JP6954525B2 - Continuous hydrogen generator and hydrogen generation method - Google Patents

Description

The present invention relates to a continuous hydrogen generating apparatus and a hydrogen producing method.

Fuel cells that generate electricity using hydrogen as fuel are used in a wide range of technical fields. A hydrogen generator that generates hydrogen to be supplied to a fuel cell by hydrolyzing magnesium hydride particles has been proposed (Patent Document 1).

JP-A-2009-99534

However, the hydrogen generating apparatus described in Patent Document 1 has a problem that it is not suitable for continuous operation for a long time.

On one aspect, it is an object of the present invention to provide a hydrogen generator or the like capable of continuous operation for a long time.

The hydrogen generator includes a first pipe for supplying water to the inside of the reaction vessel , a suspension vessel for stirring the powder of the hydrogen generating material and water to make a suspension, and a suspension in the suspension vessel. The second pipe that supplies the inside of the reaction vessel, the water that is connected to the upper part of the reaction vessel and is supplied by the first pipe and stored in the reaction vessel, and the suspension supplied by the second pipe. a third pipe for discharging the hydrogen produced by the reaction between hydrogen generating material in Nigoeki, is connected to a lower portion of the reaction vessel, to flow out of the reaction product in producing the hydrogen to flow out from the third tube It is equipped with a drain pipe.

The hydrogen generator maintains the temperature of the suspension inside the suspension container in the range of 0 degrees Celsius or more and 20 degrees Celsius or less.

In the hydrogen generator, the second tube supplies the suspension from the upper part of the reaction vessel. The second tube may supply the suspension from any place such as the middle or lower part of the reaction vessel.

In the hydrogen generator, the second tube supplies the suspension through the first tube.

In the hydrogen generating apparatus, the first pipe injects water into the inside of the reaction vessel.

In the hydrogen generator, the first tube injects water along the inner wall of the reaction vessel.

In the hydrogen generating apparatus, the first pipe sprays water into the inside of the reaction vessel via a shower head provided inside the reaction vessel.

The hydrogen generating apparatus includes a baffle plate arranged between the connection portion between the reaction vessel and the third pipe and the water surface of the water stored in the reaction vessel.

In the hydrogen generator, the baffle plate is in the form of a net, a plate with a large number of through holes, or a non-perforated plate, and is arranged with a gap through which gas can pass between the baffle plate and the inner surface of the reaction vessel. Will be done.

The hydrogen generating apparatus has a baffle plate arranged between the connection portion between the reaction vessel and the third pipe and the shower head, or between the shower head and the water surface of the water stored in the reaction vessel. Be prepared.

The hydrogen generating apparatus includes a separation tank for separating the water discharged from the drain port provided at the lower part of the reaction vessel and the reaction product, and the first pipe supplies the water separated in the separation tank.

The hydrogen generating apparatus includes a fourth pipe that supplies the suspension with the water separated in the separation tank.

In the hydrogen generator, the hydrogen generating material is magnesium hydride.

The hydrogen generation device includes a fifth pipe into which water generated by a fuel cell consuming hydrogen flowing out from the third pipe flows in, and the water flowing in from the fifth pipe is supplied to the second pipe. ..

The hydrogen generating device includes a heater for heating the water stored in the reaction vessel and a first cooling device for cooling the water stored in the reaction vessel.

The hydrogen generator maintains the temperature of the water stored in the reaction vessel in the range of 95 degrees Celsius or more and 250 degrees Celsius or less.

In the hydrogen generator, the third pipe causes the water vapor in the reaction vessel to flow out together with hydrogen.
A cooling tank for cooling hydrogen and water vapor flowing out of the third pipe is provided.

The hydrogen generation device includes a hydrogen tank for storing hydrogen flowing out from the third pipe and a reservoir tank for storing hydrogen at a pressure higher than the internal pressure of the hydrogen tank.

In the hydrogen generation method, water is supplied to the inside of the reaction vessel, powder of the hydrogen generating material and water are supplied to the suspension vessel, and the inside of the suspension vessel is stirred to prepare a suspension, and the suspension is prepared. The suspension in the turbid container is supplied to the inside of the reaction vessel, and the hydrogen generated by the reaction between the water stored in the reaction vessel and the hydrogen generating material in the suspension is discharged.

In the hydrogen production method, a mixed solution of a reaction product and water produced by a chemical reaction in the reaction vessel is discharged from the lower part of the reaction vessel, the discharged reaction product and water are separated, and the separated water is discharged. It is supplied to the inside of the reaction vessel.

In the hydrogen production method, the temperature of water in the reaction vessel is maintained in the range of 95 degrees Celsius or more and 250 degrees Celsius or less.

In the hydrogen generation method, the water vapor in the reaction vessel is discharged together with the hydrogen, the water vapor is condensed, and the water generated by the condensation is supplied to the inside of the reaction vessel.

In the hydrogen generation method, water is supplied to the inside of the reaction vessel via a shower head arranged inside the reaction vessel.

In the hydrogen generation method, water is injected and supplied along the inner wall of the reaction vessel.

On one aspect, it is possible to provide a hydrogen generator or the like capable of continuous operation for a long time.

It is a schematic diagram of a hydrogen generator. It is a graph which shows the relationship between temperature and reaction rate. It is a block diagram of the control system of a hydrogen generator. It is a flowchart which shows the process flow of a program. It is a schematic diagram of the hydrogen generation apparatus of Embodiment 2. It is a schematic diagram of the hydrogen generation apparatus of Embodiment 3. It is a schematic cross-sectional view of the reaction vessel by VII-VII line in FIG. It is a schematic cross-sectional view of the reaction vessel of Embodiment 4. It is a schematic diagram of the hydrogen generation apparatus of Embodiment 5.

[Embodiment 1]
FIG. 1 is a schematic view of a hydrogen generator. The hydrogen generation device 10 includes a reaction vessel 21, a suspension vessel 81, a hydrogen generating material vessel 31, a water tank 61, a separation tank 63, a cooling tank 65, a hydrogen tank 71, and a reservoir tank 74. The outline of the hydrogen generation apparatus 10 of this embodiment will be described with reference to FIG.

The reaction vessel 21 is a hollow vessel having a circular cross section. The cross-sectional shape of the reaction vessel 21 may be a shape other than a circular shape. A heater 58 and a first cooling device 541 are attached to the outside of the reaction vessel 21. The heater 58 is a device for warming the reaction vessel 21. The first cooling device 541 is a device that cools the reaction vessel 21 by water cooling, air cooling, or the like.

The heater 58 may be mounted inside the reaction vessel 21. For example, by using a coil heater for the heater 58, the liquid stored inside the reaction vessel 21 can be directly warmed as described later.

The connecting portion provided near the center of the top surface of the reaction vessel 21 is connected to the cooling tank 65 via the third pipe 663. The cooling tank 65 is connected to the hydrogen tank 71 via an air supply pipe. Further, the cooling tank 65 is connected to the water tank 61 via a water pipe. The water tank 61 is connected to the reaction vessel 21 via a first pipe 661 having a first valve 561 in the middle.

The bottom of the reaction vessel 21 has a tapered portion whose diameter decreases downward. At the bottom of the tapered portion, a drain port 25 for discharging water containing reaction products produced by a chemical reaction described later, such as magnesium hydroxide and magnesium oxide, is provided. The drain port 25 is connected to the separation tank 63 via a drain pipe 666 provided with a drain valve 566 in the middle. A plurality of separation tanks 63 are connected in series via an overflow pipe 67 through which the supernatant liquid flows. The final separation tank 63 is connected to the water tank 61 via a return pipe provided with a pump 57 in the middle.

A hydrogen discharge pipe 75 is connected to the hydrogen tank 71. The reservoir tank 74 is connected to the hydrogen discharge pipe 75 via a supply pipe 668 having a reservoir valve 568 in the middle.

The water tank 61 is connected to the suspension container 81 via a fourth pipe 664 having a fourth valve 564 in the middle. The hydrogen generating material container 31 is also connected to the suspension container 81 via a supply pipe 667 having a supply valve 567 in the middle.

The suspension container 81 is placed on the stirrer 821. At the bottom of the suspension container 81 is a rotor 822 that is rotated by a magnetic field generated by the stirrer 821. The stirrer 821 and the rotor 822 are examples of a stirrer 82 that agitates the liquid in the suspension container 81.

The suspension vessel 81 is connected to the upper surface of the reaction vessel 21 via a second tube 662 having a second valve 562 in the middle.

The hydrogen generating material container 31 contains powder of a hydrogen generating material that reacts with water to generate hydrogen. The hydrogen generating material is, for example, magnesium hydride. When magnesium hydride is used as the hydrogen generating material, hydrogen is generated by the following reaction formula.

MgH ₂ + 2H ₂ O → Mg (OH) ₂ + 2H ₂ ‥‥‥ (1)
MgH ₂ + H ₂ O → MgO + 2H ₂ ‥‥‥ (2)

The formula (1) is a reaction formula when magnesium hydride reacts with warm water, and the formula (2) is a reaction formula when magnesium hydride reacts with high-temperature steam. Both are reactions of hydrolysis of magnesium hydride.

The hydrogen generating material may be magnesium powder, aluminum powder, iron powder, calcium powder or the like. When these hydrogen generating materials are used, hydrogen is generated by the following reaction formulas.

Mg + 2H ₂ O → Mg (OH) ₂ + H ₂ ‥‥‥ (3)
2Al + 6H ₂ O → 2Al (OH) ₃ + 3H ₂ ‥‥‥ (4)
Fe + 6H ₂ O → 2Al (OH) ₃ + 3H ₂ ‥‥‥ (5)
Ca + 2H ₂ O → Ca (OH) ₂ + H ₂ ‥‥‥ (6)

In the following description, a case where magnesium hydride is used as the hydrogen generating material and hydrogen is mainly generated by the reaction of the formula (1) will be described as an example. Depending on the reaction conditions such as temperature and pressure, the reaction of the formula (2) may occur in parallel with the reaction of the formula (1).

FIG. 2 is a graph showing the relationship between temperature and reaction rate. The horizontal axis is the temperature inside the reaction vessel 21, and the unit is degrees Celsius. The vertical axis is the reaction rate of magnesium hydride, and the unit is percentage. The reaction rate is a value indicating the proportion of hydrogenated magnesium that causes the chemical reaction of the formula (1) or the formula (2) among the hydrogenated magnesium charged into the reaction vessel 21 by mass ratio.

As shown in FIG. 2, when the temperature inside the reaction vessel 21 rises, the reaction rate rises sharply at around 65 degrees Celsius, gradually rises at around 95 degrees Celsius, and is about 85% at around 130 degrees Celsius. To reach. After that, the reaction rate gradually increases as the temperature in the reaction vessel rises, approaching 100%.

From the above, in the present embodiment, it is desirable that the temperature inside the reaction vessel 21 is 95 degrees Celsius or higher. It is more desirable that the temperature inside the reaction vessel 21 is about 130 degrees or higher. By setting the temperature inside the reaction vessel 21 to about 150 ° C., a reaction rate of about 95% can be achieved.

As shown in FIG. 2, when the temperature inside the reaction vessel 21 is made higher than 130 degrees Celsius, the amount of increase in the reaction rate is relatively small. Therefore, when the reaction vessel 21 is heated by using the heater 58, it is desirable that the temperature inside the reaction vessel 21 is about 130 degrees Celsius from the viewpoint of energy efficiency.

Similarly, as shown in FIG. 2, when the temperature inside the reaction vessel 21 is set to 150 degrees Celsius or higher, the amount of change in the reaction rate with respect to the amount of temperature fluctuation becomes small. Therefore, it is desirable that the temperature inside the reaction vessel 21 is 150 degrees Celsius or higher from the viewpoint of stabilizing the reaction rate at a high value.

On the other hand, when the temperature inside the reaction vessel 21 is high, the reaction vessel 21 and the piping and the like are likely to be deteriorated, and the life of the hydrogen generating apparatus 10 may be shortened. Therefore, it is desirable to maintain the temperature inside the reaction vessel 21 at 350 ° C. or lower. The temperature inside the reaction vessel 21 is more preferably 250 degrees Celsius or less, and even more preferably 200 degrees Celsius or less.

Magnesium hydride is a powder having an average particle size of 1 mm or less, preferably 100 micrometers or less. The average particle size of magnesium hydride may be, for example, 60 micrometers, 15 micrometers, 5 micrometers, or 1 micrometer or less. The average particle size and particle size distribution of magnesium hydride are appropriately selected according to the required reaction rate, cost, configuration of the hydrogen generating material container 31, and the like.

Returning to FIG. 1, an outline of the operation of the hydrogen generating apparatus 10 will be described. Water is stored up to a height of about half to two-thirds of the reaction vessel 21. Inside the reaction vessel 21, the temperature is adjusted and maintained at 95 degrees Celsius or more and 350 degrees Celsius or less, and the pressure is adjusted and maintained at 0.01 megapascals or more and less than 1 megapascals.

It is desirable that the temperature inside the reaction vessel 21 be adjusted and maintained at 95 degrees Celsius or more and 250 degrees Celsius or less and the pressure be 0.2 megapascals or more and less than 1 megapascal. It is more desirable that the temperature inside the reaction vessel 21 is adjusted and maintained from 95 degrees Celsius or more to 200 degrees Celsius or less and the pressure is adjusted to 0.2 megapascals or more and less than 1 megapascal.

Water and the hydrogen generating material are supplied into the suspension container 81 to a water level higher than the opening of the second pipe 662. In the present embodiment, the particle size of the hydrogen generating material is 60 micrometer, and the amount of the hydrogen generating material is about 5% to 20% of water in terms of mass ratio. It is more desirable that the amount of hydrogen generating material is about 10% to 15% by mass ratio of water.

By rotating the rotor 822 in the suspension container 81, the particles of the hydrogen generating material are dispersed in water to form a suspension. By maintaining the temperature of the suspension container 81 at 15 degrees Celsius or less, the generation of hydrogen in the suspension container 81 is prevented.

The suspension is charged into the water in the reaction vessel 21 via the second tube 662. Hydrogen and magnesium hydroxide are generated by the reaction formula of the formula (1). Hydrogen and magnesium oxide are generated by the reaction formula of the formula (2).

The generated hydrogen mixes with the steam generated by heating the water. Hydrogen and steam enter the cooling tank 65 through the third pipe 663. Water vapor condenses in the cooling tank 65 to become water. As a result, hydrogen and water vapor are separated into hydrogen and water. The separated water enters the water tank 61 through the water pipe.

The separated hydrogen enters the hydrogen tank 71 through the air supply pipe. Hydrogen is supplied from the hydrogen tank 71 to a supply destination such as a fuel cell via a hydrogen discharge pipe 75. The amount of hydrogen released through the hydrogen discharge pipe 75 is adjusted by a pressure regulating valve and a flow rate regulating valve (not shown).

Water containing magnesium hydroxide and magnesium oxide, which are reaction products, flows out from the drain port 25 provided at the lower part of the reaction vessel 21 and flows into the separation tank 63 through the drain pipe 666. Magnesium hydroxide and magnesium oxide precipitate in the separation tank 63. The supernatant water flows from the separation tank 63 through the overflow pipe 67 into the adjacent separation tank 63.

The water purified by passing through the plurality of separation tanks 63 is pressurized by the pump 57 and returns to the water tank 61 via the return pipe. Water is supplied from the water tank 61 to the inside of the reaction vessel 21 via the first pipe 661. Water is supplied from the water tank 61 to the inside of the suspension container 81 via the fourth pipe 664. The precipitate accumulated at the bottom of the separation tank 63 is appropriately taken out and used for the production of magnesium hydride.

If the water consumed by the chemical reaction when generating hydrogen and the water supplied to the first pipe 661 and the fourth pipe 664 are insufficient due to the time lag of the production process in the separation tank 63, etc., they are appropriately replenished from the outside. NS.

When the amount of hydrogen generating material in the hydrogen generating material container 31 is reduced, the hydrogen generating material is charged from the charging port or the like provided in the upper part of the hydrogen generating material container 31. After the hydrogen generating material container 31 is emptied, the supply valve 567 may be closed and the hydrogen generating material may be replaced with the filled hydrogen generating container 31.

The capacity of the hydrogen generating material container 31 will be described by taking the case of supplying hydrogen to a 1 kW fuel cell as an example. A 1 kW fuel cell consumes 10 liters of hydrogen per minute under standard conditions. When hydrogen is produced by the chemical reaction represented by the formula (1), 5.88 grams of magnesium hydride is used to produce 10 liters of hydrogen under standard conditions.

Therefore, when the hydrogen generating material container 31 is filled with 1 kg of magnesium hydride, the hydrogen generating device 10 can be used continuously for 2.8 hours. Similarly, when the hydrogen generating material container 31 is filled with 8.6 kg of magnesium hydride, the hydrogen generating apparatus 10 can be used continuously for 24 hours.

Even if air enters the hydrogen generating material container 31 or the supply pipe 667 when replenishing the hydrogen generating material, the supply pipe 667 and the second pipe 662 are separated by a suspension. , It is possible to prevent air from entering the second pipe 662.

The reservoir tank 74 will be described. The inside of the reservoir tank 74 is filled with hydrogen at a pressure higher than that of the inside of the hydrogen tank 71. The pressure of hydrogen filled in the reservoir tank 74 is, for example, a little less than 1 megapascal. When the fuel cell requires hydrogen but the amount of hydrogen produced in the reaction vessel 21 is insufficient, the reservoir valve 568 is opened to supply hydrogen from the reservoir tank 74 to the fuel cell. It is desirable that the reservoir valve 568 automatically closes when the hydrogen in the reservoir tank 74 decreases and the pressure decreases.

A compressor may be provided between the reservoir valve 568 and the reservoir tank 74. When a sufficient amount of hydrogen is generated in the reaction vessel 21, hydrogen supplied from the hydrogen tank 71 can be pressurized via the supply pipe 668 to supply hydrogen to the reservoir tank 74.

The reservoir tank 74 can accommodate as much hydrogen as possible by increasing the pressure inside. This makes it possible to stably supply hydrogen to the fuel cell and the like.

The parts exposed to hydrogen, such as the reaction vessel 21, the hydrogen generating material vessel 31, the suspension vessel 81, the cooling tank 65, the hydrogen tank 71, the reservoir tank 74, the third pipe 663, the supply pipe 668, and the pipes of each part, are made of steel. It is preferably made of steel or aluminum.

FIG. 3 is a block diagram of the control system of the hydrogen generation device 10. The control device 40 includes a CPU (Central Processing Unit) 41, a main storage device 42, an auxiliary storage device 43, an input unit 44, an output unit 45, a communication unit 46, an input I / F (Interface) 47, an output I / F 48, and a bus. To be equipped. As the control device 40 of the present embodiment, a device dedicated to the hydrogen generation device 10 may be used, or a general-purpose personal computer or the like may be used.

The CPU 41 is an arithmetic control device that executes a program according to the present embodiment. As the CPU 41, one or more CPUs, a multi-core CPU, or the like is used. The CPU 41 is connected to each part of the hardware constituting the control device 40 via a bus.

The main storage device 42 is a storage device such as a SRAM (Static Random Access Memory), a DRAM (Dynamic Random Access Memory), and a flash memory. The main storage device 42 temporarily stores information necessary in the middle of processing performed by the CPU 41 and a program being executed by the CPU 41.

The auxiliary storage device 43 is a storage device such as a SRAM, a flash memory, a hard disk, or a magnetic tape. The auxiliary storage device 43 stores a program to be executed by the CPU 41 and various information necessary for executing the program.

The input unit 44 is, for example, a keyboard, a touch panel, a mouse, or the like. The output unit 45 is, for example, a liquid crystal display device, an organic EL display device, or the like. The output unit 45 may further include a warning light, a speaker, or the like. The communication unit 46 is an interface for communicating with the network.

The input I / F 47 is an interface in which the CPU 41 acquires data from various sensors such as a pressure gauge 51, a thermometer 52, a flow meter 53, and a water level gauge attached to various parts of the hydrogen generator 10.

The output I / F 48 is an interface in which the CPU 41 sends a control signal to a valve 56, a pump 57, a heater 58, a cooling device 54, and the like attached to various parts of the hydrogen generating device 10. A drive circuit (not shown) is provided between the output I / F 48, the valve 56, the pump 57, the heater 58, and the cooling device 54.

Here, the valve 56 includes a first valve 561, a second valve 562, a fourth valve 564, a drain valve 566, a supply valve 567, and a reservoir valve 568. The cooling device 54 includes a first cooling device 541.

The flow of substances in the hydrogen generating apparatus 10 described above will be briefly summarized. Water returns from the water tank 61 to the water tank 61 via the first pipe 661, the reaction vessel 21, the drain pipe 666, the separation tank 63 and the return pipe, and from the water tank 61, the fourth pipe 664, the suspension container. It circulates through 81, the reaction vessel 21, the third pipe 663, the cooling tank 65, and the path returning to the water tank 61 via the water supply pipe.

When the water consumed by the chemical reaction when generating hydrogen and the water supplied to the shower head 23 are insufficient due to the time lag of the production process in the separation tank 63 or the like, the water is appropriately replenished from the outside and inside the reaction vessel 21. The water level is maintained within a predetermined range.

When the hydrogen generating apparatus 10 is continuously operated for a long time, the reaction product precipitated at the bottom of the separation tank 63 is appropriately taken out and replenished with water. The extracted reaction products, magnesium hydroxide and magnesium oxide, are used in the production of magnesium hydride.

The hydrogen gas generated in the reaction vessel 21 is supplied to a fuel cell or the like connected to the hydrogen discharge pipe 75 via the third pipe 663, the cooling tank 65, and the hydrogen tank 71.

The hydrogen generating material in the hydrogen generating material container 31 is consumed by the chemical reaction of the formula (1) or the formula (2). When the hydrogen generating apparatus 10 is continuously operated for a long time, a hydrogen generating material is appropriately replenished.

As described above, the hydrogen generating apparatus 10 of the present embodiment supplies the hydrogen generating material to the hydrogen generating material container 31, removes the reaction product precipitated in the separation tank 63, and replenishes water. , It is possible to continuously generate hydrogen for a long time.

FIG. 4 is a flowchart showing the processing flow of the program. The operation of the hydrogen generating apparatus 10 will be described with reference to FIG. At the start of the program shown in FIG. 4, each valve 56 is closed. Further, the space inside the hydrogen generation device 10 is filled with hydrogen or is in a vacuum state.

The CPU 41 transmits an open signal to the drive circuit of the first valve 561. The drive circuit of the first valve 561 opens the first valve 561 according to the received open signal. When the first valve 561 is opened, water is injected into the reaction vessel 21 (step S501).

In the following description, the description of the operation of the drive circuit of the first valve 561 is omitted, and the description is as follows: "The CPU 41 opens the first valve 561 to fill the inside of the reaction vessel 21 with water." .. The same applies to the drive circuit of each valve other than the first valve 561.

The CPU 41 determines that water has been stored up to a predetermined water level based on the output of a sensor such as a water level gauge attached to the reaction vessel 21 or a sensor such as a flow meter 53 attached to the second pipe 662. ..

The CPU 41 issues a start signal to the drive circuit of the heater 58. The drive circuit of the heater 58 activates the heater 58 according to the received activation signal. The heat generated by the heater 58 heats the water in the reaction vessel 21 (step S502).

In the following description, the description of the operation of the drive circuit of the heater 58 is omitted, and the description is as follows: "The CPU 41 activates the heater 58 to heat the water in the reaction vessel 21."

The CPU 41 opens the fourth valve 564 to fill the suspension container 81 with water, and opens the supply valve 567 to fill the suspension container 81 with the hydrogen generating material (step S503). The CPU 41 closes the fourth valve 564 after a predetermined amount of water has entered the suspension container 81. The CPU 41 closes the supply valve 567 after a predetermined amount of hydrogen generating material has entered the suspension container 81.

The CPU 41 activates the stirrer 82 to stir the inside of the suspension container 81 (step S504). Specifically, the CPU 41 activates the stirrer 821 to rotate the rotor 822 in the suspension container 81 to stir the inside of the suspension container 81. The hydrogen generating material is dispersed in the water in the suspension container 81 to form a suspension.

The CPU 41 determines that the temperature of the water stored in the reaction vessel 21 has reached a predetermined temperature based on the output of a sensor such as a thermometer 52 attached to the reaction vessel 21. The CPU 41 opens the second valve 562 and injects the suspension into the reaction vessel 21 (step S505).

The CPU 41 confirms that a predetermined amount of hydrogen is generated based on the data acquired from the pressure sensor or the like inside the reaction vessel 21 (step S506). The CPU 41 normally operates the hydrogen generator 10 based on the data acquired from each sensor (step S507). An example of processing executed by the CPU 41 during normal operation will be described.

The CPU 41 controls the output of the heater 58 and the first valve 561 to keep the reaction vessel 21 at a predetermined temperature. The chemical reaction between the hydrogen generating material and water is an exothermic reaction. When the amount of heat generated is sufficient, the CPU 41 stops the heater 58. When the calorific value is further large, the CPU 41 opens the first valve 561 to increase the amount of water in the reaction vessel 21.

When the chemical reaction is intense and the calorific value is very large, the CPU 41 operates the cooling device 54 to cool the reaction vessel 21 to a predetermined temperature. When the temperature of the reaction vessel 21 is sufficiently lowered due to the supply of water and the operation of the cooling device 54, the rate of the chemical reaction described using the formula (1) or the like is lowered, and the calorific value is reduced. ..

The CPU 41 controls the drain valve 566 to take out the water containing the reaction product into the separation tank 63 while maintaining the amount of water inside the reaction vessel 21 at a predetermined amount. The CPU 41 controls the fourth valve 564 and the supply valve 567 to keep the suspension in the suspension container 81 at a predetermined amount and concentration.

When the fuel cell or the like requests an increase in the amount of hydrogen supplied, the CPU 41 controls the second valve 562 to increase the amount of suspension to be injected into the reaction vessel 21. The CPU 41 may control the supply valve 567 to charge the hydrogen generating material into the suspension container 81 to increase the concentration of the suspension.

When the fuel cell or the like requests a reduction in the hydrogen supply amount, the CPU 41 controls the second valve 562 to reduce the amount of suspension injected into the reaction vessel 21. The CPU 41 may control the fourth valve 564 to fill the suspension container 81 with water to reduce the concentration of the suspension.

The CPU 41 determines whether or not an abnormality has occurred in the hydrogen generating device 10 based on the data acquired from each sensor (step S511). The determination criteria in step S511 are stored in advance in the main storage device 42 or the auxiliary storage device 43.

When it is determined that an abnormality has occurred (YES in step S511), the CPU 41 outputs a maintenance request to the output unit 45 (step S512). When the output unit 45 is a liquid crystal display device or an organic EL display device, a screen indicating that an abnormality has occurred in the hydrogen generation device 10 is displayed. When the output unit 45 is provided with a warning light, the warning light corresponding to the occurrence of an abnormality in the hydrogen generating device 10 is turned on.

The CPU 41 may transmit a notification to a management computer or the like via a communication unit 46 and a network (not shown). The management computer or the like that has received the notification outputs the content of the received notification in a manner that can be recognized by the user of the hydrogen generating apparatus 10.

The CPU 41 determines whether or not it is possible to continue the operation safely based on the data acquired from each sensor (step S513). When it is determined that continuation is possible (YES in step S513) and when it is determined that no abnormality has occurred (NO in step S511), the CPU 41 returns to step S507.

If it is determined that the continuation is not possible (NO in step S513), the CPU 41 stops the operation of the hydrogen generator 10 (step S514). Specifically, the CPU 41 can stop the chemical reaction inside the reaction vessel 21 by, for example, stopping the heater 58 and closing the second valve 562.

After the chemical reaction is stopped, the CPU 41 closes the first valve 561 and the drain valve 566 to stop the circulation of water. When the cooling device 54 is operating, the CPU 41 also stops the cooling device 54. By the above processing, the hydrogen generator 10 stops operating. After that, the CPU 41 ends the process.

Although the description is omitted in the flowchart, each component of the actively operating hydrogen generation device 10, such as the pump 57 and the cooling tank 65, is also controlled by the CPU 41 via the respective drive circuits.

According to this embodiment, it is possible to provide a hydrogen generating apparatus 10 capable of continuous operation for a long time. According to the present embodiment, since air is not mixed when the hydrogen generating material is put into the reaction vessel 21, it is possible to provide a hydrogen generating apparatus 10 for generating high-purity hydrogen. It is also possible to provide a hydrogen generating device 10 that prevents the occurrence of a hydrogen explosion due to the mixing of hydrogen and air.

According to the present embodiment, since water and a carrier gas are circulated and used, it is possible to provide a hydrogen generating device 10 that can be operated independently without being connected to an external water pipe or the like. According to this embodiment, it is possible to provide a hydrogen generator 10 capable of automatic operation.

According to the present embodiment, it is possible to provide the hydrogen generating device 10 capable of operating for a long time by appropriately replenishing the hydrogen generating material container 31 with the hydrogen generating material. According to the present embodiment, since the reaction product can be reprocessed and the hydrogen generating material container 31 can be reused, it is possible to provide a hydrogen generating apparatus 10 having a small environmental load.

According to the present embodiment, since the hydrogen generating material is put into the reaction vessel 21 in a suspension state, it rapidly diffuses into the reaction vessel 21 to generate hydrogen. Therefore, it is possible to provide the hydrogen generation device 10 in which the time from the input of the control signal to each valve or the like to the change in the amount of hydrogen generated is short and the required amount of hydrogen is stably generated.

[Embodiment 2]
The present embodiment relates to a hydrogen generation device 10 that reuses water generated at a hydrogen supply destination. The description of the parts common to the first embodiment will be omitted.

FIG. 5 is a schematic view of the hydrogen generating apparatus 10 of the second embodiment. The hydrogen tank 71 is connected to the fuel cell 80 via a hydrogen discharge pipe 75. The fuel cell 80 is connected to the water tank 61 via a fifth pipe 665 and a pump (not shown).

Inside the fuel cell 80, hydrogen is used as fuel to generate electricity by the chemical reaction described below, and water is generated at the positive electrode.

The negative ^{_{side: 2H 2 → 4H + + 4e}} - ‥‥‥ (8)
Positive ^{_{side: O 2 + 4H + + 4e}} - → 2H 2 O ‥‥‥ (9)
e ^- indicates an electron.

The water generated at the positive electrode flows into the water tank 61 via the fifth pipe 665.

According to the present embodiment, it is possible to provide the hydrogen generator 10 used for hydrolyzing the hydrogen generating material described by using the formula (1) or the like by recovering the water generated by the fuel cell 80. be. Therefore, the amount of water replenished from the outside can be saved, and the hydrogen generation device 10 having a low environmental load can be provided.

[Embodiment 3]
The present embodiment relates to a hydrogen generator 10 that injects a suspension along the inner wall of the reaction vessel 21. The description of the parts common to the first embodiment will be omitted.

FIG. 6 is a schematic view of the hydrogen generating apparatus 10 of the third embodiment. The suspension container 81 is connected to the hydrogen generating material container 31 via a supply pipe 667 having a supply valve 567 in the middle. The suspension container 81 is connected to the water tank 61 via a fourth pipe 664 having a fourth valve 564 in the middle.

The suspension container 81 is placed on the stirrer 821. At the bottom of the suspension container 81 is a rotor 822 that is rotated by a magnetic field generated by the stirrer 821. The stirrer 821 and the rotor 822 are examples of a stirrer 82 that agitates the liquid in the suspension container 81.

A motor 823 is fixed to the upper part of the suspension container 81. The rotary shaft 824 fixed to the motor 823 projects into the suspension container 81, and the impeller 825 is fixed to the tip thereof. As the motor 823 rotates, the impeller 825 rotates and agitates the inside of the suspension container 81. The motor 823, the rotary shaft 824, and the impeller 825 are examples of the stirrer 82 that agitates the liquid in the suspension container 81.

The water tank 61 is connected to the reaction vessel 21 via a first pipe 661 provided with a jet pump 36 on the way. The suspension vessel 81 is connected to the first pipe 661 between the jet pump 36 and the reaction vessel 21 via a second pipe 662 having a second valve 562 in the middle.

The jet pump 36 intermittently sends high-pressure water to the reaction vessel 21 via the first pipe 661. When the second valve 562 is open, the suspension is pumped into the reaction vessel 21 along with the high pressure water from the jet pump 36.

FIG. 7 is a schematic cross-sectional view of the reaction vessel 21 by the line VII-VII in FIG. The first pipe 661 is connected to the injection port 24 provided along the tangential direction of the inner wall of the reaction vessel 21. As shown by arrows in FIGS. 6 and 7, the suspension is injected from the injection port 24 diagonally downward along the inner wall of the reaction vessel 21 together with high-pressure water.

The suspension reacts with water while flowing diagonally downward along the inner wall of the reaction vessel 21. The flow of high-pressure water and suspension agitates the water in the reaction vessel 21, so that the hydrogen generating material diffuses evenly into the water. The reaction vessel 21 may be provided with a plurality of injection ports 24.

According to this embodiment, it is possible to provide a hydrogen generation device 10 for preventing reaction unevenness in the reaction vessel 21. Since the second pipe 662 becomes negative pressure due to the water flow flowing through the first pipe 661, it is possible to provide the hydrogen generating device 10 for preventing the suspension from being clogged in the second pipe 662.

As in the first embodiment described with reference to FIG. 1, the second pipe 662 may be directly connected to the reaction vessel 21 and water containing no suspension may be injected from the injection port 24. It is possible to provide a hydrogen generating device 10 for preventing wear of the inner wall of the first pipe 661 due to the suspension.

[Embodiment 4]
The present embodiment relates to a hydrogen generator 10 that injects a suspension into the reaction vessel 21. The description of the parts common to the third embodiment will be omitted.

FIG. 8 is a schematic cross-sectional view of the reaction vessel 21 of the fourth embodiment. The first pipe 661 is connected to the injection port 24 provided on the side wall of the reaction vessel 21. As shown by an arrow in FIG. 8, the suspension is injected together with high-pressure water from the injection port 24 toward the inside of the reaction vessel 21.

The suspension reacts with water as it flows toward the center of the reaction vessel 21. The flow of high-pressure water and suspension agitates the water in the reaction vessel 21, so that the hydrogen generating material diffuses evenly into the water. The injection direction of the suspension may be directed to the central axis of the reaction vessel 21 or may be directed between the central axis and the side wall. The injection direction of the suspension may be diagonally downward or diagonally upward. The reaction vessel 21 may include a plurality of injection ports 24.

According to this embodiment, it is possible to provide a hydrogen generation device 10 for preventing reaction unevenness in the reaction vessel 21. Further, according to the present embodiment, it is possible to provide a hydrogen generation device 10 that prevents wear of the inner wall of the reaction vessel 21 due to the suspension.

[Embodiment 5]
The present embodiment relates to a hydrogen generating apparatus 10 for spraying a suspension into a reaction vessel 21 by a shower. The description of the parts common to the first embodiment will be omitted.

FIG. 9 is a schematic view of the hydrogen generating apparatus 10 of the fifth embodiment. Inside the reaction vessel 21, a baffle plate 22 is fixed to the upper part. That is, the baffle plate 22 is arranged between the connection portion between the reaction vessel 21 and the third pipe 663 and the water surface in the reaction vessel 21.

The baffle plate 22 is a non-perforated disk having a diameter slightly smaller than the inner diameter of the reaction vessel 21. A gap 26 through which gas can pass is provided between the edge of the baffle plate 22 and the inner surface of the reaction vessel 21. The baffle plate 22 may be in the form of a net or a punching board having a large number of holes. The baffle plate 22 may be a plate having one or a plurality of holes.

A shower head 23 is provided under the baffle plate 22. The shower head 23 may have two or more stages. The shower head 23 is connected to the water tank 61 via a first valve 561 and a first pipe 661 including a pressurizing pump (not shown) on the way. The suspension vessel 81 is connected to the first pipe 661 between the jet pump 36 and the reaction vessel 21 via a second pipe 662 having a second valve 562 in the middle.

The suspension diluted with water is supplied to the shower head 23 via the first tube 661. A suspension or water diluted substantially uniformly is sprayed from the shower head 23 toward the water surface in the reaction vessel 21.

Even when bubbles are generated by the reaction formula of the formula (1) or the formula (2), the swelling of the bubbles is suppressed by the suspension or water sprayed from the shower head 23. Even when the amount of bubbles generated is large and the bubbles rise to the upper part of the reaction vessel 21, the bubbles do not enter the inside of the third pipe 663 due to the action of the baffle plate 22.

The shapes and arrangements of the baffle plate 22 and the shower head 23 are appropriately selected so as to effectively suppress the swelling of bubbles. For example, the baffle plate 22 may be arranged between the upper shower head 23 and the lower shower head 23. The baffle plate 22 may be arranged below the lower shower head 23, that is, between the shower head 23 and the water surface in the reaction vessel 21. In these cases, the baffle plate 22 is arranged in a shape and position that does not interfere with the water discharge of the shower head 23.

By opening and closing the first valve 561 and the second valve 562, water and the suspension may be alternately sprayed from the shower 23.

A second cooling device 542 is attached to the outside of the suspension container 81. The second cooling device 542 is a device that cools the suspension container 81 by water cooling, air cooling, or the like. When the temperature of the suspension container 81 is higher than a predetermined temperature, the second cooling device 542 operates to cool the suspension container 81.

The predetermined temperature is, for example, a temperature in a range in which the temperature of the suspension in the suspension container 81 is 0 degrees Celsius or more and 20 degrees Celsius or less. It is even more desirable that the temperature of the suspension be in the range of 0 degrees Celsius or more and 15 degrees Celsius or less.

When the hydrogen generating apparatus 10 is installed in a low temperature place, the temperature of the suspension in the suspension container 81 is set to 0 ° C. or lower by arranging the suspension container 81 near the reaction container 21 or the like. It can be prevented from freezing.

By maintaining the temperature of the suspension container 81 within a predetermined range, the chemistry of the formula (1) or (2) inside the suspension container 81 is prevented while preventing the water in the suspension from freezing. The reaction can be suppressed.

According to this embodiment, it is possible to provide a hydrogen generating device 10 capable of preventing clogging of the third pipe 663 by bubbles even when bubbles are generated by a chemical reaction in the reaction vessel 21.

According to this embodiment, it is possible to provide a hydrogen generating device 10 capable of preventing the generation of hydrogen in the suspension container 81.

The technical features (constituent requirements) described in each embodiment can be combined with each other, and by combining them, a new technical feature can be formed.
The embodiments disclosed this time should be considered as exemplary in all respects and not restrictive. The scope of the present invention is indicated by the scope of claims, not the above-mentioned meaning, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims.

10 Hydrogen generator 21 Reaction vessel 22 Obstacle plate 23 Shower head 24 Injection port 25 Drainage port 26 Gap 31 Hydrogen generator container 36 Jet pump 40 Control device 41 CPU
42 Main memory 43 Auxiliary storage 44 Input unit 45 Output unit 46 Communication unit 47 Input I / F
48 Output I / F
51 Pressure gauge 52 Thermometer 53 Flow meter 54 Cooling device 56 Valve 561 1st valve 562 2nd valve 564 4th valve 566 Drainage valve 567 Supply valve 568 Reservoir valve 57 Pump 58 Heater 61 Water tank 63 Separation tank 65 Cooling tank 661 1 pipe 662 2nd pipe 663 3rd pipe 664 4th pipe 665 5th pipe 666 Drain pipe 667 Supply pipe 668 Supply pipe 67 Overflow pipe 71 Hydrogen tank 74 Reservoir tank 75 Hydrogen discharge pipe 80 Fuel cell 81 Suspension vessel 82 Stirrer 821 Stirrer 822 Rotor 823 Motor 824 Rotating shaft 825 Impeller

Claims (24)

The first tube that supplies water to the inside of the reaction vessel,
A suspension container that stirs hydrogen generating material powder and water to make a suspension,
A second tube for supplying the suspension in the suspension vessel to the inside of the reaction vessel,
Hydrogen generated by the reaction between the water connected to the upper part of the reaction vessel, supplied by the first pipe and stored in the reaction vessel, and the hydrogen generating material in the suspension supplied by the second pipe. a third pipe to efflux,
A hydrogen generating device connected to the lower part of the reaction vessel and provided with a drainage pipe for discharging a reaction product when generating hydrogen to be discharged from the third pipe. The suspension container maintains the temperature of the suspension inside in the range of 0 degrees Celsius or more and 20 degrees Celsius or less.
The hydrogen generating apparatus according to claim 1. The hydrogen generating apparatus according to claim 1 or 2, wherein the second tube supplies the suspension from the upper part of the reaction vessel. The hydrogen generating apparatus according to claim 1 or 2, wherein the second tube supplies the suspension through the first tube. The hydrogen generating apparatus according to any one of claims 1 to 4 , wherein the first pipe is a water jet into the inside of the reaction vessel. The first tube injects water along the inner wall of the reaction vessel.
The hydrogen generating apparatus according to claim 5. The hydrogen generating apparatus according to any one of claims 1 to 4 , wherein the first pipe sprays water into the inside of the reaction vessel via a shower head provided inside the reaction vessel. The invention according to any one of claims 1 to 7 , further comprising a baffle plate arranged between the connection portion between the reaction vessel and the third pipe and the water surface of the water stored in the reaction vessel. Hydrogen generator. The baffle plate is a net-like plate, a plate-like plate having a large number of through holes, or a non-perforated plate-like plate, and is arranged with a gap through which gas can pass between the baffle plate and the inner surface of the reaction vessel.
The hydrogen generating apparatus according to claim 8. A baffle plate arranged between the connection portion between the reaction vessel and the third pipe and the shower head or between the shower head and the water surface of the water stored in the reaction vessel is provided.
The hydrogen generating apparatus according to claim 7. A separation tank for separating the water discharged from the drain port provided at the bottom of the reaction vessel and the reaction product is provided.
The hydrogen generating apparatus according to any one of claims 1 to 10 , wherein the first pipe supplies water separated in the separation tank. The suspension is provided with a fourth pipe for supplying the water separated in the separation tank.
The hydrogen generating apparatus according to claim 11. The hydrogen generating apparatus according to any one of claims 1 to 12 , wherein the hydrogen generating material is magnesium hydride. A fifth pipe into which water generated by a fuel cell consuming hydrogen discharged from the third pipe flows in is provided.
The hydrogen generating apparatus according to any one of claims 1 to 13 , wherein the water flowing in from the fifth pipe is supplied to the second pipe. A heater that heats the water stored in the reaction vessel and
The hydrogen generating device according to any one of claims 1 to 14, further comprising a first cooling device for cooling the water stored in the reaction vessel. The heater maintains the temperature of the water stored in the reaction vessel in the range of 95 degrees Celsius or more and 250 degrees Celsius or less.
The hydrogen generating apparatus according to claim 15. The third tube causes the water vapor in the reaction vessel to flow out together with hydrogen.
The hydrogen generating apparatus according to any one of claims 1 to 16 , further comprising a cooling tank for cooling hydrogen and steam flowing out of the third pipe. A hydrogen tank that stores the hydrogen that has flowed out of the third pipe, and
The hydrogen generating apparatus according to any one of claims 1 to 17 , further comprising a reservoir tank that stores hydrogen at a pressure higher than the internal pressure of the hydrogen tank. Supply water to the inside of the reaction vessel,
Supply the hydrogen generating material powder and water to the suspension container, respectively,
Stir the inside of the suspension container to prepare a suspension.
The suspension in the suspension vessel is supplied to the inside of the reaction vessel, and the suspension is supplied to the inside of the reaction vessel.
A hydrogen generation method for discharging hydrogen generated by a reaction between water stored in the reaction vessel and a hydrogen generating material in the suspension. A mixed solution of a reaction product and water produced by a chemical reaction in the reaction vessel is discharged from the lower part of the reaction vessel.
Separate the discharged reaction product from water
Supply the separated water to the inside of the reaction vessel
The hydrogen production method according to claim 19. Maintain the temperature of the water in the reaction vessel in the range of 95 degrees Celsius or more and 250 degrees Celsius or less.
The hydrogen production method according to claim 19 or 20. The water vapor in the reaction vessel is allowed to flow out together with the hydrogen,
Condensate the water vapor
Water generated by condensation is supplied to the inside of the reaction vessel.
The hydrogen generation method according to any one of claims 19 to 21. Water is supplied to the inside of the reaction vessel via a shower head arranged inside the reaction vessel.
The hydrogen generation method according to any one of claims 19 to 22. Water is sprayed and supplied along the inner wall of the reaction vessel.
The hydrogen generation method according to any one of claims 19 to 22.

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