JP4659075B2 - Power generator - Google Patents

Description

The present invention, the hydrogen generated by the hydrolysis of magnesium hydride is supplied to the fuel cell, about the power generating equipment for generating power.

  Fuel cells are attracting attention as a means of solving environmental energy problems. Fuel cells use inexhaustible hydrogen as an energy source and do not release greenhouse gases, environmental pollutants, etc. generated by burning fossil fuels, so there are problems such as global warming, environmental pollution, and depletion of fossil fuels. It is expected as a means to solve.

  As a method for storing hydrogen, which is an energy source of a fuel cell, for example, a high-pressure cylinder system that stores hydrogen in a cylinder at a high pressure of 350 atm, a liquid hydrogen system that stores hydrogen by liquefying it at a cryogenic temperature of −253 ° C. or lower, Examples include a hydrogen storage alloy system that stores hydrogen in a hydrogen storage alloy. In particular, the storage alloy method does not need to store hydrogen in special conditions such as ultra-high pressure and cryogenic temperature, so it has excellent features such as easy handling, high safety, and high hydrogen storage per unit volume. is doing. An example of a power generation apparatus and a power generation method that employ an occlusion alloy system is disclosed in Patent Document 1. The power generation device according to Patent Document 1 includes a storage chamber in which a mixed powder of sodium borohydride and solid oxalic acid is stored, and hydrogen gas is injected by injecting water stored in a water storage container into the storage chamber. Is generated and supplied to the fuel cell. Further, the water generated on the air electrode side of the fuel cell by power generation is collected and recirculated to the water storage container.

On the other hand, a hybrid system for storing hydrogen in a cylinder filled with a hydrogen storage alloy has been developed. When storing 1.5 kg of hydrogen, it is necessary to store in a tank of about 60 L at a high pressure of 350 atm in the high pressure cylinder system, whereas in a hybrid system, it is stored in a tank of 40.8 L at a low pressure of 35 atm. It is possible.
JP 2006-298670 A

However, the storage alloy method has a problem that the hydrogen storage amount per unit weight is low as compared with the high pressure cylinder method and the liquid hydrogen method. This is because the hydrogen storage rate of a general hydrogen storage alloy is as low as several percent of the alloy mass. For example, when the hydrogen storage rate is 2 wt% of the alloy mass, 75 kg of hydrogen storage alloy is required to store 1.5 kg of hydrogen in the storage alloy system. In addition, when considering the water required to hydrolyze the hydrogen storage alloy and take out hydrogen, the hydrogen storage rate per unit weight of the hydrogen production material containing the hydrogen storage alloy and water is calculated. Become.
In addition, since it is the structure which circulates the water produced | generated with the fuel cell in the electric power generating apparatus which concerns on patent document 1, it seems that the hydrogen occlusion rate per unit weight of a hydrogen production material can be improved. However, since hydrogen is generated by reacting a mixed solid of sodium borohydride and oxalic acid with water, there is a possibility that impurities may be mixed into the water produced in the fuel cell in practice, and it is efficient. There is a problem that pure water cannot be recovered, and problems occur in the generation of hydrogen and power generation.

  On the other hand, even in the hybrid system, there is a problem that the hydrogen storage amount per unit weight is low as compared with the high pressure cylinder system and the liquid hydrogen system. When 1.5 kg of hydrogen is stored in the hybrid system, the total weight reaches 88.6 kg, and the hydrogen storage amount per unit weight is 1.6 wt%.

The present invention has been made in view of such circumstances, and by supplying water in a water storage container to magnesium hydride that can be hydrolyzed alone, high-purity hydrogen is generated, and water produced by a fuel cell is further generated. by refluxing the reservoir and aims to provide a power generating equipment capable of improving the hydrogen storage of hydrogen produced material per unit weight containing a hydrogen storage alloy and water 6.45～15.39Wt% And

  Another object of the present invention is to provide a hydrogen storage container that stores hydrogen generated by hydrolysis of magnesium hydride, and to supply the hydrogen stored in the hydrogen storage container to the fuel cell, thereby instantaneously. It is another object of the present invention to provide a power generator capable of supplying power to a fuel cell and starting power generation.

  Another object of the present invention is to provide water stored in a water storage container and a heat retaining means for keeping the reaction container at a temperature higher than the freezing point of water, and a heating means for heating magnesium hydride, regardless of the ambient temperature. An object of the present invention is to provide a power generation apparatus that can always have liquid water necessary for power generation, promote hydrolysis by rapid heating of magnesium hydride, and can immediately start power generation.

  Another object of the present invention is to provide water stored in a water storage container and a heat retaining means for keeping the reaction container at a temperature higher than the freezing point of water, and a heating means for heating magnesium hydride. Accordingly, by configuring the heating temperature of the magnesium hydride to rise and fall, liquid water necessary for power generation can be provided regardless of the ambient temperature, and by rapid heating of the magnesium hydride according to the required power An object of the present invention is to provide a power generation device that can accelerate hydrolysis and start power generation immediately.

  Another object of the present invention is to further improve the hydrogen storage rate per unit weight of the hydrogen production material containing hydrogen storage alloy and water by configuring the water condensed in the hydrogen storage container to circulate in the water storage container. An object of the present invention is to provide a power generator that can perform the above-described operation.

  Another object of the present invention is to provide a heat retention means and a secondary battery that supplies power to the heating means, and to charge the secondary battery with the power of the fuel cell, thereby separately providing an energy source for the heating means or the heat retention means. It is an object of the present invention to provide a power generator capable of heating and keeping heat of magnesium hydride and water inside the apparatus without preparation.

  Another object of the present invention is to provide a power generator capable of instantaneously outputting stable power prior to the start of the fuel cell by providing an output unit that outputs the power of each of the fuel cell and the secondary battery. There is to do.

  Another object of the present invention is to supply hydrogen to the fuel cell constantly or intermittently, so that hydrogen can be always stored in the hydrogen storage container and power can be stored in the secondary battery. It is in providing the electric power generating apparatus which can be prepared for an immediate start of.

  Another object of the present invention is to configure a water supply channel and a hydrogen supply pipe in two systems, respectively, a water supply valve that cuts off one system of the water supply channel, and a hydrogen supply valve that opens and closes one system of the hydrogen supply pipe By providing the above, it is an object of the present invention to provide a power generation device capable of immediately generating power by opening a water supply valve and a hydrogen supply valve as necessary to quickly start generation of hydrogen and supply of hydrogen.

  Another object of the present invention is to provide a heat storage container that contains a fuel cell, a water storage container, and a reaction container, so that the waste heat generated in the fuel cell and the reaction heat of hydrolysis are converted into a water storage container and a reaction container. Another object of the present invention is to provide a power generation device that can be reused for heat insulation and heating of a reaction vessel.

  Another object of the present invention is to use magnesium hydride having an average particle size of 45 μm to generate hydrogen by activating the reaction between magnesium hydride and water without using a catalyst, thereby effectively generating power. It is in providing the electric power generating apparatus which can do.

  Another object of the present invention is to provide a sound wave generating unit that applies sound waves to magnesium hydride, thereby effectively generating a hydrogen by activating the reaction between magnesium hydride and water without using a catalyst. An object of the present invention is to provide a power generator capable of generating electricity.

  Another object of the present invention is to generate a sound wave having a resonance frequency of magnesium hydride, thereby further activating the reaction between magnesium hydride and water without using a catalyst, thereby generating hydrogen. An object of the present invention is to provide a power generation device that can generate power and generate power effectively.

A power generation device according to the present invention is a power generation device that supplies hydrogen generated by hydrolysis of magnesium hydride to a fuel cell and generates power, and a water storage container for storing water necessary for hydrolysis of the magnesium hydride, The magnesium hydride is contained, a reaction container for generating hydrogen by reacting the water stored in the water storage container and the magnesium hydride, and the water stored in the water storage container into the reaction container. Charged with power supplied from the water supply path, heat stored in the water storage container and heat retaining means for maintaining the reaction container at a temperature higher than the freezing point of water, heating means for heating the magnesium hydride, and power of the fuel cell a secondary battery that supplies power to the thermal insulation means and said heating means, a heat switch which is provided between the secondary battery and the heating unit, the fuel cell and the secondary battery An output unit for outputting each electric power, a hydrogen storage container for storing hydrogen in the gas phase generated by hydrolysis of the magnesium hydride, and a hydrogen supply for supplying the hydrogen stored in the hydrogen storage container to the fuel cell A pipe, a circulation passage for collecting water generated in the fuel cell and circulating it to the water storage container, and when the pressure in the hydrogen storage container is lower than the first pressure in a standby state, the water supply path is opened, when in the standby state is the first pressure or more, closing the water supply passage, when there is a power supply request, a water supply valve to open the water supply passage is provided on the hydrogen supply pipe, said a standby state When the pressure in the hydrogen storage container is equal to or higher than the second pressure higher than the first pressure, the hydrogen supply pipe is opened, and when the pressure is lower than the second pressure in the standby state, the power supply is requested , to open the hydrogen supply pipe And a hydrogen supply valve, until the heating switch is opened in a standby state, when there is a power supply request, becomes closed, the secondary battery after power supply request, the power from the fuel cell starts to be output It is characterized in that power is output during the period .
A power generation device according to the present invention is a power generation device that supplies hydrogen generated by hydrolysis of magnesium hydride to a fuel cell and generates power, and a water storage container for storing water necessary for hydrolysis of the magnesium hydride, The magnesium hydride is contained, a reaction container for generating hydrogen by reacting the water stored in the water storage container and the magnesium hydride, and the water stored in the water storage container into the reaction container. First and second water supply pipes to be supplied, water stored in the water storage container and heat retaining means for maintaining the reaction container at a temperature higher than the freezing point of water, heating means for heating the magnesium hydride, and the fuel cell A secondary battery that is charged with the electric power of the battery and supplies power to the heat retaining means and the heating means, a heating switch provided between the secondary battery and the heating means, the fuel cell, and An output unit that outputs electric power of each of the secondary batteries, a hydrogen storage container that stores gaseous hydrogen generated by hydrolysis of the magnesium hydride, and hydrogen stored in the hydrogen storage container to the fuel cell First and second hydrogen supply pipes to be supplied, a circulation passage for recovering water generated in the fuel cell and circulating to the water storage container, and the first water supply pipe are provided in the hydrogen storage container. When the pressure is less than the first pressure, the first water supply pipe is opened, and when the pressure is equal to or higher than the first pressure, the first water supply valve for closing the first water supply pipe and the second water supply pipe are provided. And when the power supply is requested, the second water supply pipe is opened, and when power supply is completed, the second water supply valve for closing the second water supply pipe and the first hydrogen supply pipe are provided. The second pressure in the hydrogen storage container is higher than the first pressure. If the pressure is greater than or equal to the force, the first hydrogen supply pipe is opened, and if the pressure is lower than the second pressure, the first hydrogen supply valve is closed and the second hydrogen supply pipe is provided, and there is a power supply request. The second hydrogen supply pipe is opened, and when the power supply is completed, the second hydrogen supply valve is closed, and the heating switch is open in a standby state, and when the power supply is requested, the heat switch is closed. Thus, the secondary battery is configured to output electric power after a power supply request and before starting to output electric power from the fuel cell.

The power generation device according to the present invention is characterized by including a second annular flow path for circulating water condensed in the hydrogen storage container to the water storage container.

The power generation device according to the present invention includes a heat insulating container that houses the fuel cell, the water storage container, and the reaction container.

The power generator according to the present invention is characterized in that the magnesium hydride is granular having an average particle size of less than 45 μm.

The power generation device according to the present invention is characterized in that the magnesium hydride is obtained by mechanically pulverizing magnesium hydride coarse particles having an average particle diameter of 45 μm or more.

The power generation device according to the present invention includes a sound wave generator that applies sound waves to the magnesium hydride in the reaction vessel.

In the power generator according to the present invention, the frequency of the sound wave is a resonance frequency of the magnesium hydride.

In the power generator according to the present invention, the frequency of the sound wave is 28 kHz or 100 kHz, and the average particle size of the magnesium hydride is 1.87 μm.

In the present invention, water (H ₂ O) supplied from the water storage container to the reaction container reacts with magnesium hydride (MgH ₂ ) to generate hydrogen (H ₂ ). Hydrogen generated in the reaction vessel is supplied to the fuel cell through a hydrogen supply pipe. The fuel cell generates power by reacting hydrogen and oxygen supplied from a reaction vessel to generate water. The water produced by the fuel cell is collected and circulated to the water storage container through the circulation channel.
The hydrolysis reaction in the reaction vessel is represented by the following chemical formula (1), and the chemical reaction in the fuel cell is represented by the following chemical formula (2).
MgH ₂ + 2H ₂ O → Mg (OH) ₂ + 2H ₂ (1)
2H ₂ + O ₂ → 2H ₂ O (2)
As can be seen from the chemical formulas (1) and (2), all the water necessary for generating hydrogen can be covered with water generated by the fuel cell. Accordingly, the substantial hydrogen storage rate per unit weight of the hydrogen production material reaches 4/26 = 15.39 wt% because the atomic weights of magnesium (Mg) and hydrogen (H) are 24 and 1, respectively.
However, when a predetermined amount of water is required to start the water recirculation, the hydrogen occlusion rate per unit weight of the hydrogen production material is 4 / (26 + 36) = 6 even when the water is not recirculated at all. .45 wt% is reached.
Therefore, even when taking into account the water that initiates the reflux of water, the hydrogen storage rate per unit weight of the hydrogen product reaches 6.45 to 15.39 wt%.
In addition, since high-purity hydrogen generated by hydrolysis of magnesium hydride alone is supplied to the fuel cell, there is no risk of impurities being mixed into the water recovered from the fuel cell, and high-purity water is easily and efficiently added. Can be recovered and circulated.
The power generation device according to the first invention includes a stationary type and a mobile type, and also includes those mounted on a moving body. Examples of the stationary type include a household fuel cell system that is stationary outdoors, and a fuel cell system that is stationary in buildings such as hotels, hospitals, factories, and the like. Examples of the mobile type include a portable power source that can be used for leisure and outdoor concerts. Moreover, you may mount the electric power generating apparatus which concerns on 1st invention in moving bodies, such as a motor vehicle, a forklift truck, a cart, an airport work vehicle, a ship, a mobile telephone, a laptop computer.

Further , hydrogen generated by hydrolysis of magnesium hydride is stored in a hydrogen storage container, and hydrogen is supplied from the hydrogen storage container to the fuel cell as necessary. Therefore, hydrogen can be instantaneously supplied to the fuel cell, and power can be generated using the hydrogen stored in the hydrogen storage container until the hydrolysis of magnesium hydride is started.

Furthermore , since the heat retaining means keeps the water in the water storage container and the reaction container at a temperature higher than the freezing point of the water, liquid water necessary for hydrolysis of magnesium hydride can be always provided regardless of the ambient temperature. , Can be supplied instantaneously to the reaction vessel. In addition, the heating means can heat magnesium hydride, so that the hydrolysis of magnesium hydride can be promoted as needed, and hydrogen is generated more rapidly than when hydrolysis is performed at room temperature. Can be made. Therefore, it is possible to quickly supply hydrogen to the fuel cell and start power generation.
Since the freezing point varies depending on the atmospheric pressure, the heat retention temperature is set according to the environment in which the power generation device is used.
Furthermore, the secondary battery supplies power to the heat retaining means and the heating means, and the secondary battery is charged using the power of the fuel cell. Therefore, the energy required for heating and heat retention of magnesium hydride and water is provided inside the apparatus.
Furthermore, the output unit outputs the power of each of the fuel cell and the secondary battery. Although it takes time to start the fuel cell, the secondary battery can output power prior to starting the fuel cell. Accordingly, power output can be started instantaneously. In addition, when the output of the fuel cell decreases or becomes unstable, the secondary battery outputs power, so that the power output can be stabilized.
Furthermore, when hydrogen is supplied from the hydrogen storage container to the fuel cell and the pressure in the hydrogen storage container drops below the first pressure, the water supply valve is opened and the water in the storage container is supplied to the reaction container. When water is supplied to the reaction vessel, the magnesium hydride is hydrolyzed to generate hydrogen, and the hydrogen is stored in the hydrogen storage vessel. When the pressure in the hydrogen storage container rises above the second pressure, the hydrogen supply valve is opened, hydrogen is supplied from the hydrogen storage container to the fuel cell, and the fuel cell generates power. Moreover, when the secondary battery is provided, the electric power generated by the fuel cell is stored in the secondary battery.
Accordingly, hydrogen that is higher than the first pressure and lower than the second pressure is always stored in the hydrogen storage container. In addition, power is stored in the secondary battery. By storing hydrogen or electric power that can be supplied instantaneously, power generation can be started immediately.

In the present invention, water becomes steam during the hydrolysis reaction (exothermic reaction), and the water vapor accompanies hydrogen, and the water condensed in the hydrogen storage container is circulated to the water storage container through the second circulation channel. Therefore, water that may be discharged to the outside or stay in the hydrogen storage container can be recovered, and the hydrogen storage rate per unit weight of the hydrogen production material can be further improved.

In the present invention, regardless of the pressure in the hydrogen storage container, by opening the second water supply valve and the second hydrogen supply valve, hydrogen is supplied to the fuel cell, and water necessary for hydrolysis is supplied. The reaction vessel can be supplied. Therefore, by opening the second water supply valve and the hydrogen supply valve, generation and supply of hydrogen can be started instantaneously and the fuel cell can be started.

In the present invention, the heat insulating container accommodates the fuel cell, the water storage container, and the reaction container. Therefore, the waste heat generated in the fuel cell and the reaction heat of hydrolysis can be reused for heat retention and heating of the water storage container and the reaction container.

In the present invention, hydrogen is generated by reacting granular magnesium hydride having an average particle size of less than 45 μm with water. Therefore, the reaction between magnesium hydride and water is activated as compared with the conventional power generation apparatus using magnesium hydride having an average particle size of 45 μm or more. Magnesium hydride having an average particle size of less than 45 μm can be obtained by mechanically pulverizing magnesium hydride coarse particles having an average particle size of 45 μm or more produced by a predetermined method.

In the present invention, the sound wave generator applies sound waves to the magnesium hydride in the reaction vessel. The sound wave means a sound wave in a broad sense including an ultrasonic wave. When magnesium hydride and water react to generate hydrogen, gaseous hydrogen adheres to the magnesium hydride particles and inhibits the hydrolysis reaction. However, by oscillating magnesium hydride with sound waves, it is possible to quickly release hydrogen.
Therefore, the reaction between magnesium hydride and water is activated.

In the present invention, since the frequency of the sound wave generated by the sound wave generator is the resonance frequency of magnesium hydride, the magnesium hydride vibrates greatly compared to the non-resonant state, and the hydrogen gas is quickly released. Is possible.
Therefore, the reaction between magnesium hydride and water is activated more effectively.

According to the present invention, the hydrogen storage rate per unit weight of the hydrogen production material including the hydrogen storage alloy and water reaches 6.45 to 15.39, and the power generation device can be reduced in size and weight. For example, the volume of the hydrogen production material capable of supplying 1.5 kg of hydrogen can be reduced to 27.3 to 40.8 L, and the total weight can be reduced to 9.75 to 23.3 kg.

Also , compared with a case where hydrogen is supplied to the fuel cell after the start of the hydrolysis reaction, hydrogen can be instantaneously supplied to the fuel cell and power generation can be started.

Furthermore , liquid water necessary for power generation can be provided regardless of the ambient temperature, and hydrolysis can be promoted by rapid heating of magnesium hydride and power generation can be started immediately.
Furthermore, magnesium hydride and water can be heated and kept inside the apparatus without separately preparing an energy source for a heating means or a heat retaining means for quickly starting power generation.
Furthermore, when power supply is started, stable power can be instantaneously output from the secondary battery prior to the start of the fuel cell.
Furthermore, hydrogen can be always stored in the hydrogen storage container to prepare for the immediate start of power generation. Moreover, electric power can be stored in a secondary battery, and it can prepare for the immediate start of electric power generation.

ADVANTAGE OF THE INVENTION According to this invention, the hydrogen storage rate per unit weight of hydrogen production materials containing a hydrogen storage alloy and water can further be improved.

According to the present invention, regardless of the pressure in the hydrogen storage container, the second water supply valve and the hydrogen supply valve are opened to quickly start the generation of hydrogen and the supply of hydrogen, and to immediately generate power. it can.

According to the present invention, waste heat generated in a fuel cell and hydrolysis reaction heat can be reused for heat retention of the water storage container and the reaction container and heating of the reaction container, and energy can be used without waste. Can do.

According to the present invention, it is possible to generate electric power effectively by activating the reaction between magnesium hydride and water without using a catalyst to generate hydrogen.

According to the present invention, by applying sound waves to magnesium hydride, the reaction between magnesium hydride and water can be activated without using a catalyst to generate hydrogen, thereby effectively generating power.

According to the present invention, by resonating magnesium hydride with sound waves, without using a catalyst, the reaction between magnesium hydride and water can be further activated to generate hydrogen and effectively generate power. it can.

Hereinafter, the present invention will be described in detail with reference to the drawings illustrating embodiments thereof.
FIG. 1 is a block diagram schematically showing a power generator according to an embodiment of the present invention. In the figure, reference numeral 1 denotes a heat insulating container, and the container 1 houses a fuel cell 7 and a reaction vessel 4 and a water storage vessel 2 for generating hydrogen necessary for power generation.

The water storage container 2 is made of, for example, a cylindrical metal or resin and stores water necessary for generating hydrogen. The reaction vessel 4 is connected to the bottom of the water storage container 2 via first and second water supply pipes 31 and 32 (water supply passages), and the water stored in the water storage container 2 is the first and second water supply pipes 31. , 32 to be supplied to the reaction vessel 4. First water supply valves 31 a and 31 a are respectively provided on the water storage container 2 side and the reaction container 4 side of the first water supply pipe 31. The first water supply valves 31a and 31a are closed when the internal pressure on the reaction vessel 4 side rises to 2 atmospheres (first pressure) or more, and opened when the internal pressure on the reaction vessel 4 side drops to less than 2 atmospheres to open a fixed amount of water to the reaction vessel 4. To supply. The two first water supply valves 31a and 31a are provided for the reason that the back flow of hydrogen is prevented and the flow rate controllability of water is improved. The second water supply pipe 32 has a larger diameter than the first water supply pipe 31, and opens and closes the water supply container 2 side and the reaction container 4 side of the second water supply pipe 32 regardless of the internal pressure on the reaction container 4 side. 2nd water supply valves 32a and 32a which can perform are provided, respectively. The second water supply valves 32 a and 32 a are, for example, electromagnetic valves, and the opening and closing of the second water supply valves 32 a and 32 a is controlled by the control unit 14. The reason why two second water supply valves 32a and 32a are provided is the same as that of the first water supply valves 31a and 31a.
In addition, when the water pressure for supplying water to the reaction vessel 4 is insufficient, for example, a pressurizing unit such as a pressurizing pump may be provided at an appropriate place. Further, the value of the first pressure is an example, and the first water supply valves 31a and 31a may be opened and closed at other pressures as long as the pressure satisfies the legal regulations, for example, less than 10 atm. Of course, it may be configured to open and close at a pressure of 10 atm or higher as long as it can receive a security check and obtain approval.

The control unit 14 is a microcomputer including a CPU, a ROM, a RAM, an input / output port, and the like, and controls operations of the second water supply valves 32a and 32a and other various components. In addition, the control unit 14 acquires a power supply request input from an external device via the input unit 15, and performs processing related to power generation, which will be described later, according to the power supply request.
In addition, a hydrogen detector 18 and an alarm 19 are connected to the controller 14. The control unit 14 determines whether or not the hydrogen detection unit 18 has detected hydrogen. When the hydrogen detection unit 18 detects hydrogen, the control unit 14 forces the first water supply valves 31a and 31a and the second water supply valves 32a and 32a. And the alarm unit 19 outputs an alarm. Thus, by providing the hydrogen detection unit 18 and the alarm unit 19, hydrogen leakage can be minimized and the safety of the power generation device can be improved.
The first and second water supply pipes 31 and 32 may be separately provided with a water supply valve (not shown) for preventing hydrogen leakage, and when the hydrogen detection unit 18 detects hydrogen, the water supply valve is closed. good.

  The reaction vessel 4 accommodates magnesium hydride occluded with hydrogen in appropriate places. When the first water supply valve 31a, 31a or the second water supply valve 32a, 32a is opened and the water in the water storage container 2 is supplied to the reaction container 4, the supplied water reacts with the contained magnesium hydride. As a result, hydrogen is generated. The reaction between magnesium hydride and water is a hydrolysis reaction represented by the above chemical formula (1). The higher the temperature of magnesium hydride, the faster the reaction rate. For example, when the temperature of magnesium hydride is 15 ° C., the hydrolysis reaction proceeds gradually, and a trace amount of hydrogen is always generated. When the temperature of magnesium hydride is 110 ° C. or higher, the hydrolysis reaction is completed instantaneously, so that hydrogen corresponding to the amount of water supplied from the water storage container 2 is generated instantaneously.

A hydrogen storage container 5 is provided above the reaction container 4 so as to communicate with the reaction container 4, and a fuel cell 7 is connected to the hydrogen storage container 5 via first and second hydrogen supply pipes 61 and 62. ing. The hydrogen storage container 5 stores hydrogen generated in the reaction container 4 at 2 atm or more and less than 7 atm (second pressure), and stores the stored hydrogen through the first and second hydrogen supply pipes 61 and 62 as necessary. The fuel cell 7 is supplied. A filter 5b that removes impurities such as sulfur S, carbon monoxide CO, and methane gas CH ₄ is provided on the outlet side of the hydrogen storage container 5, and high-purity hydrogen from which impurities have been removed is supplied to the fuel cell 7. In addition, a pressure reducing valve (not shown) for reducing the pressure of hydrogen is interposed in the middle of the first and second hydrogen supply pipes 61 and 62 so that the fuel cell 7 is not damaged. The hydrogen storage container 5 has a hydrogen storage capacity capable of storing at least hydrogen necessary for starting power supply described later.
In addition, you may comprise so that the hydrogen storage alloy may be enclosed in the hydrogen storage container 5, and the hydrogen storage amount of the hydrogen storage container 5 may be improved. Further, the value of the second pressure is an example, and other pressures may be used as long as the pressure satisfies the legal regulations, for example, less than 10 atm. Of course, as long as the above approval can be obtained, the pressure may be 10 atmospheres or more.

A water recovery unit 81 that recovers water condensed in the hydrogen storage container 5 is provided at the bottom of the hydrogen storage container 5. The water recovery unit 81 is a recess formed at the bottom of the hydrogen storage container 5, for example, and the water recovery unit 81 and the water storage container 2 are connected by a reflux pipe 91, and the water recovered by the water recovery unit 81 is The recirculation pipe 91 is configured to recirculate to the water storage container 2. In the middle of the reflux pipe 91, a backflow prevention means, for example, a backflow prevention valve is provided for preventing the water from flowing back from the water storage container 2 to the hydrogen storage container 5. Since the hydrolysis reaction is an exothermic reaction, water becomes steam at the time of hydrolysis, and there is a possibility that the water vapor enters the hydrogen storage container 5 along with hydrogen, but enters the hydrogen storage container 5 and condenses. Water can be returned to the water storage container 2 through the water recovery part 81 and the reflux pipe 91.
The water recovered by the water recovery unit 81 may be returned to the reaction vessel 4. Further, the water recovered by the water recovery unit 81 may be selectively returned to either the reaction container 4 or the water storage container 2. For example, since water for hydrolysis is required during power generation, the water recovered by the water recovery unit 81 is returned to the reaction vessel 4, and when the power is not generated, the water recovered by the water recovery unit 81 is stored in the water storage container 2. What is necessary is just to comprise so that it may return.

  Furthermore, a pressure detection unit 5a for detecting the pressure in the hydrogen storage container 5 is disposed at an appropriate location of the hydrogen storage container 5, and the pressure detection unit 5a gives a signal indicating the detected pressure to the control unit 14. It is configured.

  First and second hydrogen supply valves 61a and 62a are provided on the hydrogen storage container 5 side of the first and second hydrogen supply pipes 61 and 62, respectively. The first hydrogen supply valve 61a is closed when the pressure in the hydrogen storage container 5 is less than 7 atm. The first hydrogen supply valve 61a is opened when the pressure in the hydrogen storage container 5 is 7 atm or more, and hydrogen is supplied to the fuel cell 7. Supply. The second hydrogen supply valve 62 a is an electromagnetic valve that can be opened and closed regardless of the pressure of the hydrogen storage container 5, and the opening and closing of the second hydrogen supply valve 62 a is controlled by the control unit 14.

  The fuel cell 7 is, for example, a solid polymer fuel cell (PEFC) operable at a low temperature. The fuel cell 7 has a plurality of electrical energy extractions based on hydrogen supplied from the hydrogen storage container 5 and oxygen in the air supplied from the air supply unit 16 disposed at an appropriate location of the container 1. It has a single cell. At both ends in the stacking direction of the single cells, there are provided a rectangular flat plate-shaped positive electrode current collector 7a and negative electrode current collector 7b that collect power generated by each single cell.

  FIG. 2 is a schematic exploded perspective view showing an example of a single cell. The single cell has a rectangular flat plate-shaped electrolyte 71, an air electrode 72a and a fuel electrode 72b that are pressure-bonded to both surfaces of the electrolyte 71, and an air electrode 72a and a fuel electrode 72b that are further sandwiched from the outside, and a separator 73 that partitions the single cells. And. In addition, the joined body of the electrolyte 71, the air electrode 72a, and the fuel electrode 72b is called a membrane / electrode assembly (MEA: Membrane Electrode Assembly).

  The electrolyte 71 is a fluorine-based ion exchange membrane such as perfluorocarbon sulfonic acid resin, and prevents oxygen and hydrogen in the air supplied to the air electrode 72a and the fuel electrode 72b, respectively, from reacting directly, and only ions. It has a function of transmitting.

  The fuel electrode 72b has a rectangular flat plate shape narrower than the electrolyte 71, and includes a catalyst layer that ionizes hydrogen supplied from the hydrogen storage container 5 at room temperature, a carbon sheet that supports the catalyst layer, and the like. Hydrogen ions ionized at the fuel electrode 72b move in the electrolyte 71 from the fuel electrode 72b side to the air electrode 72a side. On the other hand, electrons generated by ionization flow through an external load (not shown) from the fuel electrode 72b and move to the air electrode 72a to supply electric power.

  Like the fuel electrode 72b, the air electrode 72a has a catalyst layer, a carbon sheet, and the like for activating oxygen supplied from the air supply unit 16, and the oxygen supplied to the air electrode 72a is the air electrode. Ionized by the electrons moved to 72a, and the ionized oxygen ions react with the hydrogen ions that have moved through the electrolyte 71 and reached the air electrode 72a, thereby generating water.

FIG. 3 is a schematic front view of the separator 73 having a surface facing the air electrode 72a on the front side. The separator 73 is formed of a rectangular carbon plate having substantially the same vertical and horizontal dimensions as the electrolyte 71, and has a function of separating hydrogen and air between adjacent single cells and electrically connecting the single cells. An air inlet 73a through which air flows is formed at one apex portion of the separator 73, and an air exhaust port 73c through which air and water are discharged is formed at the other apex portion that forms a diagonal with the apex portion. . Similarly, a hydrogen inlet 73d through which hydrogen flows in and a gas outlet 73e through which the exhaust gas flowing through the fuel electrode 72b is discharged are formed at the remaining vertex portions.
On the air electrode 72a side of the separator 73, as shown by a broken line arrow in FIG. 3, a parallel groove 73b for discharging the water generated by power generation is formed while air flows through the entire surface of the air electrode 72a. ing. In addition, the parallel groove 73b is formed so that the longitudinal direction becomes a vertical direction so that water generated by power generation can be efficiently discharged. Similar to the air electrode 72a side, a parallel groove is formed on the fuel electrode 72b side of the separator 73 so that the hydrogen flowing in from the hydrogen inlet 73d flows through the entire surface of the fuel electrode 72b.

In the vicinity of the fuel cell 7, a water recovery unit 82 that recovers water generated by the fuel cell 7 is provided. The water recovery device 82 includes, for example, a recovery tray installed vertically below the fuel cell 7. The water recovery device 82 and the water storage container 2 are connected by a circulation pipe 92 (circulation flow path), and the water recovered by the water recovery device 82 is configured to circulate to the water storage container 2 through the circulation pipe 92. The water recovery unit 82 is connected to an exhaust unit 17 that exhausts exhaust gas that has passed through the air electrode 72a and the fuel electrode 72b from the exhaust unit 17 to the outside of the housing 1.
In order to improve the water recovery rate, the air exhausted from the air outlet 73c of the fuel cell 7 may be cooled to condense the water in the air. Further, a water cooling groove (not shown) may be provided in the single cell of the fuel cell 7 so that the water generated by the air electrode 72a is condensed and recovered. Furthermore, the fuel cell 7 may be configured to be water-cooled using water stored in the water storage container 2. Furthermore, water may be recovered from the gas flowing through not only the air electrode 72a but also the fuel electrode 72b side of the fuel cell 7.

  As shown in FIG. 1, the positive electrode current collector 7 a and the negative electrode current collector 7 b of the fuel cell 7 are connected to the positive electrode output unit 13 a and the negative electrode output unit 13 b (output unit) provided at appropriate positions of the container 1 through leads. Connected. The positive electrode current collector 7a and the negative electrode current collector 7b are connected to a positive electrode 12a and a negative electrode 12b of a secondary battery 12 such as a nickel metal hydride battery or a lithium ion battery, respectively. For this reason, the electric power of each of the secondary battery 12 and the fuel cell 7 can be output, and the electric power output of a fuel cell can be assisted. Further, the secondary battery 12 can be charged with the electric power of the fuel cell 7.

  Further, the positive electrode 12a and the negative electrode 12b of the secondary battery 12 have a heat retaining coil 10 for preventing the water in the water storage container 2 and the reaction container 4 from freezing, and heating for promoting the hydrolysis reaction of magnesium hydride. The coil 11 is connected. The white arrows in FIG. 1 indicate the flow of heat from the heat retaining coil 10 and the heating coil 11.

  The heat retaining coil 10 is disposed below the water storage container 2 and retains the water stored in the water storage container 2 at a temperature higher than the freezing point, for example, 15 ° C. or higher. The heat retaining coil 10 is provided with a temperature switch 10 a that cuts off the electric power from the heat retaining coil 10. The temperature switch 10a is, for example, a bimetal type, and is turned on when the ambient temperature becomes lower than a predetermined temperature, for example, 15 ° C., and turned off when the ambient temperature becomes higher than the predetermined temperature. In addition, you may comprise so that the control part 14 may control opening and closing of the temperature switch 10a.

The heating coil 11 is, for example, a high-frequency induction coil, and heats magnesium hydride to 60 to 110 ° C. or more, thereby promoting the hydrolysis of magnesium hydride and instantaneously generating and supplying hydrogen. The heating coil 11 is provided with heating switches 11 a and 11 a, and the opening and closing of the heating switches 11 a and 11 a is controlled by the control unit 14. The control unit 14 controls the opening and closing of the heating switches 11a and 11a so as to be in a closed state when electric power is required, and in an open state when electric power is unnecessary. Moreover, the control part 14 raises / lowers the heating temperature of magnesium hydride within the range of 60 to 110 degreeC or more based on the detection result of the pressure detection part 5a, when outputting electric power. Specifically, when the pressure inside the hydrogen storage container 5 is high, the heating temperature is lowered, and when the pressure inside the hydrogen storage container 5 is low, the heating temperature is raised. The heating temperature does not necessarily need to be accurately controlled. When the pressure in the hydrogen storage container 5 is simply high / low, the heating value is controlled so that the heating value of the heating coil 11 becomes large / small. Just do it.
Further, the magnesium hydride may be simply heated to 110 ° C. or higher without raising or lowering the heating temperature. When the temperature is 110 ° C. or higher, magnesium hydride and water supplied to the reaction vessel 4 react instantaneously, and a large amount of hydrogen corresponding to the amount of water supplied is generated. In addition, what is necessary is just to select heating temperature suitably in the range of 60-110 degreeC according to required electric power, ie, the required amount of hydrogen. In view of reaction rate and economy, 100 ° C. is preferable. Moreover, you may make it heat to 90 degreeC or 60 degreeC below 100 degreeC in order to suppress generation | occurrence | production of water vapor | steam.
Furthermore, when the control unit 14 outputs electric power, the opening of the second water supply valves 32a and 32a is adjusted based on the detection result of the pressure detection unit 5a to increase or decrease the water supply amount. good. For example, the heat generation amount of the heating coil 11 is increased, and the water supply amount is decreased when the pressure in the hydrogen storage container 5 is high, and the water supply amount is increased when the pressure in the hydrogen storage container 5 is low.

  Next, the operation of the power generation device will be described. The operating state of the power generator is roughly divided into three states. There are three states: a standby state in which power is not output, a power generation start state in which power output is started, and a power generation state in which power is output.

  FIG. 4 is an explanatory diagram conceptually showing the operation in the standby state. First, as shown in FIG. 4A, when the pressure in the hydrogen storage container 5 is less than 2 atmospheres, the first water supply valves 31a and 31a are opened, and the water stored in the water storage container 2 is converted into the reaction container 4 To be supplied. Note that the first and second hydrogen supply valves 61 a and 62 a are closed, and hydrogen is not supplied to the fuel cell 7.

  When water is supplied to the reaction vessel 4, the magnesium hydride accommodated in the reaction vessel 4 reacts with water to generate hydrogen as shown in FIG. 4B. In the standby state, since the water storage container 2 and the reaction container 4 are at room temperature of 15 degrees or more, the hydrolysis reaction of magnesium hydride proceeds gradually, and a small amount of hydrogen is constantly generated and stored in the hydrogen storage container 5. The

  When a certain amount of hydrogen is stored in the hydrogen storage container 5 as a result of the hydrolysis reaction, specifically, when the pressure in the hydrogen storage container 5 is 7 atm or more, it is shown in FIG. As described above, the first hydrogen supply valve 61 a is opened, and the hydrogen stored in the hydrogen storage container 5 is supplied to the fuel cell 7. The fuel cell 7 supplied with hydrogen starts power generation and charges the secondary battery 12 with the electric power of the fuel cell 7. Further, the water generated by the power generation of the fuel cell 7 circulates to the water storage container 2 through the water recovery device 82 and the circulation pipe 92. Since the amount of water required for hydrolysis of magnesium hydride and the amount of water recovered from the fuel cell 7 are substantially the same, as shown in FIGS. 4 (a) and 4 (c), in the water storage container 2 before and after power generation. The amount of water does not change.

When the pressure in the hydrogen storage container 5 becomes less than 2 atm again due to the supply of hydrogen, the state transitions to the state shown in FIG. 4A, and the operations in FIGS. 4A to 4C are repeated thereafter. In addition, you may comprise so that the operation | movement between FIG.4 (b) and (c) may be repeated.
By repeating the operations shown in FIGS. 4A to 4C, the water generated in the power generation method according to the present invention, that is, the fuel cell 7, is recovered, and the recovered water reacts with magnesium hydride alone to generate hydrogen. A power generation method of generating and supplying the generated hydrogen to the fuel cell 7 is performed.
In the standby state described above, the single magnesium hydride is hydrolyzed at room temperature, and the fuel cell 7 can be caused to generate electric power by constantly generating a small amount of hydrogen, and the secondary battery 12 can be charged with the electric power of the fuel cell 7. A certain amount of hydrogen can be stored in the hydrogen storage container 5. By storing hydrogen and electric power, it is possible to instantaneously output electric power according to a power supply request.

  FIG. 5 is a flowchart showing a processing procedure of the control unit 14 related to power generation. The control unit 14 constantly monitors the power supply request and determines whether or not the power supply request has been acquired via the input unit 15 (step S1). When it determines with not having acquired the electric power feeding request | requirement (step S1: NO), the control part 14 complete | finishes the process which concerns on electric power generation. When it determines with having acquired the electric power feeding request | requirement (step S1: YES), the control part 14 opens the 2nd hydrogen supply valve 62a (step S2). And the control part 14 closes heating switch 11a, 11a (step S3), open | releases 2nd water supply valve 32a, 32a (step S4), and complete | finishes the process which concerns on electric power generation.

FIG. 6 is an explanatory diagram conceptually showing the operation in the power generation start state. When the control unit 14 obtains a power supply request and executes the processes of steps S2 to S4, as shown in FIG. 6A, hydrogen is supplied from the hydrogen storage container 5 to the fuel cell 7 and magnesium hydride rapidly Heated, and further water is supplied to the reaction vessel 4. However, since it takes a certain period of time until the power starts to be output from the fuel cell 7 after obtaining the power supply request, as shown in FIG. 6, the secondary battery 12 supplementarily outputs the necessary power during that time. .
Further, since it takes more time to heat the magnesium hydride to 110 ° C. or higher to promote the hydrolysis reaction, the hydrogen stored in the hydrogen storage container 5 is supplied to the fuel cell 7 during that time. .

  Next, as shown in FIG. 6B, the fuel cell 7 starts power generation using the hydrogen stored in the hydrogen storage container 5. However, at the stage shown in FIG. 6B, the amount of hydrogen generated is insufficient, so the fuel cell 7 continues to generate power using the hydrogen stored in the hydrogen storage container 5. . Needless to say, at this stage, the pressure of the hydrogen storage container 5 need not be 7 atm.

  When magnesium hydride is heated to 110 ° C. or higher, as shown in FIG. 6C, hydrogen necessary for power generation can be supplied to the fuel cell 7 only by hydrolysis reaction, and stable power is continued from the fuel cell 7. Is output automatically. Thereafter, the fuel cell 7 is stabilized in the state shown in FIG. In addition, in the stable state shown in FIG.6 (c), the electric power generation method which concerns on this invention is implemented.

  When the above-described power supply is completed, the control unit 14 closes the second water supply valves 32a and 32a, opens the heating switches 11a and 11a, and closes the second hydrogen supply valve 62a.

  In the power generation device and the power generation method according to the present embodiment configured as described above, hydrogen is generated by hydrolysis of magnesium hydride, and water generated in the fuel cell 7 is returned to the water storage container 2 to be refluxed. Therefore, the hydrogen storage rate per unit weight of the hydrogen production material containing magnesium hydride and water reaches 6.45 to 15.39 wt%, and the power generation device can be reduced in size and weight.

In this case, the weight and volume of the hydrogen production material containing magnesium hydride and water necessary for 1 kW power generation are as follows.
For example, when the weight of magnesium hydride necessary for the fuel cell 7 to output 1 kW of electric power is 0.580 kg / kW, 0 to 0.804 kg / kW of water is required, and magnesium hydride and water The weight of the hydrogen production material containing 0.580 to 1.384 kg / kW.
The capacity of the water storage container 2 is 0.804 L / kW at the maximum, and assuming that the specific gravity of magnesium hydride is 0.300 to 0.357, the capacity of the reaction container 4 containing magnesium hydride is 1 .629 to 1.933 L / kW. Accordingly, the total volume of the water storage container 2 and the reaction container 4 necessary for power generation is 1.629 to 2.737 L / kW.

On the other hand, when evaluating the weight and capacity of the hydrogen production material when storing 1.5 kg of hydrogen, the total weight of the hydrogen production material is 9.75 to 23.3 kg, and the volume is 27.3 to 40.8 L. It can be seen that the device can be made smaller and lighter than conventional power generation devices.
The weight of magnesium hydride necessary to generate 1.5 kg of hydrogen is 1.5 × (26/4) = 9.75 kg, and the weight of water required to generate 1.5 kg of hydrogen. Is 9.75 × (36/26) = 13.5 kg when water is not circulated, and 0 kg when water is circulated 100%. Accordingly, the weight of the hydrogen production material containing magnesium hydride and water is 9.75 to 23.3 (≈9.75 + 13.5) kg.
Further, assuming that the specific gravity of magnesium hydride is 0.357, the volume of 9.75 kg of magnesium hydride is 27.3 (= 9.75 / 0.357) L and the specific gravity of water is 1, The volume of 0 to 13.5 kg of water is 0 to 13.5 L. Therefore, the volume of the hydrogen production material containing magnesium hydride and water is 27.3 to 40.8 L.

  Further, since the power generation device according to the present embodiment includes the hydrogen storage container 5, hydrogen is instantaneously supplied to the fuel cell 7 as compared with the case where hydrogen is supplied to the fuel cell 7 after the start of the hydrolysis reaction. Supply and start power generation.

  Furthermore, since the power generation device includes a heat retaining coil 10 that retains the temperature of the water storage container 2 and a heating coil 11 that rapidly heats the magnesium hydride to 110 ° C. or more when power feeding is started, the liquid generator necessary for power generation regardless of the ambient temperature. Water can be kept available, and hydrolysis can be accelerated instantaneously by rapid heating of magnesium hydride and power generation can be started.

  Furthermore, when the output power is large and the pressure in the hydrogen storage container 5 is lowered, the amount of hydrogen generation is increased by increasing the heating temperature of the magnesium hydride, the output power is small, and the pressure in the hydrogen storage container 5 is increased. When the temperature rises, the amount of hydrogen generation can be reduced by lowering the heating temperature of the magnesium hydride. Therefore, it is possible to adjust the hydrogen generation amount and output the necessary power.

  Furthermore, since the water condensed in the hydrogen storage container 5 is collected and recirculated to the water storage container 2 through the recirculation pipe 91, water that may be discharged to the outside or stay in the hydrogen storage container 5 is also included. It can collect | recover and the recovery rate of water can be improved. Therefore, the hydrogen storage rate per unit weight of the hydrogen production material containing magnesium hydride and water can be further improved.

  Furthermore, since the secondary battery 12 that supplies power to the heat retaining coil 10 and the heating coil 11 is provided and the secondary battery 12 is charged with the power of the fuel cell 7, an energy source for heat retaining and heating is separately provided. Insulation and heating can be performed inside the apparatus without preparation.

  Furthermore, by connecting the fuel cell 7 and the secondary battery 12 to the positive electrode output unit 13a and the negative electrode output unit 13b, respectively, when starting the supply of power, the secondary battery 12 Stable power can be output instantaneously.

  Furthermore, as shown in FIG. 4, the first hydrogen supply valves 31 a and 31 a and the first hydrogen supply valve 61 a are appropriately opened and closed according to the pressure in the hydrogen storage container 5, so that hydrogen is constantly supplied to the hydrogen storage container 5. The secondary battery 12 can store electric power, and can be prepared for immediate start of power generation.

  Furthermore, when the output of electric power is started, regardless of the pressure in the hydrogen storage container 5, the second water supply valves 32a, 32a and the second hydrogen supply valve 62a are opened to generate hydrogen and supply hydrogen. It can be started quickly and can generate electricity immediately.

  Furthermore, since the water storage container 2, the reaction container 4 and the fuel cell 7 are accommodated in the heat insulating container 1, the water storage container 2 and the reaction container 4 can be kept warm by the waste heat of the fuel cell 7, Energy can be used without waste.

  Furthermore, most of the hydrogen contained in the power generation device is stored in magnesium hydride, and when hydrogen leaks from the hydrogen storage container 5, fuel cell 7, etc., the supply of water is stopped and an alarm is issued. Therefore, high safety can be ensured.

(Modification 1)
The power generator according to Modification 1 contains magnesium hydride particles having an average particle size of less than 45 μm, particularly magnesium hydride particles having an average particle size of 1.87 μm. The average particle diameter of the magnesium hydride particles is a 50 wt% diameter obtained by measuring the particle size distribution of the magnesium hydride. The particle size distribution of magnesium hydride is measured by, for example, a wet method (medium: IPA) using a laser diffraction particle size distribution analyzer (product name: CILAS 1064, manufactured by CILAS). The 50 wt% diameter is a particle diameter having a 50% cumulative frequency. That is, the particle size is obtained when the magnesium hydride particles having a smaller particle size are accumulated in order and the accumulated value reaches 50%.

Next, a method for producing magnesium hydride particles having an average particle size of less than 45 μm will be described.
FIG. 7 is a schematic view showing a magnesium hydride particle production apparatus for producing magnesium hydride particles having an average particle size of less than 45 μm. The apparatus for producing magnesium hydride particles includes an inter-particle collision type jet pulverizer 101, for example (Aisin Nanotechnology, product name Nano Jet Mizer NJ-50 (manufactured by Zirconia)).

  The jet crusher 101 includes a cylindrical mill, and a plurality of crushing nozzles and one raw material supply port are equally arranged in the circumferential direction on the inner peripheral surface of the mill. The raw material supply port is provided with a feeder vibratory feeder 102 for supplying magnesium hydride coarse particles having an average particle size of 45 μm or more to the jet crusher 101. The pulverizing nozzle is provided with a compressor 103 for supplying compressed gas to the jet pulverizer 101 via an air filter 104. The maximum discharge pressure by the crushing nozzle is 1.57 MPa. Further, the mill is appropriately equipped with a collector 105 that collects magnesium hydride particles having an average particle diameter of 45 μm pulverized by the jet pulverizer 101. The collector 105 is, for example, a cylindrical filter cloth.

  The magnesium hydride coarse particles supplied from the raw material supply port to the inside of the mill are accelerated while swirling by the high-pressure jet stream injected from the pulverizing nozzle, and are pulverized by collision between particles. In addition, since the magnesium hydride coarse particles are configured to rotationally accelerate inside the cylindrical mill, there are few particle collisions with the inner peripheral wall of the mill, and there is little risk of contamination due to scraping of the mill wall surface.

FIG. 8 is a process diagram showing a method for producing magnesium hydride particles having an average particle size of less than 45 μm. First, magnesium hydride coarse particles having an average particle size of 45 μm or more are generated (step S101). Magnesium hydride coarse particles are obtained by reacting raw material particles containing magnesium as a main component with hydrogen gas (for example, Japanese Patent No. 4083786). The detailed reaction procedure is as follows.
First, the raw material particles containing magnesium as a main component are kept in a hydrogen gas atmosphere sealed in a sealed container, and the pressure of the hydrogen gas atmosphere in the sealed container is maintained at a predetermined pressure. The temperature of the hydrogen gas atmosphere in the enclosure is increased from room temperature, and the temperature of the hydrogen gas atmosphere in the enclosure corresponds to the predetermined pressure on the equilibrium curve between the reaction in which the magnesium and hydrogen molecules combine to produce magnesium hydride and the reverse reaction. The first temperature is maintained at a first temperature that is higher than the temperature at which the temperature difference from the temperature is 100 ° C. or less. Specifically, the pressure of hydrogen gas is 4 MPa, the first temperature is 550 ° C., and the first period is 1 hour. The coating on the surface of the raw material particles is removed by the above-described treatment.
Next, without returning the temperature of the hydrogen gas atmosphere in the enclosure to room temperature, the temperature is lower than the temperature corresponding to the predetermined pressure on the equilibrium curve, and the temperature difference from the temperature is within 100 ° C. The second period is maintained. Specifically, the second temperature is 400 ° C., and the second period is 20 hours. By this treatment, magnesium hydride can be produced from the raw material particles.

  When the process of step S101 is completed, the magnesium hydride coarse particles are supplied to the jet pulverizer 101 using the feeder vibration feeder 102 (step S102). Next, by supplying high-pressure gas to the jet pulverizer 101, the magnesium hydride coarse particles are pulverized into magnesium hydride particles having an average particle size of less than 45 μm (step S103), and the pulverized magnesium hydroxide particles are recovered. (Step S104), the manufacturing process is finished.

FIG. 9 is a chart showing conditions for pulverizing magnesium hydride and pulverization results. As shown in FIG. 9, the average particle diameter D50 value and the maximum particle diameter D100 value of the magnesium hydride coarse particles are 61.22 μm and 180.00 μm, respectively, and the indentation pressure is 1.5 MPa. As shown in the raw material “T-1”, when 20.0 g of magnesium hydride coarse particles were added and pulverization was performed at a treatment amount of 120 g / hr, the average particle size D50 value was 1.87 μm, and the maximum particle size D100. Magnesium hydride particles having a value of 10.00 μm could be recovered. The recovered amount is 16.23 g, and the recovery rate is 81.1%.
Further, as shown in the raw materials “T-2” and “T-3”, as a result of performing the same experiment with different treatment amounts and input amounts, hydrogen having an average particle diameter D50 value of 2.31 μm and 2.09 μm, respectively. Magnesium halide particles could be obtained. Note that the recovery rate shown for the raw material “T-2” exceeds 102.5% and 100% because the experiments for the raw materials “T-1” to “T-3” were continuously performed using the same filter. This is thought to be due to the implementation. That is, the magnesium hydride of the raw material “T-1” adhered to the filter of the collector 105 and could not be recovered sufficiently. A part of the raw material “T-1” was the raw material “T-2”. It is thought that it was recovered. The raw material “T-3” is judged to have a substantially normal recovery rate.

  In the power generation device according to the modified example 1, hydrolysis is performed using magnesium hydride particles having an average particle diameter of 1.87 μm, and therefore, compared with conventional magnesium hydride particles having an average particle diameter of 45 μm or more. The decomposition reaction can be activated, and hydrogen can be effectively generated and electric power can be generated without using a catalyst (see FIG. 13 described later).

  In the method for producing magnesium hydride particles according to Modification 1, in order to ensure safety, magnesium hydride coarse particles are generated using raw material particles having an average particle diameter of 45 μm or more, and then the magnesium hydride coarse particles are produced. Since the particles are pulverized by the jet pulverizer 101, magnesium hydride particles having an average particle diameter of less than 45 μm can be produced safely and easily.

(Modification 2)
FIG. 10 is a block diagram schematically illustrating a power generation device according to the second modification. The power generation device according to Modification 2 further includes an ultrasonic wave generation unit 211 that applies ultrasonic waves to the magnesium hydride in the reaction vessel 4.

  The ultrasonic generator 211 is provided at the bottom of the reaction vessel 4, for example, and is configured to be supplied with power from the fuel cell 7 or the secondary battery 12. The operation of the ultrasonic generator 211 is controlled by the controller 14 and can emit ultrasonic waves having a frequency of at least about 20 kHz to 100 kHz, particularly 28 kHz or 100 kHz. The frequency of 28 kHz or 100 kHz is estimated to be the resonance frequency of magnesium hydride having an average particle size of 1.87 μm.

  Further, as in Modification 1, the power generation device according to Modification 2 accommodates magnesium hydride particles having an average particle diameter of less than 45 μm, particularly magnesium hydride particles having an average particle diameter of 1.87 μm.

  FIG. 11 is a flowchart illustrating a processing procedure of the control unit 14 related to power generation according to the second modification. When acquiring the power supply request, the control unit 14 opens the second hydrogen supply valve 62a and the second water supply valves 32a and 32a, and thereafter periodically executes the following processing. The control part 14 detects the pressure in the hydrogen storage container 5 by the pressure detection part 5a (step S201). The pressure in the hydrogen storage container 5 varies depending on the relationship between the amount of hydrogen consumed by the fuel cell 7 and the amount of hydrogen generated. When the hydrogen generation amount is large compared to the hydrogen consumption amount, the pressure increases, and when the hydrogen generation amount is small compared to the hydrogen consumption amount, the pressure decreases.

  Next, the control unit 14 determines whether or not the detected pressure is a predetermined pressure, for example, less than 7 atm (step S202). The predetermined pressure is not limited to 7 atmospheres, and may be less than 10 atmospheres that satisfy the legal regulations. When it determines with the pressure detected by step S201 being less than predetermined pressure (step S202: YES), the control part 14 drives the ultrasonic generation part 211 (step S203), and complete | finishes a process. When it determines with the pressure detected by step S201 being more than predetermined pressure (step S202: NO), the control part 14 stops the ultrasonic generation part 211 (step S204), and complete | finishes a process.

  According to the above processing, when the internal pressure of the hydrogen storage container 5 becomes less than 7 atm, the ultrasonic generator 211 is driven and ultrasonic waves are given to the magnesium hydride particles. Magnesium hydride particles vibrate by ultrasonic waves, and the hydrogen gas adhering to the magnesium hydride particles is released early, so the hydrolysis reaction between the magnesium hydride particles and water is activated. The amount increases.

  Next, an experiment showing the relationship between the average particle diameter and ultrasonic wave of magnesium hydride particles and the hydrolysis rate will be described.

  FIG. 12 is a schematic diagram showing a hydrolysis experimental apparatus. In the figure, 204 is a hydrolysis reaction tube 204. The hydrolysis reaction tube 204 is charged with magnesium hydride particles in advance and sealed with a rubber stopper. The rubber stopper is provided with an argon gas supply pipe connected to the argon gas cylinder 202, a syringe 203 for supplying distilled water, and a discharge pipe for discharging hydrogen generated by the hydrolysis reaction. The argon gas cylinder 202 is provided to replace the inside of the hydrolysis reaction tube 204 with argon gas in advance. The discharge pipe reaches the water tank 207 via the ammonia recovery pipe 206 for recovering ammonia, and hydrogen discharged from the discharge pipe is collected in the hydrogen collection container 208 by water replacement. The lower part of the hydrolysis reaction tube 204 is immersed in an oil bath 205 a of the ultrasonic tank 205. The ultrasonic tank 205 is, for example, a table-type ultrasonic cleaner (Yamato Scientific Co., Ltd., product name JT-MT), which keeps the temperature of the hydrolysis reaction tube 204 at a constant temperature and gives ultrasonic waves. it can.

FIG. 13 is a chart showing the experimental results of hydrolysis. In the first experiment, as shown in FIG. 9, the temperature of the ultrasonic tank 205 is set to 20 ° C., the state in which no ultrasonic wave is applied, and the state in which ultrasonic waves having a frequency of 28 kHz, 45 kHz, and 100 kHz are applied are averaged. Experiments were conducted in which 0.1 g of magnesium hydride particles having a particle size (50 wt% size) of 61.2 μm were reacted with 2 ml of distilled water. And the hydrolysis rate was computed by measuring the quantity of the hydrogen collected by the hydrogen collection container 208 at the time of 60-minute progress. The hydrolysis rate is represented by the following formula.
Hydrolysis rate (%) = (amount of collected hydrogen) / (amount of hydrogen generated when magnesium hydride particles are 100% hydrolyzed) × 100
In addition, when 0.1 g of magnesium hydride particles are 100% hydrolyzed, 185.9 ml of hydrogen is generated at 1 atm. Therefore, in this experiment, the volume of collected hydrogen is divided by 185.9. The hydrolysis rate can be calculated. Further, 185.9 ml is a value calculated on the assumption that impurities are not contained in the magnesium hydride particles, but more precisely, the hydrolysis rate calculated by the above-described method is the purity (0 in this experiment). .94). However, since the purpose of this experiment is to make a relative evaluation of the hydrolysis rate, such correction is unnecessary.

In the second experiment, the average particle diameter (50 wt% diameter) was set in a state where the temperature of the ultrasonic bath 205 was set to 20 ° C. and no ultrasonic wave was applied, and ultrasonic waves with frequencies of 28 kHz, 45 kHz, and 100 kHz were applied. Experiments were performed in which 0.1 g of 1.87 μm magnesium hydride particles and 2 ml of an aqueous citric acid solution were reacted.
Furthermore, as a reference experiment, the temperature of the ultrasonic tank 205 is set to 20 ° C., no ultrasonic waves are applied, 0.1 g of magnesium hydride particles having an average particle diameter (50 wt% diameter) of 61.2 μm, and 2 ml of distilled water. An experiment was conducted to react with.

  From the first and second experiments, it can be seen that the hydrolysis rate is higher when the average particle size of the magnesium hydride particles is smaller. However, when the reaction temperature is 20 ° C., the hydrolysis rate is about 10% even when magnesium hydride particles having an average particle size of 1.87 μm are used in the state where no ultrasonic wave is applied. The hydrolysis rate does not reach 84% when using. However, when an ultrasonic wave having a frequency of 28 kHz or 100 kHz is applied, even if the reaction temperature is 20 ° C., the hydrolysis rate reaches 85% or 82%, and a reaction rate higher than that of citric acid can be realized.

  On the other hand, in the third and fourth experiments, the same experiment as described above was performed with the temperature of the ultrasonic bath 205 set to 70 ° C. It can be seen that even when the reaction temperature is 70 ° C., the hydrolysis rate is higher when the average particle size of the magnesium hydride particles is smaller. When magnesium hydride particles having an average particle size of 1.87 μm are used, the hydrolysis rate reaches about 60% (66%, 59%, 62%) without applying ultrasonic waves.

FIG. 14 is a graph showing the relationship between the average particle size of magnesium hydride particles and the hydrolysis rate. The horizontal axis indicates the temperature of the ultrasonic bath 205, and the vertical axis indicates the hydrolysis rate. The curve indicated by rhombus marks indicates the hydrolysis rate when magnesium hydride particles having an average particle diameter of 61.2 μm are hydrolyzed, and the curve indicated by square marks indicates magnesium hydride pulverized to an average particle diameter of less than 45 μm. The hydrolysis rate when the particles are hydrolyzed is shown.
As can be seen from FIG. 14, the effect of improving the hydrolysis rate due to the refinement of the magnesium hydride particles is effective in a low temperature region below 90 ° C., and no effect is observed in a high temperature region of 90 ° C. or higher. This is because the Brownian motion of water is small in the low temperature range, and the effect of improving the reaction area by miniaturization is significant. In the high temperature range, it is estimated that the Brownian effect contributes more than the effect of improving the reaction area by miniaturization.

  From the above experimental results, it is understood that magnesium hydride particles having an average particle diameter of 1.87 μm should be adopted. It can also be seen that, at the start of the hydrolysis reaction, it is possible to generate hydrogen effectively and generate electricity without using citric acid by giving a frequency of 28 kHz or 100 kHz. Furthermore, when the temperature in the reaction vessel 4 reaches about 70 to 75 ° C., it can be seen that it is possible to generate electricity to some extent without generating ultrasonic waves and generate power. Since the hydrolysis reaction is an exothermic reaction, the temperature of the reaction vessel 4 reaches about 70 to 75 ° C. without being heated by the heating coil 11. The heating coil 11 of Modification 2 is provided mainly to prevent the reaction vessel 4 from freezing. If there is no possibility of freezing, it is possible to reduce the cost by reducing the components of the power generation device by eliminating the heating coil 11.

  In the power generation device according to the modified example 2, by applying ultrasonic waves to the magnesium hydride particles, without using a catalyst, the reaction between the magnesium hydride particles and water is activated to generate hydrogen, It can generate electricity effectively.

  In addition, by resonating the magnesium hydride particles with sound waves, the reaction between the magnesium hydride particles and water can be further activated without using a catalyst to generate hydrogen, thereby effectively generating power.

  In the second modification, the case where the operation of the ultrasonic generator 211 is controlled by the pressure in the hydrogen storage container 5 has been described. However, the temperature in the reaction container 4 is detected, and the operation is performed based on the temperature. You may comprise so that operation | movement of the sound wave generation part 211 may be controlled. For example, when the temperature in the reaction container 4 is less than 75 ° C., the ultrasonic generator 211 is driven to apply ultrasonic waves, and when the temperature in the reaction container 4 is 75 ° C. or higher, the ultrasonic generator 211 May be configured to stop.

(Modification 3)
FIG. 15 is a block diagram schematically illustrating a power generation device according to the third modification. The power generation apparatus according to Modification 3 realizes smooth power generation while minimizing the input amount of citric acid.

The power generator according to Modification 3 further includes a citric acid charging unit 303 in the first water supply pipe 31. The citric acid charging unit 303 includes a citric acid storage unit that stores an aqueous citric acid solution having a concentration of about 20% or more, and a connection pipe that connects the input port provided in the first water supply pipe 31 and the citric acid storage unit. And an electromagnetic valve for controlling the addition of the citric acid aqueous solution, and configured to supply the citric acid aqueous solution to the reaction vessel 4 through the first water supply pipe 31 in accordance with the control of the control unit 14. The concentration of citric acid stored in the citric acid reservoir is 20% or more, and may be less than 20% as long as the hydrolysis of magnesium hydride can be activated.
In addition, the power generation device includes a temperature detection unit 304 a that detects the temperature in the reaction container 4.

  FIG. 16 is a flowchart illustrating a processing procedure of the control unit 14 related to power generation according to the third modification. When acquiring the power supply request, the control unit 14 opens the second hydrogen supply valve 62a and the second water supply valves 32a and 32a, and thereafter periodically executes the following processing. The control unit 14 detects the temperature of the reaction vessel 4 using the temperature detection unit 304a (step S301). And the control part 14 determines whether the temperature of the reaction container 4 is less than 75 degreeC (step S302). In addition, 75 degreeC is an example and should just select suitably according to required electric power generation amount.

  When it determines with the temperature of the reaction container 4 being less than 75 degreeC (step S302: YES), the control part 14 throws a citric acid solution into the reaction container 4 in the citric acid charging part 303 (step S303), and processing Finish. The amount of citric acid is preferably adjusted so that the citric acid concentration in the reaction vessel 4 is about 10%.

  When it determines with the temperature of the reaction container 4 being 75 degreeC or more (step S302: NO), the control part 14 stops injection | throwing-in of the citric acid solution by the citric acid input part 303 (step S304), and complete | finishes a process.

  FIG. 17 is a graph showing the relationship between temperature and hydrolysis rate. The horizontal axis represents temperature, and the vertical axis represents the hydrolysis rate of magnesium hydride having an average particle diameter of 61.2 μm. The hydrolysis rate can be measured by the above-described method using the hydrolysis experimental apparatus shown in FIG. As shown in FIG. 17, it can be seen that the reaction rate of magnesium hydride increases at about 75 ° C. or more.

  FIG. 18 is a graph showing the effect of citric acid on hydrolysis. The horizontal axis represents the time elapsed from the start of the hydrolysis reaction, and the vertical axis represents the hydrolysis rate. The hydrolysis rate can be measured by the same method as described above using the hydrolysis experimental apparatus shown in FIG. That is, the hydrolysis rate was measured by adding 2 ml or 4 ml of citric acid having a concentration of 10% instead of the distilled water charged in FIG. Magnesium hydride has an average particle size of 61.2 μm and a reaction temperature of 20 ° C. Stoichiometrically, about 4.8 ml of a 10% strength citric acid solution is required to hydrolyze magnesium hydride to 100%.

  It is presumed that there is no causal relationship between the citric acid concentration and the hydrolysis rate, and as can be seen from FIG. 18, the reaction amount can be adjusted by changing the input amount of the citric acid solution. .

  In the power generation device according to Modification 3, the citric acid solution is charged when the temperature in the reaction vessel 4 is less than 75 ° C., and the charging of the citric acid solution is stopped when the temperature exceeds 75 ° C. Therefore, it is possible to generate hydrogen smoothly and generate power while minimizing the input amount of citric acid.

Moreover, since citric acid also reacts with magnesium Mg which is not hydrogenated, it can generate hydrogen more effectively. The chemical reaction formula is
3Mg + 2C ₆ H ₁₂ O ₇ → (C ₆ H ₁₂ O ₇ ) ₂ Mg ₃ + 3H ₂
It is represented by

In the present embodiment, the water storage container and the fuel cell are connected by a recirculation pipe, but the recirculation flow path for recirculating water generated by the fuel cell is not limited to the pipe member. For example, a water storage container may be provided below the fuel cell so that water generated by the fuel cell is directly circulated to the water storage container.
Similarly, the water supply path for supplying water from the water storage container to the reaction container is not limited to a pipe member such as the first and second water supply pipes. For example, the water storage container and the reaction container may be disposed adjacent to each other so as to form a hole-like water supply channel in which the water storage container and the reaction container communicate with each other.

  Further, in the present embodiment, two systems of first and second water supply pipes and first and second hydrogen supply pipes are provided, but two systems of water supply pipes and hydrogen supply pipes branched in the middle You may comprise so that it may be provided. Moreover, the valve which can control the interruption | blocking and flow volume of water and hydrogen may be provided, and a power generator may be comprised by one water supply pipe | tube and a hydrogen supply pipe | tube.

  Further, in order to further improve the quality of hydrogen, a filter for removing impurities may be provided in the middle of the circulation path.

  Furthermore, although the solid polymer fuel cell is illustrated as the fuel cell, other fuel cells such as an alkaline type and a phosphoric acid type may be provided.

  Furthermore, the power generation device according to the present embodiment is not limited to a stationary type and a mobile type, and the power generation device may be mounted on a moving body such as an automobile, and its application is not limited.

Furthermore, although the power generation device according to the present embodiment includes a hydrogen storage container, a heat insulation coil, a heating coil, a secondary battery, and the like, these are not essential components and may be omitted as appropriate. For example, when there is no risk of freezing, it is not necessary to provide a heat retaining coil. In addition, when the hydrogen necessary for one power supply can be covered by the hydrogen in the hydrogen storage container, the heating coil is unnecessary, and the power required for heating can be reduced. Similarly, when the secondary battery can supply the power necessary for one power supply, the heating coil and the hydrogen storage container are unnecessary. Furthermore, when the heating rate of the heating coil and the power start rate of the fuel cell are sufficiently high, the hydrogen storage container is not necessary.
Further, if the water recovery device on the fuel cell side can sufficiently recover water, it is configured not to include a water recovery part in the hydrogen storage container and a return pipe connecting the water recovery part and the return pipe. You may do it.

Furthermore, although magnesium hydride has been described as a hydrogen storage alloy, it can be replaced with magnesium hydride, such as Mg, AL, NaAlH ₄ , Zn, and Ca, if it can be hydrolyzed at room temperature to generate high-purity hydrogen. Other hydrogen storage alloys may be used.

Furthermore, it should be thought that embodiment disclosed this time is an illustration and restrictive at no points. The scope of the present invention is defined by the terms of the claims, rather than the meanings described above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
(Appendix 1)
A power generation device that supplies hydrogen generated by hydrolysis of magnesium hydride to a fuel cell to generate electricity,
A water storage container for storing water necessary for hydrolysis of the magnesium hydride;
A reaction vessel for generating hydrogen by reacting the water stored in the water storage vessel and the magnesium hydride alone;
A hydrogen supply pipe for supplying hydrogen generated in the reaction vessel to the fuel cell;
An annular flow path for recovering water generated in the fuel cell and circulating it to the water storage container;
A power generation device comprising:
(Appendix 2)
A hydrogen storage container for storing hydrogen generated by hydrolysis of the magnesium hydride,
Hydrogen stored in the hydrogen storage container is supplied to the fuel cell.
The power generation device according to appendix 1, wherein:
(Appendix 3)
Heat retaining means for maintaining the water stored in the water storage container and the reaction container at a temperature higher than the freezing point of water;
Heating means for heating the magnesium hydride;
Detection means for detecting the pressure in the hydrogen storage container;
With
The heating means includes
The heating temperature is raised or lowered according to the pressure detected by the detection means.
The power generation device according to Supplementary Note 2, wherein
(Appendix 4)
A power generation method for generating power by supplying hydrogen generated by hydrolysis of magnesium hydride to a fuel cell,
Recovering water produced in the fuel cell;
Recovered water and magnesium hydride alone react to generate hydrogen,
Supply the generated hydrogen to the fuel cell
A power generation method characterized by the above.
(Appendix 5)
Magnesium hydride coarse particles are produced by reacting raw material particles containing magnesium and having an average particle size of 45 μm or more and hydrogen,
The produced magnesium hydride coarse particles are mechanically pulverized into magnesium hydride particles having an average particle size of less than 45 μm.
The manufacturing method of the magnesium hydride particle | grain characterized by the above-mentioned.
In Appendix 3, since the heat retaining means keeps the water in the water storage container and the reaction container at a temperature higher than the freezing point of the water, the liquid water necessary for the hydrolysis of magnesium hydride is supplied regardless of the ambient temperature. It can be always available and can be supplied to the reaction vessel instantaneously. In addition, the heating means can heat magnesium hydride, so that the hydrolysis of magnesium hydride can be promoted as needed, and hydrogen is generated more rapidly than when hydrolysis is performed at room temperature. Can be made. Therefore, it is possible to quickly supply hydrogen to the fuel cell and start power generation.
Also, when the output power is large and the pressure in the hydrogen storage container drops, the heating temperature of magnesium hydride is increased to increase the amount of hydrogen generated, and the output power is small and the pressure in the hydrogen storage container increases The amount of hydrogen generation can be reduced by lowering the heating temperature of magnesium hydride. Therefore, it is possible to output the necessary power by adjusting the hydrogen generation amount.
According to the invention of Supplementary Note 3, liquid water necessary for power generation can be prepared regardless of the ambient temperature, hydrolysis is accelerated by rapid heating of magnesium hydride according to the required power, and power generation can be performed immediately. Can start.
In Appendix 5, magnesium hydride coarse particles are produced by reacting raw material particles containing magnesium and having an average particle size of 45 μm or more and hydrogen gas. The main component of the raw material particles is magnesium, but magnesium is very reactive. For this reason, when the average particle diameter of magnesium hydride is less than 45 μm, it becomes difficult to handle it safely. Moreover, since magnesium has high ductility and malleability, it is difficult to grind itself to an average particle size of less than 45 μm. Accordingly, first, magnesium hydride coarse particles are generated using raw material particles having an average particle size of 45 μm or more.
Next, the produced magnesium hydride coarse particles are mechanically pulverized into magnesium hydride particles having an average particle size of less than 45 μm. Magnesium hydride is less reactive than magnesium, so it can be handled safely even if the average particle size is less than 45 μm. In addition, since ductility and malleability are low and brittle, magnesium hydride coarse particles can be mechanically pulverized to obtain magnesium hydride particles having an average particle size of less than 45 μm.
According to the invention of appendix 5, magnesium hydride particles having an average particle size of less than 45 μm can be produced safely.

It is a block diagram showing typically the power generator concerning an embodiment of the invention. It is a typical exploded perspective view showing an example of a single cell. It is a typical front view of the separator which made the surface which opposes an air electrode the front side. It is explanatory drawing which shows notionally the operation | movement of a standby state. It is a flowchart which shows the process sequence of the control part which concerns on electric power generation. It is explanatory drawing which shows notionally the operation | movement of a power generation start state. It is a schematic diagram which shows the magnesium hydride particle manufacturing apparatus which manufactures a magnesium hydride particle | grain with an average particle diameter of less than 45 micrometers. It is process drawing which shows the manufacturing method of a magnesium hydride particle | grain with an average particle diameter of less than 45 micrometers. It is a graph which shows the grinding | pulverization process conditions and grinding | pulverization result of magnesium hydride. It is a block diagram which shows typically the electric power generating apparatus in the modification 2. 10 is a flowchart illustrating a processing procedure of a control unit related to power generation according to Modification 2; It is a schematic diagram which shows a hydrolysis experiment apparatus. It is a graph which shows the experimental result of a hydrolysis. It is a graph which shows the relationship between the average particle diameter of magnesium hydride particle | grains, and a hydrolysis rate. It is a block diagram which shows typically the electric power generating apparatus in the modification 3. 10 is a flowchart illustrating a processing procedure of a control unit related to power generation according to Modification 3; It is a graph which shows the relationship between temperature and a hydrolysis rate. It is a graph which shows the effect which a citric acid has on hydrolysis.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Container 2 Water storage container 4 Reaction container 5 Hydrogen storage container 5a Pressure detection part (detection means)
7 Fuel cell 10 Thermal insulation coil (thermal insulation means)
11 Heating coil (heating means)
12 Secondary battery 13a Positive electrode output part (output part)
13b Negative electrode output part (output part)
DESCRIPTION OF SYMBOLS 14 Control part 18 Hydrogen detection part 19 Alarm part 31 1st water supply pipe 32 2nd water supply pipe 31a, 31a 1st water supply valve 32a, 32a 2nd water supply valve 61 1st hydrogen supply pipe 62 2nd hydrogen supply pipe 61a 1st hydrogen Supply valve 62a Second hydrogen supply valve 81 Water recovery unit 82 Water recovery device 91 Circulation tube (second circulation channel)
92 Circulation tube (circulation channel)
211 Ultrasonic generator

Claims (9)

A power generation device that supplies hydrogen generated by hydrolysis of magnesium hydride to a fuel cell to generate electricity,
A water storage container for storing water necessary for hydrolysis of the magnesium hydride;
Containing the magnesium hydride, and a reaction vessel for generating hydrogen by reacting the water stored in the water storage vessel and the magnesium hydride;
A water supply channel for supplying water stored in the water storage container to the reaction container;
Heat retaining means for maintaining the water stored in the water storage container and the reaction container at a temperature higher than the freezing point of water;
Heating means for heating the magnesium hydride;
A secondary battery that is charged with electric power of the fuel cell and supplies power to the heat retaining means and the heating means;
A heating switch provided between the secondary battery and the heating means;
An output unit for outputting electric power of each of the fuel cell and the secondary battery;
A hydrogen storage container for storing gaseous hydrogen generated by hydrolysis of the magnesium hydride;
A hydrogen supply pipe for supplying hydrogen stored in the hydrogen storage container to the fuel cell;
An annular flow path for recovering the water produced in the fuel cell and circulating it to the water storage container;
When the pressure in the hydrogen storage container is lower than the first pressure in the standby state, the water supply channel is opened. When the pressure is higher than the first pressure in the standby state, the water supply channel is closed and there is a power supply request. A water supply valve for opening the water supply channel ;
Is provided in the hydrogen supply pipe, when the pressure of the hydrogen storage container in a standby state is higher second pressure higher than the first pressure, opening the hydrogen supply pipe, said second pressure in a standby state And a hydrogen supply valve that closes and opens the hydrogen supply pipe when power supply is requested ,
The heating switch is in an open state in a standby state, and when a power supply request is made, the heating switch is in a closed state, and the secondary battery outputs power after the power supply request is made until power starts to be output from the fuel cell. A power generator characterized by being configured as described above . A power generation device that supplies hydrogen generated by hydrolysis of magnesium hydride to a fuel cell to generate electricity,
A water storage container for storing water necessary for hydrolysis of the magnesium hydride;
Containing the magnesium hydride, and a reaction vessel for generating hydrogen by reacting the water stored in the water storage vessel and the magnesium hydride;
First and second water supply pipes for supplying water stored in the water storage container to the reaction container;
Heat retaining means for maintaining the water stored in the water storage container and the reaction container at a temperature higher than the freezing point of water;
Heating means for heating the magnesium hydride;
A secondary battery that is charged with electric power of the fuel cell and supplies power to the heat retaining means and the heating means;
A heating switch provided between the secondary battery and the heating means;
An output unit for outputting electric power of each of the fuel cell and the secondary battery;
A hydrogen storage container for storing gaseous hydrogen generated by hydrolysis of the magnesium hydride;
First and second hydrogen supply pipes for supplying hydrogen stored in the hydrogen storage container to the fuel cell;
An annular flow path for recovering the water produced in the fuel cell and circulating it to the water storage container;
The first water supply pipe is provided in the first water supply pipe, and when the pressure in the hydrogen storage container is less than the first pressure, the first water supply pipe is opened, and when the pressure is equal to or higher than the first pressure, the first water supply pipe A first water supply valve for closing
A second water supply valve that is provided in the second water supply pipe, opens the second water supply pipe when there is a power supply request, and closes the second water supply pipe when power supply is completed;
Provided in the first hydrogen supply pipe, and when the pressure in the hydrogen storage container is equal to or higher than a second pressure higher than the first pressure, the first hydrogen supply pipe is opened and less than the second pressure. A first hydrogen supply valve that closes;
A second hydrogen supply valve that is provided in the second hydrogen supply pipe, opens the second hydrogen supply pipe when there is a power supply request, and closes when power supply is completed;
With
The heating switch is in an open state in a standby state, and when a power supply request is made, the heating switch is in a closed state, and the secondary battery outputs power after the power supply request is made until power starts to be output from the fuel cell. A power generator characterized by being configured as described above. The power generator according to claim 1 or 2 , further comprising a second annular flow path for circulating water condensed in the hydrogen storage container to the water storage container. The power generator according to any one of claims 1 to 3, further comprising a heat insulating container that houses the fuel cell, the water storage container, and the reaction container. The power generation apparatus according to any one of claims 1 to 4, wherein the magnesium hydride is in a granular form having an average particle size of less than 45 µm. The magnesium hydride is
The power generator according to claim 5, wherein the magnesium hydride coarse particles having an average particle diameter of 45 µm or more are mechanically pulverized. The power generation device according to any one of claims 1 to 6, further comprising a sound wave generation unit that applies sound waves to the magnesium hydride in the reaction vessel. The power generation device according to claim 7, wherein the frequency of the sound wave is a resonance frequency of the magnesium hydride. The frequency of the sound wave is 28 kHz or 100 kHz,
The power generator according to claim 7 or 8, wherein an average particle diameter of the magnesium hydride is 1.87 µm.

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