to the sixteenth aspect, the differential pressure detector includes a light-shielding plate that moves in conjunction with an external magnetic body,
It is characterized in that it is composed of a display plate having an opening that is shielded by a light shielding plate and a photoelectric meter that converts the amount of transmitted light that has passed through the opening into an electric signal.

The invention according to claim 18 of the present invention is the high-pressure hydrogen production apparatus according to claim 16, wherein the differential pressure detector slides on an electric resistor in conjunction with an external magnetic body. The present invention is characterized by having a sliding element as a constituent element.

According to a nineteenth aspect of the present invention, in the high-pressure hydrogen production apparatus according to the eleventh aspect, one end of the pressure regulator communicates with pure water in the hydrogen high-pressure container and the other end. Hollow cylinder made of a non-magnetic material that communicates with pure water in an oxygen high-pressure container, an internal slider and hollow that is made of a magnetic material that blocks both pure water and slides in close contact with the inner surface of the hollow cylinder. It is characterized by comprising a device main body composed of an external slider made of a magnetic material that slides in close contact with the outer surface of a cylinder, and a position detector for detecting the position of the external slider. is there.

According to a twentieth aspect of the present invention, in the high-pressure hydrogen production apparatus according to the nineteenth aspect, the hollow cylinder has springs at both ends, and the internal slider is extended to the end. When it slides, it has a flow path for passing pure water at both ends.

According to a twenty-first aspect of the present invention, in the high-pressure hydrogen production apparatus according to the nineteenth aspect, the hollow cylinder has springs at both ends, and the inner slider is extended to the end. It is characterized in that it has a switch at both ends for opening and closing a shut-off valve provided in a pipe through which pure water flows, which operates when sliding.

According to a twenty-second aspect of the present invention, in the high-pressure hydrogen producing apparatus according to the nineteenth aspect, the hollow cylinder has an amount of hydrogen stored in a hydrogen high-pressure container,
It is characterized by having a substantial volume equal to or less than the smaller volume of either the amount of oxygen stored in the oxygen high-pressure container.

According to a twenty-third aspect of the present invention, in the high-pressure hydrogen production apparatus according to any one of the tenth to twenty-second aspects, the center electrode and the cylindrical electrode centering on the center electrode are formed. It is a high-pressure hydrogen production apparatus characterized by having a water gauge as an element.

Further, the invention according to claim 24 of the present invention is the high-pressure hydrogen production apparatus according to claim 23, wherein the water level indicator is a main electrode in which external electrodes are concentrically arranged outside a rod-shaped central electrode. The present invention is characterized by having an electrode and a sub-electrode in which an external electrode is concentrically arranged outside a rod-shaped center electrode whose outer end is covered with an electrically insulating cylinder.

Furthermore, the invention according to claim 25 of the present invention is the high-pressure hydrogen production apparatus according to any one of claims 10 to 23, in which the hydrogen high-pressure container is provided with a normally open hydrogen emergency release valve, pure water oxygen. The high-pressure hydrogen production apparatus is characterized in that a normally open oxygen emergency release valve is provided in the high-pressure container, and an emergency power-off switch is provided for the power source of the water electrolysis cell.

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the high-pressure hydrogen production method and apparatus of the present invention will be described below with reference to the accompanying drawings.

FIG. 1 is a schematic explanatory view showing an embodiment of the high-pressure hydrogen producing apparatus of the present invention. This high-pressure hydrogen producing apparatus is basically arranged in the hydrogen atmosphere generated by the water electrolysis cell 1. Hydrogen high-pressure container 2 arranged so as to fit, raw material pure water to be electrolyzed, oxygen high-pressure container 62 for storing return pure water and generated oxygen, pure water in hydrogen high-pressure container 2, and oxygen high-pressure container 62 Pure water pipes 16a, 16b for communicating pure water inside
And a differential pressure detector 53 for sensing the pressure difference between hydrogen and oxygen in the hydrogen high pressure vessel 2 and the oxygen high pressure vessel 62 and controlling the pressure difference.

In the high-pressure hydrogen producing apparatus shown in FIG. 1, pure water to be electrolyzed is supplied from the oxygen high-pressure container 62 to the pump 7
When the electric power necessary for water electrolysis is supplied from the power supply 61 to the water electrolysis cell 1, the pure water is electrolyzed and hydrogen and pure water are released from the hydrogen release port 3 into the hydrogen high-pressure container 2 to generate. The oxygen and the undecomposed pure water are sent to the oxygen high pressure container 62 through the return pipe 4.

The hydrogen high pressure vessel 2 and the oxygen high pressure vessel 62 are pressurized by the generated hydrogen and oxygen, respectively, and are brought to a predetermined pressure, for example, 400 atmospheric pressure. When there is no demand for hydrogen, this state is maintained. When the hydrogen is needed, the valve 57 is opened and the needle valve 56 is gradually opened, so that the hydrogen supply port 55 is stopped.
Is supplied with hydrogen.

When the pressure gauge 54 measures that the pressure in the hydrogen high-pressure container 2 is lowered by the supply of hydrogen, a command from a control device (not shown) interlocking with the pressure gauge 54 causes
The power supply from the power supply 61 to the water electrolysis cell 1 is restarted, and the power is supplied until the pressure of the pressure gauge 54 returns to the original value again.

When the pressure of the pressure gauge 54 is restored, the opening degree of the needle valve 56 is further increased and the power of the power source 61 is increased until the pressure of the pressure gauge 54 is restored. In this way, if the pressure does not drop even if the opening degree of the needle valve 56 is increased, or if the power supplied from the power supply 61 reaches the maximum allowable power, that state is maintained and hydrogen supply is continued.

Oxygen generated in the water electrolysis cell 1 together with hydrogen in the electrolysis of pure water is stored in the oxygen storage portion 5 above the oxygen high pressure vessel 62.
It is stored in 2.

The differential pressure between the pressure of oxygen stored in the oxygen storage section 52 and the pressure of hydrogen in the hydrogen high-pressure vessel 2 is the differential pressure shown below as an example of the specific example during electrolysis and during hydrogen supply. Measured by the detector 53, the control signal (not shown) normally causes the control device (not shown) to open and close the valve 44 and the needle valve 43 based on the measurement signal.
Is controlled to control the amount of oxygen released from the oxygen release port 45 so that the differential pressure signal from the differential pressure detector 53 becomes zero.

In this way, electrolysis is performed and hydrogen is supplied from the hydrogen supply port 55 while controlling the pressure in the hydrogen high-pressure container 2 and the pressure in the pure water oxygen high-pressure container 62 to be equal. .

In the conventional high-pressure hydrogen production apparatus, as described above, the differential pressure between the oxygen high-pressure vessel 62 and the hydrogen high-pressure vessel 2 is adjusted by releasing oxygen and hydrogen, particularly oxygen. Since the allowable pressure that can be expected from the pressure resistance of the cell 1 is about 4 atm, as described above, when using this water electrolysis cell 1 to generate hydrogen and oxygen at 400 atm, for example, 1% or more. High precision pressure control is required.

Therefore, in the present invention, the pressure difference is caused by fluctuations in the amount of hydrogen consumed by the device connected to the hydrogen supply port 55 and receiving hydrogen, fluctuations in pressure control due to fluctuations in the power supplied from the power supply 61, and the like. In order to avoid the occurrence of a differential pressure exceeding the allowable withstand voltage of the water electrolysis cell 1, that is, due to pressure control disturbance, generation of a differential pressure exceeding the allowable withstand pressure of the water electrolysis cell 1, pure water in the hydrogen high pressure vessel 2 and pure water in the oxygen high pressure vessel 62 are avoided. Pure water pipes 16a and 16b communicating with water and open valves 8 and 17 connected to the pure water pipes 16a and 16b, respectively, and operated based on the differential pressure are provided.

Therefore, when the hydrogen pressure in the hydrogen high-pressure vessel 2 becomes lower than the oxygen pressure in the oxygen high-pressure vessel 62, and the differential pressure thereof may exceed the allowable pressure value of the cell 1, Pure water in the oxygen high-pressure container 62 is released from the release valve 8 into the hydrogen high-pressure container 2, which reduces the pure water volume in the oxygen high-pressure container 62 and increases the oxygen volume in the oxygen storage section 52. As the oxygen pressure in the container 62 decreases, the pressure in the hydrogen high-pressure container 2 increases, and the differential pressure is maintained below the allowable withstand pressure.

At this time, the hydrogen volume in the hydrogen high-pressure container 2 is 2
0L, the oxygen volume in the oxygen high pressure vessel 62 is 0.4L (2% of hydrogen), and the generated pressure is 400 atm, 0.4
Pure water of 4 cc, which is 1% of L, flows out from the oxygen high pressure container 62 and flows into the hydrogen high pressure container 2, and the oxygen pressure is 400
Reduced by 4 atm, which is 1% of atmospheric pressure, and hydrogen pressure was 0.08
Since the atmospheric pressure is increased, the total differential pressure of 4.08 atm can be efficiently resolved by the inflow and outflow of pure water of only 4 cc.

It is important to control the water level 51 in the oxygen high pressure vessel 62, especially when hydrogen is generated at 350 atm or higher.
Is placed in the oxygen high-pressure container 62, the water surface 51 is constantly measured, and when the water surface 51 falls below a predetermined position, the valve 38 is opened and the pure water in the high-pressure pure water supply tank 41 is utilized by utilizing its gravity. It is poured into the oxygen high-pressure container 62 and supplied to the high-pressure pure water supply tank 41.
When pure water flows into the oxygen high pressure container 62 from the same, the same amount of oxygen simultaneously flows into the high pressure pure water supply tank 41 through the valve 39.

In order to flow the pure water in the high-pressure pure water supply tank 41 into the oxygen high-pressure container 62 by using gravity, the high-pressure pure water supply tank 41 is placed at a position higher than the oxygen high-pressure container 62, and the high-pressure pure water supply tank 41. The pure water supply tank 40 that supplies pure water to the water supply tank 41 also
It is important to install at the same position or higher position.

The pure water is supplied to the high-pressure pure water supply tank 41 by the valve 3
This is done by closing valves 8 and 39 and opening valves 36 and 37. That is, the valves 38 and 39 are closed and the oxygen high pressure container 6
2, and valves 36 and 37 are opened, and pure water supply tank 4
Pure water of 0 is supplied by the pump 32 through the ion exchange resin cylinder 33 and the filter 34.

At this time, the specific resistance of pure water is measured by the specific resistance meter 35. If the specific resistance value is low, the catalyst electrode of the water electrolysis cell 1 is poisoned and the life of the water electrolysis cell 1 is shortened. By circulating pure water, until the specific resistance becomes higher than a predetermined value,
The ion exchange resin cylinder 33 is passed through a plurality of times to perform an ion exchange process.

When the pure water supply tank 40 is installed above the high pressure pure water supply tank 41, the inside of the high pressure pure water supply tank 41 is filled with pure water and bubbles and the like can be removed.
The pressure fluctuation when the valve is closed and the valves 38 and 39 are opened is only the volume change of pure water, and can be almost ignored in terms of pressure control.

Since the pure water is circulated by the pump 32 at normal pressure, the pump 32, the ion exchange resin cylinder 33, the filter 34 and the resistivity meter 35 all operate at normal pressure.
The end of the pure water circulation by the pump 32 is determined by the resistivity meter 35.
It is determined by the pure water specific resistance value measured by.

Further, by providing a spare tank having the same function as the high-pressure pure water supply tank 41, if either one is always on standby, there will be no delay in the pure water supply to the oxygen high-pressure container 62.

The pure water in the oxygen high-pressure container 62 is sent to the water electrolysis cell 1 and used as a raw material for water electrolysis, so that it is stored for a long period of time and the specific resistance of pure water is, for example, 6 MΩ / cm ² or less. When the water quality is deteriorated, the catalyst electrode or the like of the water electrolysis cell 1 may be poisoned and the life of the water electrolysis cell 1 may be shortened. Therefore, in order to prevent deterioration of the water quality of the pure water in the oxygen high pressure vessel 62, It is desirable to replace some of the pure water with fresh pure water.

The pure water in the oxygen high pressure vessel 62 is replaced by the valve 1
8 is opened, pure water in the pure water oxygen high-pressure container 62 is poured into the pure water discharge tank 19, the valve 18 is closed, the valve 21 is opened, and the pure water in the pure water discharge tank 19 is discharged to the water receiving tank 23, This is done by replenishing that amount of pure water from the high-pressure pure water supply tank 41.

At this time, in order to reduce the pressure fluctuation during the pure water exchange operation, the volume of the pure water discharge tank 19 is set to the oxygen storage portion 52.
However, the frequency of deionized water replacement is about 10 times per day (about 10%), although it depends on the amount of deionized water used.

In the hydrogen high-pressure container 2, the pure hydrogen permeated from the anode to the cathode of the water electrolysis cell 1 is discharged from the hydrogen discharge port 3 together with the generated hydrogen, and accumulates at the bottom of the hydrogen high-pressure container 2.

It is preferable that the amount of pure water stored is at least about twice the volume of the oxygen storage portion 52 of the oxygen high pressure container 62. The amount of pure water is controlled by detecting the water surface 9 by the water level gauge 10. When the amount of pure water increases, the valve 11 is opened and the pure water receiving tank 1
Pour into 2. The volume of the pure water receiving tank 12 is set so that the pressure fluctuation due to the operation of opening the valve 11 and pouring the pure water into the pure water receiving tank 12 is equal to or less than the allowable withstand pressure determined by the withstand voltage of the water electrolysis cell 1.

For example, when the maximum hydrogen generation pressure in the hydrogen high-pressure vessel 2 is 400 atm, the stored hydrogen volume is 20 liters, and the allowable pressure of the water electrolysis cell 1 is 4 atm, the volume of the pure water receiving tank 12 is If it is less than 0.2 liter (1%),
The hydrogen pressure fluctuation in the operation of opening the valve 11 and flowing the pure water into the pure water receiving tank 12 is 400 × 1% = 4 atm at the maximum.

At this time, even if some factors overlap and a differential pressure of 4 atm or more is generated by this operation, the action of the release valves 8 and 17 exceeds the allowable pressure resistance of the water electrolysis cell 1. No differential pressure is generated.

In FIG. 1, 5 is a heat exchanger for cooling heat generated by electrolysis of water, and 6 is a heat exchanger for bringing pure water supplied to the water electrolysis cell 1 to a desired temperature. ,
13 is an electric resistance type water level gauge, 15 is a pure water discharge pipe, 20 is an electric type water level gauge, 24 is a float type water level gauge, 25 is a water supply port, 27 is a pump, 28 is an ion exchange tube, 29 is A filter, 30 is a pure water resistivity meter for measuring the pure water specific resistance, 31 is a float type water level gauge, 46 is an oxygen emergency release port, 47 is an oxygen emergency release valve, 48 is a pressure gauge, and 49 is in oxygen. Is a gas leak detector for detecting the hydrogen concentration of the hydrogen, 58 is a hydrogen emergency release valve, 59 is a hydrogen emergency release port, and 60 is a leak detector for measuring the oxygen concentration in hydrogen.

FIG. 2 is a partial cross-sectional view showing an example of the differential pressure detector used in the present invention. As shown in the drawing, the differential pressure detector 53 is a hydrogen high pressure container 2 or an oxygen high pressure container 62.
With the pressure of, the both ends are sealed by bellows 106 and 107 that expand and contract in the axial direction, and the cylinder 101 made of a non-magnetic material filled with an inert fluid inside and the inner surface of the cylinder 101 are in close contact and slidable in the axial direction. An apparatus main body 1 including an internal magnetic body 104 provided on the outer peripheral surface of the cylinder 101 and an external magnetic body 105 that is closely attached to the outer surface of the cylinder 101 and interlocks with the internal magnetic body 104 and is slidably arranged in the axial direction.
00 and a detector 120 for detecting the differential pressure in cooperation with the external magnetic body 105 that slides by the expansion and contraction of the bellows 106 and 107.
It consists of

The detector 120 includes a light shielding plate 119 that moves in conjunction with the external magnetic material 105, a display plate 116 having openings 117 and 118 shielded by the light shielding plate 119, and openings 117 and 118. It is composed of a photoelectric meter (not shown) that converts the transmitted light amount into an electric signal.

In the differential pressure detector 53 shown in FIG. 2, hydrogen in the hydrogen high-pressure vessel 2 is sent to the hydrogen pressure chamber 110 through the hydrogen pipe 112, and oxygen in the oxygen high-pressure vessel 62 is sent from the oxygen pipe 113 to the oxygen pressure chamber 111. Are sent to the bellows 106 and 107, respectively.

Since the bellows 106 and 107 and the cylinder 101 are filled with a fluid such as mechanical oil, the volume hardly changes even when pressure is applied, and the bellows 106 and 107 are connected to the hydrogen pipe 112.
Also, even if pressure is applied from high-pressure hydrogen and oxygen sent through the oxygen pipe 113, the pressure does not cause crushing.

When the pressures of hydrogen and oxygen sent through the hydrogen pipe 112 and the oxygen pipe 113 are equal, bellows 106 and 107 are used.
Since the forces pushed by the hydrogen pressure chamber 110 and the oxygen pressure chamber 111 are equal to each other, the internal magnetic body 104 remains stopped in the center of the cylinder 101.

However, when the pressure of hydrogen sent through the hydrogen pipe 112 is higher than that of oxygen sent through the oxygen pipe 113, the differential pressure causes the spring 114 to expand and the spring 115 to contract, so that the differential pressure and the spring 114 and Oxygen pressure chamber 111 until the position where the force due to expansion and contraction of 115 is balanced.
The internal magnetic body 105 is pushed to the side by the fixing rods 102 and 103 to move.

Since the inner magnetic body 104 and the outer magnetic body 105 exert a magnetic force on each other and are magnetically coupled to each other, the outer magnetic body 105 moves as the inner magnetic body 104 moves, and the outer magnetic body 105 moves. The fixed shading plate 119 moves to cover a part of the opening 118 on the oxygen side and the amount of light transmitted through the opening 117 does not change, but the amount of light transmitted through the opening 118 decreases.

On the contrary, when the pressure of hydrogen sent through the hydrogen pipe 112 is lower than the pressure of oxygen sent through the oxygen pipe 113, a part of the opening 117 on the hydrogen side is covered with the light shielding plate 119, and the opening is opened. The amount of light that passes through 117 decreases.

Therefore, by measuring the amount of light transmitted through the openings 117 and 118, whichever is higher, the difference in pressure between the hydrogen pressure sent through the hydrogen pipe 112 and the oxygen pressure sent through the oxygen pipe 113 is higher. Which is lower, the opening 11 can be controlled by controlling the opening / closing of the valve 44 and the needle valve 43 in FIG. 1 to control the amount of released oxygen.
Make sure there is no difference in the amount of light passing through 7 and 118, and set the differential pressure to 0.
Can be

In the above description, the method of measuring the position of the internal magnetic body 104 by measuring the light amount has been described, but the measurement can also be performed by using the slide resistance. That is, the external magnetic body 10
It is also possible to measure the amount of movement of the internal magnetic body 104 by fixing the slider to 5 and allowing the slider to move on the slide resistance in accordance with the movement of the slider integrated with the external magnetic body 105. it can.

FIG. 3 shows the release valves 8 and 1 used in the present invention.
7 is a sectional view (a) and a side view (b) showing the structure of FIG.
As shown in the figure, the open valves 8 and 17 are provided with a cylindrical valve main body 130, a discharge port 132 for discharging pure water, a cylinder 131, and a spring 133 interlocking with the cylinder 131 therein. And the spring 133 is fixed by a screw 135 and a fixing nut 136 so that the biasing force of the spring 133 can be adjusted, and pure water pipe 16a for moving pure water in the hydrogen high pressure container 2 or the oxygen high pressure container 62 or 16b
It has a connection pipe 138 for connection with and a vent 137.

The open valves 8 and 17 are pushed up by the pure water pressure transmitted by the connecting pipe 138 by loosening the fixing nut 136 and rotating the screw head 134 to adjust the pressing strength of the spring 133. The cylinder 131 is located above the discharge port 132, and the pure water in the connection pipe 138 is discharged from the discharge port 13
The pressure released from 2 can be set to the desired pressure (permissible pressure determined by the pressure resistance of the cell).
It is also possible to tighten 136 so that the setting does not change.

In the cylinder 131, when the pressure of the atmosphere in which the valve main body 130 is placed becomes higher than the pure water pressure in the connecting pipe 138, the spring 133 contracts due to the pressure difference, and the cylinder 131
When the pressure of pure water in the connection pipe 138 further increases, the cylinder 131 crosses the discharge port 132, and the pure water in the connection pipe 138 is discharged from the discharge port 132. Although the pressure in 138 is reduced, by making the shape of the discharge port 132 an inverted triangular shape, the amount of pure water discharged is small when the differential pressure is small, and increases when the differential pressure is large, The differential pressure can be quickly eliminated.

FIG. 4 is a cross-sectional view of a water level gauge 50 utilizing the fact that the electric conductivity characteristics of a gas such as oxygen and pure water are greatly different. The water level gauge 50 in FIG. 1 has a rod-shaped central electrode. 150a and a main electrode 150 composed of an outer electrode 150b arranged concentrically on the outside of the center electrode 150a, and a rod-shaped center electrode 151a having a portion other than the tip end covered with an electrically insulating cylinder.
And a sub-electrode 151 composed of an outer electrode 151b arranged concentrically outside the center electrode 151a.

In the figure, reference numeral 152 is the pure water surface, and 153a and 153.
b is a vent hole, 154a and 154b are attachment parts of the external electrodes 150b and 151b, 155a and 155b are attachment parts of the center electrodes 150a and 150b,
156a and 156b are insulators, and 157a and 157b are external electrodes 150.
Fixing jigs for mounting b and 151b, 158 mounting flanges, 159a and 159b nuts for fixing fixing jigs 157a and 157b, 160a and 160b insulating plates, 161a and 161b washers, 162a and 162b is a lead wire, 163a and 163b are washers, 16
4a and 164b are nuts for fixing the center electrodes 150a and 150b, and 165a to 167b are O-rings.

In the water level gauge 50 having such a structure, when the center electrode 150a and the outer electrode 150b are immersed in pure water, the resistance of the pure water immersed between the center electrode 150a and the outer electrode 150b becomes
Since an electric resistance meter can be connected between the lead wire 162a and the ground to perform measurement, this resistance value is defined as Rm.

On the other hand, when the electric resistance between the lead wire 162b and the ground is measured, the resistance of pure water between the tip of the center electrode 150b exposed without being covered with the insulating cylinder 168 and the external electrode 151b can be measured. Therefore, this resistance value is set to Rr.

Let Lr be the length of the tip of the center electrode 151a not covered by the insulating cylinder 168, and Lx be the length of the center electrode 150a and the outer electrode 150b immersed in pure water.
Lx can be calculated by the following equation (1).

[0094]

[Formula 1] Lx = Lr (Rr / Rm) (1)

When Lx is obtained from the above equation (1), the position of the pure water surface 152 can be known. The pure water specific resistance is about 18 MΩ / cm ² when it exits the ion exchange resin cylinder, but it decreases with time as the ion concentration increases by dissolving the pure water container wall and the like. Even if the water resistivity changes with time, Rr is measured and corrected each time, so that the accurate water surface position can always be detected.

Since gases such as oxygen and hydrogen are electrically insulating, the electric resistance between the lead wire 164a and the ground is only the electric resistance of pure water in which the center electrode 150a and the outer electrode 150b are immersed. Therefore, the influence of the electrical resistance of oxygen or hydrogen is negligible.

Further, since the structure including the center electrode 150a and the outer electrode 150b is excellent in pressure resistance, it is possible to use a material having high pressure resistance, as in the conventional float type water level gauge. There is no pressure limit.

Further, in the water level meter 50, applying electricity between the electrodes in an atmosphere in which high-pressure oxygen and water coexist may cause electrolytic corrosion, but the measurement may be performed in a pulsed manner or in the center. Electrodes 150a, 151a and external electrode 150
These problems can be avoided by plating b, 151b, etc. with a noble metal such as titanium or platinum that is resistant to electrolytic corrosion, and further, the electrical resistance Rr between the lead wire 164a and the ground is reduced.
Since the measurement of 1 is a measurement of the specific resistance of pure water, it can also be used as evaluation data for the quality of pure water, and the frequency with which the pure water in the pure water oxygen high-pressure container 62 is replaced can also be obtained.

FIG. 5 shows another embodiment of the high-pressure hydrogen producing apparatus according to the present invention, which is similar to the above-mentioned embodiment, in the water electrolysis cell 1.
Is similarly provided with an oxygen high-pressure container 62 which is arranged so as to be contained in the hydrogen atmosphere generated in the hydrogen high-pressure container 2 and which stores the pure water to be electrolyzed, the return pure water and the generated oxygen. However, instead of the differential pressure detector 53, a pressure regulator 70 is provided, and the release valves 8 and 17 are omitted.

This pressure regulator 70 is composed of an oxygen high pressure container 62.
Due to the pressure difference between the pure water and the hydrogen high-pressure container 2, the pure water between the two has a function of moving from higher pressure to lower pressure to eliminate the differential pressure.

That is, when the pressure in the oxygen high pressure vessel 62 becomes higher than the pressure in the hydrogen high pressure vessel 2, the oxygen high pressure vessel 6
Since the pure water in 2 flows into the pressure regulator 70 and the same amount of pure water is pushed back from the pressure regulator 70 into the hydrogen high pressure vessel 2, the pressure in the oxygen high pressure vessel 62 decreases with the amount of pure water. Since the volume of the oxygen storage portion 52 increases, the pressure decreases, and the amount of pure water in one hydrogen high pressure container 2 increases, so the pressure increases and the differential pressure is eliminated.

Further, the pressure regulator 70 detects the amount of movement of pure water, controls the opening / closing of the valve 44 and the needle valve 43 by a control device (not shown), and moves to the hydrogen high pressure container 2 side. It also has a function of returning the water to the oxygen high pressure container 62 and adjusting the amount of oxygen released from the oxygen release port 45 to make the pressure uniform so that such movement does not occur.

The amount of hydrogen generated from the water electrolysis cell 1 is controlled by controlling the amount of current supplied from the power supply 61 to the water electrolysis cell 1 so that the pressure measured by the pressure gauge 54 becomes a predetermined pressure. The replenishment of pure water to the oxygen high pressure vessel 62 and the drainage thereof and the drainage of the hydrogen high pressure vessel 2 are the same as the method of the embodiment shown in FIG.

FIG. 6A is a partial sectional view of a specific pressure regulator 70 used in the above embodiment, and FIG. 6B is a sectional view taken along the line AA 'in FIG. 6A. In the figure, this pressure regulator 70 shows a hollow cylinder 170 made of a non-magnetic material.
And an internal slider 171 made of a magnetic material that slides in close contact with the inner surface of the hollow cylinder 170, and an external slider 172 made of a magnetic material that slides in close contact with the outer surface of the hollow cylinder 170. 190 and a position detector 200 that detects the position of the outer slider 172.
At one side of the hollow cylinder 170 divided into
Pure water 184 inside is introduced into the other side, and pure water 185 inside the oxygen high pressure vessel 62 is introduced into the other side.

Since the pure water 184 from the hydrogen high pressure container 2 and the pure water 185 from the oxygen high pressure container 62 are separated and separated by the internal slider 171, the pure water 184 and the pure water 185 are mixed. In a state where the pressure inside the hydrogen high pressure vessel 2 and the pressure inside the oxygen high pressure vessel 62 are equal and no differential pressure is generated between them, the internal slider 171 is positioned at the center of the hollow cylinder 170. Is set to.

Therefore, the pressure in the hydrogen high-pressure container 2 becomes
If it becomes higher than the pressure in the oxygen high-pressure vessel 62, the pure water in the hydrogen high-pressure vessel 2 will flow from the pipe 175 into the hollow cylinder 170 to lower the pressure in the hydrogen high-pressure vessel 2 and the internal slider 171 will push it. Then, the pure water flows into the hollow cylinder 170 and the pure water
The volume of 184 has increased, and the volume of pure water that has been pushed down has decreased.
After passing through 176 and flowing into the pure water oxygen high-pressure vessel 62, the volume of oxygen in the oxygen high-pressure vessel 62 is reduced, so that the pressure of oxygen increases and the generated differential pressure is automatically canceled.

At this time, the inner slider 171 moves to the position displaced from the center toward the spring 183, and the inner slider 171 and the outer slider 172 are magnetically coupled to each other.
Also moves to the same position, and the light blocking plate 177 fixed to the outer slider 172 by the fixing rod 181 also moves to cover part of the opening 180, and the amount of light transmitted through the opening 180 decreases.

Therefore, by comparing the amount of light transmitted through the opening 180 and the opening 179, it can be known to which side and how much the internal slider 171 has moved.
And the amount of light transmitted through the opening 179 are compared, the opening degree of the needle valve 43 is controlled by a controller (not shown) so as to return the internal slider 171 to the original central position.

The position detector 200 for comparing the light amount of the pressure adjuster 70 has the same structure and function as the detector 120 of the differential pressure detector 53.

In this way, the internal slider 171 controls the opening of the needle valve 43 so that it is always in the center position, and supplies the oxygen from the oxygen release port 45 or the hydrogen supply port 55. By adjusting the amount of hydrogen, high-pressure hydrogen can be generated without applying a differential pressure to the water electrolysis cell 1.

Even with the above control, the hydrogen high-pressure container 2
When the internal pressure continues to be higher than the internal pressure of the oxygen high-pressure vessel 62 and the movement of the internal slider 171 cannot be stopped, the internal slider 171 hits the spring 183 and the spring 171
Since the internal slider 171 cannot be further moved unless is pressed, there is no restriction on the movement of the internal slider 171 while the internal slider 171 is moving to this position, so that a differential pressure is hardly generated.

However, when the internal slider 171 hits the spring 183, it cannot move any further unless the internal slider 171 pushes the spring 183. That is, the differential pressure cannot be adjusted by moving the internal slider 171. However, by providing the bypass flow passage 174, if the differential pressure becomes larger than that, the spring 183 contracts and pure water in the hydrogen high-pressure container 2 is removed. It does not flow into the oxygen high-pressure container 62 directly via the bypass flow path 174, and the differential pressure does not increase above a certain level.

Pure water in the hydrogen high-pressure container 2 is bypassed by the bypass passage 17
The fact that the oxygen flows directly into the oxygen high-pressure container 62 via 4 causes some abnormality, which cannot be controlled only by controlling the opening degree of the needle valve 43 by a control device (not shown). In the case of such an abnormal situation, an emergency stop is performed to shut off the power supply 61 of the water electrolysis cell 1 and close all except the valve 58 to generate hydrogen and oxygen from the water electrolysis cell 1. An emergency cutoff switch (not shown) and emergency release valves 47 and 58 are provided to stop the operation of the hydrogen gas and rapidly reduce the pressure of the hydrogen high pressure container 2.

Although not shown in FIG. 5, in order to safely stop the apparatus, a nitrogen pipe is provided so that the oxygen high pressure vessel 62 and the hydrogen high pressure vessel 2 are replaced with nitrogen gas. ing.

The internal slider 171 pushes the spring 183, and the strength of the springs 182 and 183 is adjusted so that the differential pressure at which pure water flows into the bypass passage 173 or 174 falls within the allowable withstand pressure of the water electrolysis cell 1. Is also one means for preventing the water electrolysis cell 1 from being damaged by receiving a pressure higher than the withstand pressure even in such an emergency stop.

Also, the volume of the hollow cylinder 170 is set to the internal slider 1
The oxygen reservoir 52 in the oxygen high-pressure container 62 except for the volume of 71
Equal to the volume of
50% differential pressure can be eliminated.

7 and 8 are partial sectional views of another pressure regulator 70. The pressure regulator 70 shown in these figures is
Instead of the bypass flow path 173 or 174 of the pressure regulator 70, a pure water pipe 213 having a shutoff valve 220 in parallel with the pressure regulator 70 and switches 211 and 21 for operating the opening and closing thereof.
2 is provided.

In these pressure regulators 70, when the internal pressure of the internal slider 171 contracts the spring 183 and the internal pressure of the internal slider 171 becomes larger than that which can be adjusted by the movement of the internal slider 171. The shutoff valve 220 is opened by the provided switches 211 and 212, and, for example, pure water in the hydrogen high-pressure container 2 is allowed to directly flow into the oxygen high-pressure container 62 via the pure water pipe 213 so that the differential pressure is equal to or higher than a certain level. It's a function that doesn't grow much.

[0119]

In the method and apparatus for producing high-pressure hydrogen according to the present invention, pure water existing in both the hydrogen high-pressure container and the oxygen high-pressure container is used, and the differential pressure between hydrogen and oxygen is set to a predetermined value (water electrolysis). Since the pressure inside the container is adjusted so that it does not exceed the withstand pressure of the cell), pressure control is facilitated, and the pressure of 350 atm required for hydrogen energy utilization is achieved by simply electrolyzing water without using a compressor. The above-mentioned production of high-pressure hydrogen is extremely easy.

Further, the pure water used for pressure adjustment is such that a part of the pure water supplied to the anode side where oxygen is generated enters the hydrogen high-pressure container and permeates to the cathode side where hydrogen is generated. Therefore, pure water is naturally supplied without specially supplying pure water, which effectively uses what has been treated as unnecessary in the past. It is an effective differential pressure control means that does not require any operation and can efficiently control the differential pressure with a small amount of pure water discharged.

Further, the higher the pressure of hydrogen and oxygen generated, the lower the differential pressure can be with a small amount of pure water, so that the optimum effect can be expected by applying to the high-pressure hydrogen production necessary for utilizing the energy of hydrogen. .

Further, in the present invention, the amount of pure water in the hydrogen high-pressure container is made larger than the volume of the portion of the oxygen high-pressure container where oxygen is stored, and the amount of pure water in the oxygen high-pressure container is set to be high. By making the volume larger than that of the portion in which hydrogen is stored, it is possible to reliably prevent the generation of detonation by mixing hydrogen and oxygen.

Furthermore, the oxygen storage amount is set to 4 times the hydrogen storage amount.
% Or less, even if mixed or even lower than the explosion lower limit, a large amount of pure water and a small amount of oxygen can be stored in the oxygen high-pressure container, and a small amount of pure water and a large amount of hydrogen can be stored in the hydrogen high-pressure container. By storing, the amount of pure water in the hydrogen high-pressure container is made larger than the volume of the portion of the oxygen high-pressure container in which oxygen is stored, and the amount of pure water in the oxygen high-pressure container is increased. By increasing the volume of the hydrogen storage part, oxygen in the oxygen high pressure container leaks and the pressure drops due to equipment failure or some inconvenience, and the pure water in the hydrogen high pressure container becomes oxygen high pressure container. Even if an accident occurs, the oxygen in the oxygen high-pressure container must be completely leaked and replaced with pure water, and the hydrogen in the hydrogen high-pressure container will not flow into the pure water oxygen container. , On the contrary, hydrogen leaks and Even if the power decreases and pure water in the oxygen high-pressure container flows in, oxygen in the oxygen high-pressure container will not be high unless the hydrogen in the hydrogen high-pressure container is completely replaced with pure water in the oxygen high-pressure container. Since it does not flow into the container, it is possible to avoid an accident in which explosion noise is generated.

Further, in the present invention, instead of the conventional float type water level gauge, a water level gauge for detecting the water level is utilized by utilizing the fact that the electric conductivity characteristics of gas such as oxygen and pure water are greatly different. Even if the density difference between high pressure oxygen and pure water becomes small by using it, the water surface can be detected stably and with high precision, and the pressure generated by the float being crushed by high pressure hydrogen or oxygen I lost the limit.

As described above, according to the present invention,
It is possible to automatically control the pressure difference between hydrogen and oxygen generated in water electrolysis within the pressure resistance of the water electrolysis cell, and the high pressure hydrogen required for the energy use of hydrogen, which has been strongly demanded so far, can be It can be manufactured safely, stably and at low cost without using a conventional compressor, and its practical and economic effects are immeasurable.

[Brief description of drawings]

FIG. 1 is a layout view of a high-pressure hydrogen production apparatus that is an embodiment of the present invention.

FIG. 2 is a partial cross-sectional view showing the structure of the differential pressure detector used in the present invention.

FIG. 3 is a sectional view (a) and a side view (b) showing a structure of an opening valve used in the present invention.

FIG. 4 is a cross-sectional view showing the structure of a water level gauge used in the present invention.

FIG. 5 is a layout view of a high-pressure hydrogen production apparatus which is another embodiment of the present invention.

FIG. 6 is a partial sectional view (a) and an AA ′ sectional view (b) of the pressure regulator used in the present invention.

FIG. 7 is a partial cross-sectional view of another pressure regulator used in the present invention.

FIG. 8 is a partial sectional view of another pressure regulator used in the present invention.

[Explanation of symbols]

1 Water electrolysis cell 2 Hydrogen high-pressure container 5,6 heat exchanger 8,17 Open valve 16a, 16b Pure water piping 28,33 Ion exchange resin cylinder 35 resistivity meter 40 Pure water supply tank 41 High-pressure pure water supply tank 50 water gauge 53 Differential pressure detector 62 oxygen high pressure container 70 Pressure regulator

Claims (25)

[Claims] 1. When a pure water is electrolyzed by a water electrolysis cell composed of a solid polymer electrolyte membrane to generate hydrogen, a hydrogen high-pressure container for storing the generated hydrogen and an oxygen high-pressure container for storing oxygen are provided. A high-pressure hydrogen production method, characterized in that the pressure difference is adjusted by moving the pure water existing in each container to one side. 2. When a pure water is electrolyzed to generate hydrogen by a water electrolysis cell composed of a solid polymer electrolyte membrane, a hydrogen high-pressure container for storing the generated hydrogen and an oxygen high-pressure container for storing oxygen are provided. A high-pressure hydrogen production method, characterized in that the pressure difference is controlled by adjusting the hydrogen pressure and the oxygen pressure in each container, and by moving the pure water existing in each container to either side. 3. The high-pressure hydrogen production method according to claim 1, wherein the pressure difference is suppressed to be equal to or lower than the pressure resistance of the water electrolysis cell. 4. The movement of the pure water is performed by operating an open valve connected to a pure water pipe connecting the hydrogen high pressure container and the oxygen high pressure container and provided in each container. Item 3. The method for producing high-pressure hydrogen according to Item 1 or 2. 5. The high-pressure hydrogen production method according to claim 4, wherein the operation of the open valve is performed while the open valve is immersed in pure water in a container. 6. The movement of the pure water is automatically performed by a pressure regulator provided in a pure water pipe connecting the hydrogen high pressure vessel and the oxygen high pressure vessel. The high-pressure hydrogen production method described. 7. The high pressure according to claim 1, wherein the pure water is moved by opening and closing a valve provided in a pure water pipe connecting the hydrogen high pressure container and the oxygen high pressure container. Hydrogen production method. 8. The high-pressure hydrogen production method according to claim 1, wherein the pure water volume stored in the hydrogen high-pressure vessel is equal to or larger than the oxygen volume stored in the oxygen high-pressure vessel, and the oxygen high-pressure vessel is also stored. A method for producing high-pressure hydrogen, characterized in that the volume of pure water stored in is controlled to be equal to or larger than the volume of hydrogen stored in a hydrogen high-pressure container. 9. The high-pressure hydrogen production method according to claim 1, wherein the amount of oxygen stored in the oxygen high-pressure container is controlled within 4% of the amount of hydrogen stored in the hydrogen high-pressure container. A method for producing high-pressure hydrogen, characterized by: 10. A water electrolysis cell composed of a solid polymer electrolyte membrane, a hydrogen high-pressure container for storing generated hydrogen and pure water accompanying hydrogen, an oxygen high-pressure container for storing raw materials, return pure water and generated oxygen, and hydrogen. Pure water pipe connecting the pure water in the high-pressure vessel and the pure water in the oxygen high-pressure vessel, and the difference for sensing the pressure difference between hydrogen and oxygen in the hydrogen high-pressure vessel and the oxygen high-pressure vessel and controlling the pressure difference. A high-pressure hydrogen production apparatus comprising a pressure detector. 11. A water electrolysis cell comprising a solid polymer electrolyte membrane, a hydrogen high-pressure container for storing generated hydrogen and pure water accompanying hydrogen, an oxygen high-pressure container for storing raw pure water and generated oxygen, and a hydrogen high-pressure container. The pure water pipe that connects the pure water inside and the pure water inside the oxygen high-pressure container and the pure water pipe are installed, and slide according to the pressure difference between the pure water in the hydrogen high-pressure container and the pure water in the oxygen high-pressure container A high-pressure hydrogen production apparatus comprising a pressure regulator having a sliding member inside. 12. The high-pressure hydrogen production apparatus according to claim 10, wherein the water electrolysis cell is installed in a hydrogen high-pressure container or a pure water oxygen high-pressure container. 13. The high-pressure hydrogen production apparatus according to claim 10 or 11, further comprising a high-pressure pure water supply tank and a pure water supply tank above the oxygen high-pressure container, and a water pump for connecting the bottoms of the tank and the ion pump. Pure water circulation feed pipe with exchange resin cylinder and filter,
Pure water circulation return pipe connecting the upper part of the high pressure pure water supply tank and the upper part of the pure water supply tank, oxygen supply pipe connecting the upper part of the oxygen high pressure container and the upper part of the high pressure pure water supply tank, the bottom part of the high pressure pure water supply tank and the oxygen high pressure container A high-pressure hydrogen production apparatus comprising a pure water production / supply system in which a pure water injection pipe connecting the inside is arranged. 14. The pure water pipe for communicating the pure water in the hydrogen high pressure container with the pure water in the oxygen high pressure container comprises a pipe provided with an open valve in the hydrogen high pressure container and an open valve in the oxygen high pressure container. The high-pressure hydrogen production apparatus according to claim 10, comprising two pipes provided. 15. The high-pressure hydrogen production apparatus according to claim 14, wherein the release valve has a discharge port having a triangular shape in a front view. 16. A cylinder made of a non-magnetic material, the both ends of which are sealed by bellows that expand and contract in the axial direction under the pressure of a hydrogen high pressure container or an oxygen high pressure container, and the inside of which is filled with an inert fluid. And an apparatus main body composed of an inner magnetic body that is movably provided in close contact with the inner surface of the cylinder and an outer magnetic body that is movably provided in close contact with the outer surface,
11. The high-pressure hydrogen production apparatus according to claim 10, wherein the high-pressure hydrogen production apparatus comprises a detector that detects a differential pressure based on the position of the external magnetic body that has changed due to expansion and contraction of a bellows. 17. The differential pressure detector comprises a light-shielding plate that moves in conjunction with an external magnetic body, a display plate having an opening that is shielded by the light-shielding plate, and the amount of light transmitted through the opening to an electric signal. 17. The high-pressure hydrogen production apparatus according to claim 16, which is composed of a photoelectric meter that operates. 18. The differential pressure detector has as a component a slider that slides on an electric resistor in conjunction with an external magnetic body.
The high-pressure hydrogen production device according to item 6. 19. The pressure regulator comprises a hollow cylinder made of a non-magnetic material, one end of which communicates with pure water in a hydrogen high pressure container and the other end of which communicates with pure water in an oxygen high pressure container. And a device main body consisting of an inner slider made of a magnetic material that slides in close contact with the inner surface of the hollow cylinder and an outer slider made of a magnetic material that slides in close contact with the outer surface of the hollow cylinder. The high-pressure hydrogen production apparatus according to claim 11 or 13, which comprises a position detector that detects the position of the external slider. 20. The hollow cylinder has springs at both ends, and the internal slider has a flow path at both ends for passing pure water when the internal slider slides to the ends. Item 20. The high-pressure hydrogen production device according to Item 19. 21. The hollow cylinder has springs at both ends, and a switch for opening and closing a shut-off valve provided in a pipe for circulating pure water, which operates when the internal slider slides to both ends, is provided at both ends. 20. The high-pressure hydrogen production apparatus according to claim 19, wherein the high-pressure hydrogen production apparatus has the above-mentioned. 22. The hollow cylinder has a substantial volume equal to or less than the smaller volume of the amount of hydrogen stored in the hydrogen high-pressure container and the amount of oxygen stored in the oxygen high-pressure container. 20. The high-pressure hydrogen production apparatus according to claim 19, which has a volume. 23. The high-pressure hydrogen production apparatus according to claim 10, further comprising a water level gauge including a center electrode and a cylindrical electrode centered on the center electrode. High-pressure hydrogen production equipment. 24. The water level gauge comprises a main electrode in which an external electrode is concentrically arranged outside a rod-shaped center electrode, and an external electrode in the outside of a rod-shaped center electrode covered with an electrically insulating cylinder except the tip. The high-pressure hydrogen production apparatus according to claim 23, further comprising sub-electrodes arranged on concentric circles. 25. The high-pressure hydrogen production apparatus according to claim 10, wherein the hydrogen high-pressure vessel has a normally open hydrogen emergency release valve, the pure water oxygen high-pressure vessel has a normally-open oxygen emergency release valve, and water electrolysis. A high-pressure hydrogen production system characterized in that the cell power supply is also equipped with an emergency power-off switch.