JP2003137501A - Apparatus for generating hydrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for generating hydrogen which can generate a needed volume of hydrogen when necessary, even if the apparatus is left without carrying out the hydrogen generation reaction for a long time. SOLUTION: The apparatus 1 for generating hydrogen is provided with a tank 4 having a hydride storing part 2 and a liquid storing part 3 separated from each other with a separation wall 4a, a mixing vessel 5, an intermediate tank 6, a reaction vessel 7, and a recovery tank 8. Fine particles of the hydride 9 stored in the tank 4 and water are fed to the mixing vessel 5 by a predetermined amount, and the mixed liquid which is mixed in the mixing vessel 5 is fed to the reaction vessel 7 through a pipe line 22a, the intermediate tank 6 and a pipe line 22b. The upper part of the reaction vessel 7 is interconnected with the upper part of the recovery tank 8 through a pipe 24 which transfers a reaction product generated in the reaction vessel 7 to the recovery tank 8. A pipe 25 to take out hydrogen is connected to the upper part of the recovery tank 8, and an electromagnetic valve 26 is installed to the pipe 25.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to hydrogen which produces hydrogen by mixing a hydride which reacts with water or alcohol to produce hydrogen and water or alcohol, and sends the mixed solution to a reaction tank to react therewith. It relates to a generator.

[0002]

2. Description of the Related Art As a hydrogen source which is a fuel of a fuel cell for electrochemically reacting hydrogen and oxygen to directly convert chemical energy into electric energy, a fossil fuel such as methanol or natural gas is steam-reformed. A method of using hydrogen as a hydrogen fuel, a method of directly storing hydrogen in a hydrogen storage alloy, a high-pressure cylinder, or the like to use as a fuel have been considered. However, in the method of reforming fossil fuel or the like with steam to obtain hydrogen, the size of the apparatus becomes large. Further, the method of storing hydrogen in a hydrogen storage alloy or a high-pressure cylinder becomes heavy, and the method of using a hydrogen storage alloy requires a heating means to take out hydrogen.
Therefore, miniaturization is difficult.

As a device for generating hydrogen, which is a fuel for a fuel cell, which solves the above problems, Japanese Patent Application Laid-Open No. 10-64572 discloses a chamber containing at least water and a substance which reacts with water to generate hydrogen. A chamber containing the water and an isolation means for isolating the chamber containing the water from the chamber containing the substance that reacts with the water to generate hydrogen, and when operating the fuel cell, generates hydrogen by reacting with the water. A device has been proposed in which a hole is formed in the isolation means in order to generate hydrogen by causing a reaction by adding water to the substance. As a substance which reacts with water to generate hydrogen, a borohydride compound, lithium borohydride, aluminum borohydride and the like are disclosed.

[0004]

However, the above-mentioned conventional hydrogen generator is mainly applied to a fuel cell used as a portable power source for office automation equipment such as a notebook computer, and generates hydrogen by reacting with water. Water is supplied to a chamber containing a substance, and the chamber also serves as a reaction chamber (reaction tank). As a result, the reaction cannot be interrupted halfway.

As a method for solving the above-mentioned inconvenience, a substance in which a hydrolysis reaction which produces hydrogen in the state of being mixed with water at a room temperature is slow in progress is used, and a substance which reacts with water to produce hydrogen and water are used. A method is considered in which the mixed solution obtained by mixing is gradually reacted in the reaction tank little by little, the product after the reaction is recovered from the reaction tank, and a new mixed solution is supplied to the reaction tank.

However, if a substance that reacts with water to generate hydrogen is left in a mixed state with water for a long time, the reaction proceeds little by little and hydrogen is released. When a large amount of the mixed solution is stored, the surface area becomes smaller than the volume, the heat dissipation efficiency deteriorates, the solution temperature rises due to the reaction heat, and the reaction proceeds further. There is a problem when it is used as the fuel source of the fuel cell of the power source.

The present invention has been made in view of the above problems, and an object thereof is to provide a necessary amount of hydrogen when needed, even if the hydrogen generation reaction is left for a long period of time. It is to provide a hydrogen generator capable of generating hydrogen.

[0008]

In order to achieve the above object, in the invention according to claim 1, a hydride which reacts with water or alcohol to generate hydrogen and water or alcohol are mixed, A hydrogen generator that sends a mixed solution to a reaction tank to cause a reaction to generate hydrogen, wherein a powdered one is used as the hydride, and the hydride contained in the hydride container is placed in a mixing chamber. A predetermined amount was supplied, and a mixed liquid mixed with water or alcohol in the mixing chamber was sequentially transferred to the reaction tank, and a reaction product was collected in a recovery tank.

In the present invention, water is not limited to pure water, but a substance that promotes or suppresses the reaction between the hydride and water or reacts with the hydride in the state of an aqueous solution to generate hydrogen. It also means an aqueous solution containing a substance.

According to the present invention, the powdered hydride contained in the hydride container is supplied to the mixing chamber by a predetermined amount.
It is mixed with water or alcohol in the mixing chamber. The mixed liquid is sequentially transferred from the mixing chamber to the reaction tank. The reaction product after the hydrogen generation reaction is carried out in the reaction tank is transferred from the reaction tank and collected in the collection tank. Therefore, unlike the conventional device in which the entire amount of hydride and water are mixed in the mixing chamber to carry out the hydrogen generation reaction, the amount of hydride required to generate the required hydrogen is adjusted to water or water in the mixing chamber. Mix with alcohol,
The amount of hydrogen generated can be controlled by changing the amount sent to the reaction tank according to the required amount of hydrogen. Further, since the hydride is stored in a state where it does not come into contact with water or alcohol until hydrogen is needed, there is no possibility that the hydrogen generation reaction will proceed even if it is stored for a long time.

According to the second aspect of the present invention, powdery hydride which reacts with water or alcohol to generate hydrogen is mixed with water or alcohol, and the mixed solution is sent to a reaction tank for reaction. A hydrogen generator for generating hydrogen, which is provided with a plurality of hydride accommodating parts for accommodating the hydride, and connects each hydride accommodating part and the reaction tank with a pipe line equipped with a valve after the reaction. The product is configured to be recoverable in an empty hydride accommodation unit, the hydrides accommodated in the plurality of hydride accommodation units are sequentially supplied to the mixing chamber by a predetermined amount, and water or alcohol is supplied in the mixing chamber. The mixed liquid mixture is sequentially transferred to the reaction tank, the product after the reaction in the reaction tank is first collected in a tank for collection, and then the hydride is used to empty the hydride storage unit. Product after reaction is sequentially collected in the reaction tank Was to so that.

In the present invention, the powdered hydride contained in the hydride container is supplied to the mixing chamber by a predetermined amount and mixed with water or alcohol, and the mixed liquid is sequentially transferred to the reaction chamber to generate hydrogen. Is the same as the invention described in claim 1. According to the first aspect of the invention, all the reaction products are collected in the dedicated recovery tank, so that a recovery tank having a volume at least equal to the total volume of the hydride storage unit is required. However, in this invention, a plurality of hydride accommodation parts are provided,
The hydrides in each hydride storage are sequentially used, and the empty hydride storage is used as a recovery tank. Therefore, it suffices to prepare a recovery tank for collecting the reaction product of the hydride supplied from the hydride storage unit used first, and the reaction product of the hydride supplied from the other hydride storage unit. Are recovered in the previously emptied hydride container. As a result, the volume occupied by the recovery tank can be significantly reduced.

According to a third aspect of the present invention, in the first or second aspect of the present invention, the hydride storage portion, the hydride stored in the hydride storage portion, and the mixed liquid are prepared. The hydride and water or alcohol are contained in a tank that is partitioned by a partition wall with a liquid container that contains water or alcohol necessary for the operation.

According to the present invention, since the hydride storage portion and the liquid storage portion are provided in one tank, it is easy to downsize the entire apparatus and the powdered hydride and water or alcohol. It becomes easy to supply and to the mixing chamber.

According to a fourth aspect of the present invention, in the invention according to any one of the first to third aspects, a metering valve is provided in the middle of a path connecting the mixing chamber and the hydride storage section. Is provided, and the metering valve is configured to be able to supply the hydride by a predetermined amount to the mixing chamber. In the present invention, the valve (measuring valve) for controlling the supply and stop of the hydride to the mixing chamber has a metering function, and the opening and closing of the valve automatically causes a predetermined amount of powdered hydride to be mixed in the mixing chamber. And a predetermined amount of hydride can be easily supplied to the mixing chamber.

According to a fifth aspect of the invention, in the fourth aspect of the invention, a sensor for detecting the amount of liquid in the mixing chamber is provided, and the opening / closing control of the metering valve is performed based on the amount of liquid in the mixing chamber. Is done. In the present invention, since the liquid amount in the mixing chamber is detected by the sensor, it is easy to know how much the mixed liquid prepared in the mixing chamber is transferred to the reaction tank, and the opening / closing of the metering valve is controlled based on the liquid amount. To be done. Therefore, the hydride can be supplied to the mixing tank at an appropriate time.

According to a sixth aspect of the present invention, in the invention according to the fourth or fifth aspect, the hydride is supplied to the mixing chamber side when the hydride measured by the measuring valve is supplied to the mixing chamber side. Hydrogen injection means for injecting hydrogen so as to send it to the mixing chamber side is provided. In this invention, when the powdered hydride measured by the metering valve is sent to the mixing chamber side, the transfer is assisted by the pressure of the hydrogen injected from the hydrogen injection means, so that the powdered hydride is removed. It can be smoothly supplied to the mixing chamber.

According to a seventh aspect of the present invention, in the invention according to any one of the first to sixth aspects, the mixing chamber or the path connecting the mixing chamber and the reaction tank is provided in the middle. A stirring means for stirring the mixed liquid is provided.
In the present invention, the powdered hydride and water are surely mixed and uniformly supplied to the reaction tank. Therefore, the hydrogen generation reaction in the reaction tank is smoothly performed.

According to an eighth aspect of the present invention, in the invention according to any one of the first to seventh aspects, the hydride containing portion contains the hydride contained in the hydride containing portion. Pressurizing means for applying pressure is provided. In this invention, since the powdered hydride contained in the hydride container is pressurized by the pressurizing means, even if the hydride is in powder form, the hydride is discharged from the outlet of the hydride container. Can be sent out smoothly.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION (First Embodiment) A first embodiment of the present invention will be described below with reference to FIGS.

As shown in FIG. 1, in the hydrogen generator 1, a tank 4 in which a hydride container 2 and a liquid container 3 are partitioned by a partition 4a and a mixing chamber as a mixing chamber for mixing water and hydride are mixed. A tank 5, an intermediate tank 6, a reaction tank 7, and a recovery tank 8 are provided. The partition wall 4a is formed in a shape such that its diameter decreases toward the lower side. The hydride container 2 contains a powdered hydride 9 that reacts with water to generate hydrogen, and the liquid container 3 contains water. In this embodiment, sodium borohydride (Na
BH ₄ ) is used. The tank 4 has a lid 4b,
The lid 4b can be hermetically sealed with the lid 4b closed and can be filled with hydrogen for pressurizing the hydride 9 and water.
The hydrogen filled in the hydride container 2 constitutes a pressurizing means for pressurizing the hydride 9 contained in the hydride container 2.

The mixing tank 5 is arranged in the lower part of the tank 4, and as shown in FIGS. 2 and 3, a metering valve 10 is integrally incorporated so as to cover the upper opening of the mixing tank 5. The metering valve 10 is provided with a spool 12 which is slidable in an axial direction in a housing 11. The spool 12 is formed such that a first storage portion 12a capable of storing a predetermined amount of hydride 9 and a second storage portion 12b capable of storing a predetermined amount of water extend in the vertical direction.

A valve plate 13 is provided between the lower surface of the tank 4 and the upper surface of the housing 11, and the hydride accommodating portion 2 is provided above the valve plate 13 and the housing 11.
And a first supply hole 14a that communicates with the spool storage portion, and a second supply hole 14 that communicates with the liquid storage portion 3 and the spool storage portion.
b are formed. A first discharge hole 15a and a second discharge hole 15b, which communicate the mixing tank 5 and the spool accommodating portion, are formed in the lower portion of the housing 11 at positions out of phase with the supply holes 14a and 14b. Both supply holes 14
The distance between a and 14b and the distance between both the discharge holes 15a and 15b are set to be the same as the distance between the accommodating portions 12a and 12b, respectively. The spool 12 has an actuator 16 at a first position in which both housing portions 12a and 12b correspond to both supply holes 14a and 14b, and a second position in which both housing portions 12a and 12b correspond to both discharge holes 15a and 15b. And is configured to be moved by the action of the spring 17. An explosion-proof solenoid is used for the actuator 16, and the spool 12 is arranged in the first position by the urging force of the spring 17 in the demagnetized state, and the spool 12 is arranged in the second position by the action of the solenoid in the excited state. It has become so.

As shown in FIG. 3, the valve plate 13 and the housing 11 are formed with a hole 13a opened at a position facing the first discharge hole 15a. Hole 13a
Is connected to a first end of a hydrogen supply pipe 18 (only shown in FIG. 3), and a second end of the hydrogen supply pipe 18 is connected to the tank 4
Is connected to the lid 4b of the above and communicates with the hydride storage unit 2. The hydrogen supply pipe 18 is provided with a solenoid valve 19. When the spool 12 is placed in the second position by the operation of the actuator 16, the electromagnetic valve 19 is opened for a predetermined time.

The mixing tank 5 is provided with a liquid level gauge 20 as a sensor for detecting the amount of liquid in the mixing tank 5. Based on the amount of liquid in the mixing tank 5, opening / closing control of the metering valve 10, that is, hydride 9 is carried out.
And water is supplied. In this embodiment, the liquid level gauge 2
An ultrasonic level gauge is used as 0. In this metering valve 10, the state in which the spool 12 is arranged in the first position is the state in which the metering valve 10 is closed and the state in which the spool 12 is arranged in the second position (the hydride 9 and water in the accommodating portions 12a and 12b are The state of being discharged) is defined as the open state.

A stirring means 21 for stirring a mixed solution of the hydride 9 and water is provided in the mixing tank 5. In this embodiment, a static mixer is provided as a stirring means. That is, when the mixed liquid in the mixing tank 5 is transferred to the intermediate tank 6, the mixed liquid is agitated.

The mixing tank 5 and the intermediate tank 6 are connected by a pipe line 22a. The pipe line 22a is constituted by a pipe whose first end is connected to the bottom of the mixing tank 5 and whose second end is connected to the upper part of the intermediate tank 6. The pipe 22a is mixed from the intermediate tank 6 side in the middle thereof. A check valve 23 is provided to prevent the gas from moving toward the tank 5. The intermediate tank 6 and the reaction tank 7 are connected by a pipe line 22b. The pipe line 22b is composed of a pipe whose first end is connected to the bottom of the intermediate tank 6 and whose second end is connected to the bottom of the reaction tank 7. The mixed solution is fed into the reaction tank 7 from below the reaction tank 7 via the intermediate tank 6. When the pressure on the upper side of the reaction tank 7 becomes equal to or higher than a predetermined pressure, a part of the mixed liquid in the reaction tank 7 can be returned to the intermediate tank 6.

The upper part of the reaction tank 7 and the upper part of the recovery tank 8 are connected by a pipe 24 as a conduit for transferring the reaction product generated in the reaction tank 7 to the recovery tank 8. Pipe 2
Reference numeral 4 is connected to a gas-liquid separation device (not shown) provided above the recovery tank 8. A hydrogen extraction pipe 25 is connected to the upper portion of the recovery tank 8, and the hydrogen extraction pipe 25 is provided with a solenoid valve 26. The mixing tank 5 and the recovery tank 8 are connected by a pipe 27, and a throttle valve 28 and a check valve 29 for preventing the pressure in the mixing tank 5 from exceeding a predetermined pressure in the middle of the pipe 27. Is provided.

Next, the operation of the device configured as described above will be described. The hydride container 2 of the tank 4 is filled with a predetermined amount of hydride 9, and the liquid container 3 is filled with the entire amount of hydride 9.
The operation of the hydrogen generator 1 is started from a state in which a predetermined amount of water larger than the amount necessary for the reaction is stored and the tank 4 is filled with hydrogen.

First, the metering valve 10 is driven to drive the mixing tank 5.
Hydride 9 and water are supplied therein. As shown in FIG. 3, when the spool 12 is arranged at the first position,
The first container 12a is filled with hydride 9, and the second container 12b is filled with water. Then, when the spool 12 is moved to the left in FIG. 3 by the drive of the actuator 16 and is arranged at the second position, each of the accommodating portions 12a, 12b.
Is in a state of facing the discharge holes 15a and 15b, and the hydride 9 and water in the storage portions 12a and 12b are supplied to the mixing tank 5. Since the hydride 9 is a powder, it is difficult for the hydride 9 to be discharged from the storage portion 12a only when the storage portion 12a faces the discharge hole 15a. However, when the spool 12 is arranged in the second position, the solenoid valve 19 is opened for a predetermined time and the hydrogen supply pipe 1
Hydrogen is released from the container 8 through the hole 13a into the container 12a, so that the hydride 9 is smoothly supplied to the mixing tank 5.

After the spool 12 is placed in the second position, the excitation of the actuator 16 is released when a predetermined time has elapsed, the spool 12 is returned to the first position by the urging force of the spring 17, and each accommodation portion 12a, 12b is filled with the hydride 9 and water, and the state shown in FIG. 3 is obtained. And mixing tank 5
The actuator 16 is driven intermittently until the amount of liquid in the mixture reaches a predetermined value, and the hydride 9 and water are sequentially mixed in the mixing tank 5.
Is supplied to. When the amount of liquid in the mixing tank 5 reaches a predetermined amount,
The drive of the actuator 16 is stopped based on the signal from the liquid level gauge 20, and the supply of the hydride 9 and water to the mixing tank 5 is stopped. Then, when the amount of the mixed liquid in the mixing tank 5 becomes a predetermined amount or less, the driving of the actuator 16 is restarted based on the signal from the liquid level gauge 20, and the supply of the hydride 9 and water to the mixing tank 5 is restarted. To be done.

Hydrogen is also supplied into the mixing tank 5 together with the hydride 9, and the hydride 9 and water supplied into the mixing tank 5 depend on the pressure of the hydrogen in the mixing tank 5, and the pipeline 22a and the intermediate tank 6
And is transferred to the reaction tank 7 via the conduit 22b. The mixed solution is uniformly mixed by the stirring means 21 in the reaction tank 7
Be transferred to. The mixing tank 5 has a throttle valve 28 and a check valve 29.
Since it is connected to the recovery tank 8 via the pipe 27 provided with, the pressure in the mixing tank 5 is suppressed from becoming higher than a predetermined pressure.

When the mixed liquid transferred to the reaction tank 7 passes through the reaction tank 7, the hydride 9 is hydrolyzed by the following reaction formula. Due to the presence of NaBH ₄ + 2H ₂ O → 4H ₂ + NaBO ₂ catalyst, the above reaction proceeds well. Since this reaction is an exothermic reaction, part of the water becomes steam due to the heat of reaction. Then, the hydrogen generated by the hydrolysis and the reaction product are led in a mist state from the upper part of the reaction tank 7 to the recovery tank 8 through the pipe 24. The reaction product is separated into a liquid and a gas (hydrogen) by a gas-liquid separation device (not shown), the liquid is stored in the recovery tank 8, and the hydrogen is discharged through the hydrogen extraction pipe 25 with the solenoid valve 26 open to, for example, fuel. Supplied to the battery.

This embodiment has the following effects. (1) The hydride 9 and water are stored in the hydride storage unit 2 and the liquid storage unit 3, respectively, until the operation of the hydrogen generator 1 is started. Therefore, when the hydrogen generator 1 is used as a hydrogen source of a fuel cell as an emergency power source, unlike the configuration in which the hydride 9 is stored in the state of an aqueous solution, there is no possibility that the hydrogen generation reaction will proceed during storage, When the hydrogen generator 1 is operated, it is possible to secure a planned hydrogen generation amount.

(2) The powdered hydride 9 contained in the hydride container 2 is supplied to the mixing tank 5 by a predetermined amount,
It is mixed with water in the mixing tank 5 and sequentially transferred to the reaction tank 7. Therefore, unlike the conventional device in which the entire amount of hydride and water are mixed in the mixing chamber (mixing tank) to carry out the hydrogen generation reaction, the amount of hydride required to generate the required hydrogen is generated. The amount of hydrogen generated can be controlled by mixing with water in the mixing tank 5.

(3) Since the powdered hydride 9 is used, it can be quickly dissolved when mixed with water. (4) Since the mixing means 5 is provided with the stirring means 21, the powdered hydride 9 and water are reliably mixed and supplied to the reaction tank 7 in a uniform state. Therefore, the hydrogen generation reaction in the reaction tank 7 is smoothly performed.

(5) Since the static mixer is provided as the stirring means 21, a driving unit is not required for the stirring means 21, and the structure is simplified. (6) The hydride 9 and water are contained in the tank 4 in which the hydride container 2 and the liquid container 3 are partitioned by the partition wall 4a. Therefore, it is easy to reduce the size of the entire device.

(7) Hydride container 2 and liquid container 3
Since the mixing tank 5 is integrally provided below the tank 4 having the above, it becomes easy to supply the powdered hydride 9 and water to the mixing tank 5.

(8) A metering valve 10 is provided in the middle of the path connecting the mixing tank 5 and the hydride container 2, and the metering valve 10 is configured to supply a predetermined amount of the hydride 9 to the mixing tank 5. ing. That is, the valve for controlling the supply and stop of the hydride 9 to the mixing tank 5 has a metering function, and when the metering valve 10 is opened / closed, the powdered hydride 9 is automatically supplied in a predetermined amount in a predetermined amount. And a predetermined amount of hydride 9 can be easily supplied to the mixing tank 5.

(9) When the hydride 9 measured by the measuring valve 10 is supplied to the mixing tank 5, the hydride 9 is added to the mixing tank 5.
A hydrogen injection means (hydrogen supply pipe 18) for injecting hydrogen so as to send it out to is provided. Therefore, the powdery hydride 9 measured by the measuring valve 10 can be smoothly mixed with the mixing tank 5
Can be supplied to.

(10) A level gauge 20 for detecting the amount of liquid in the mixing tank 5 is provided, and the opening / closing control of the metering valve 10 is performed based on the amount of liquid in the mixing tank 5. Therefore, it is possible to easily understand how much the mixed solution prepared in the mixing tank 5 is transferred to the reaction tank 7, and the hydride 9 can be supplied to the mixing tank 5 at an appropriate time.

(11) Since the mixed liquid is transferred to the intermediate tank 6 by the pressure of hydrogen in the mixing tank 5, the structure is simpler than the case where a transfer pump is provided. (12) Since the pressure in the hydride container 2 and the liquid container 3 is made higher than the pressure in the mixing tank 5 by filling the tank 4 with hydrogen, it is stored in the hydride container 2. The powdered hydride 9 present is smoothly sent out from the outlet of the hydride accommodation part 2. Water is also smoothly supplied to the mixing tank 5.

(13) Since the hydrogen supply means (hydrogen supply pipe 18) uses hydrogen in the tank 4 as a hydrogen source, it is not necessary to separately prepare a hydrogen tank, and the structure is simplified. (14) Since the mixing tank 5 and the recovery tank 8 are connected by the pipe 27 equipped with the throttle valve 28 and the check valve 29, the pressure in the mixing tank 5 is prevented from becoming excessive, and hydrogen is released into the atmosphere. The mixed solution in the mixing tank 5 can be smoothly transferred to the intermediate tank 6 without being discharged to the intermediate tank 6.

(Second Embodiment) Next, a second embodiment will be described with reference to FIGS. In this embodiment, the powdered hydride 9 stored in the hydride storage unit 2 is used.
Is supplied to the mixing tank 5 by a predetermined amount and mixed with water, and the mixed solution is sequentially transferred to the reaction tank 7 through the intermediate tank 6 to generate hydrogen, which is the same as the above-mentioned embodiment. But,
In this embodiment, a plurality of hydride storage units 2 are provided, the hydrides 9 in each hydride storage unit 2 are sequentially used, and the hydride storage unit 2 that has become empty is used as a recovery tank. The point is largely different from the above embodiment. The same parts as those in the above-mentioned embodiment are designated by the same reference numerals and detailed description thereof will be omitted.

FIG. 4 is a schematic plan view showing the arrangement of the tank 4 and the reaction tank 7, and FIG. 5 is a schematic side view showing the arrangement of the tank 4, the intermediate tank 6 and the reaction tank 7. As shown in FIGS. 4 and 5, one intermediate tank and one reaction tank 7 are provided,
A plurality of tanks (11 in this embodiment) are provided.

Each mixing tank 5 has a conduit 31 equipped with a solenoid valve 30.
Are respectively connected to the intermediate tank 6 via. Each tank 4 is provided with a gas-liquid separation device 32 (shown only in FIG. 5) on the upper part thereof, and the inlet of the gas-liquid separation device 32 and the reaction tank 7
Is connected to the upper part of the via a pipe line 33. Pipeline 33
An electromagnetic valve 34 is provided as a valve corresponding to each tank 4, and one tank 4 is configured to be in a state in which it can communicate with the reaction tank 7 by controlling the opening / closing of each electromagnetic valve 34. .

The mixing tank 5 is provided with a safety valve (not shown) in order to prevent the pressure inside the mixing tank 5 from becoming overpressure. In this hydrogen generator 1, one tank 4 is emptied, hydride 9 is stored in the hydride storage part 2 of the remaining tank 4, and water is stored in the liquid storage part 3 respectively. Be started. Since the empty tank 4 is used as a recovery tank, only the electromagnetic valve 34 corresponding to the empty tank is opened among the electromagnetic valves 34 provided in the pipe line 33 connecting the reaction tank 7 and each tank 4. The remaining solenoid valve 34 is kept closed. Also,
One of the remaining tanks 4 containing the hydride 9 and water is selected and the mixing tank 5 to reaction tank 7 of that tank 4 is selected.
In order to enable the supply of a mixed solution of hydride 9 and water,
The electromagnetic valve 30 of the conduit 31 corresponding to the mixing tank 5 is held in an open state. Then, from this state, the hydrogen generator 1
The operation of is started.

Similar to the above-described embodiment, the metering valve 10 provided in the mixing tank 5 is controlled to be opened and closed to supply the hydride 9 and water from the tank 4, and the mixed liquid is supplied to the pipe 31, the intermediate tank 6 and the pipe. It is supplied to the reaction tank 7 via the path 22b.
Then, the reaction product that has reacted in the reaction tank 7 is recovered in the hydride storage unit 2 of the tank 4 via the conduit 33. Hydride 9 and hydride 9 in tank 4 supplying water
After a predetermined time has passed after all the
The solenoid valve 34 of the pipe line 33 corresponding to is opened, and the solenoid valve 34 that has been open until then is held in the closed state. As a result, the reaction product is switched to a state in which the reaction product is collected in the hydride storage unit 2 of the empty tank 4.

When the hydride 9 and the hydride 9 in the tank 4 which had been supplying water until then are all supplied and the amount of the mixed liquid in the mixing tank 5 of the tank 4 becomes equal to or less than a predetermined amount, The solenoid valve 30 corresponding to the mixing tank 5 of the tank 4 of FIG.
The supply of hydride 9 and water to the Thereafter, in the same manner, the tank 4 that was supplying the hydride 9 and water
When the hydride container 2 of the above is empty, the tank 4 thereof functions as a recovery tank, and the solenoid valves 30 and 34 are controlled to open and close so as to supply the hydride 9 and water from the next tank 4. .

This embodiment has the following effects in addition to the effects (1) to (13) of the above embodiment. (15) A plurality of hydride accommodation units 2 are provided, the hydrides 9 in each hydride accommodation unit 2 are sequentially used, and the empty hydride accommodation unit 2 is used as a recovery tank.
Therefore, it suffices to prepare a recovery tank for recovering the reaction product of the hydride 9 supplied from the hydride accommodating section 2 used first, and the volume occupied by the recovery tank can be greatly reduced.

(16) The recovery tank at the start of operation does not have a structure dedicated to recovery and the tank 4 is used. Therefore, during the operation of the hydrogen generator 1, by performing the operation of taking out the recovered reaction product, the cleaning of the inside of the hydride container 2, the operation of filling the hydride 9, etc., the continuous operation with a small number of tanks 4 is possible. Will be able to do.

(17) Since the tank 4 and the mixing tank 5 are integrated (unit), the tank 4 to be installed
The duration of the hydrogen supply of the hydrogen generator 1 can be easily extended by increasing the number of.

The embodiment is not limited to the above, but may be configured as follows, for example. The metering valve 10 may have a structure including a rotatable spool 35 as shown in FIG. 6, instead of the structure in which the spool 12 linearly reciprocates. The spool 35 includes a storage portion 35a for hydride 9 and a storage portion (not shown) for water, and each storage portion 35a or the like is 90 degrees from a position facing the outlets of the hydride storage portion 2 and the liquid storage portion 3. In the rotated state, hydrogen can be supplied from the hydrogen supply pipe 18 to the storage portion 35a for the hydride 9. Similarly, hydrogen can be supplied from the hydrogen supply pipe 18 to a water container (not shown). In this case, it is not necessary to secure a space before and after the spool, and the device can be downsized.

In the first embodiment, the arrangement of the tank 4, the intermediate tank 6, the reaction tank 7 and the recovery tank 8 may be changed as appropriate. For example, instead of the configuration in which the tank 4, the intermediate tank 6, the reaction tank 7, and the recovery tank 8 are arranged in parallel, they may be arranged side by side in the vertical direction as shown in FIG. 7.

The intermediate tank 6 may be omitted. As shown in FIGS. 8 and 9, the intermediate tank 6 is omitted, the mixing tank 5 and the reaction tank 7 are connected by a pipe line 36, and the mixed liquid is supplied from the upper side of the reaction tank 7, The reaction product may be discharged to the recovery tank 8 from below. However, the mixed solution is supplied from the lower side of the reaction tank 7 and the reaction product is collected from the upper side of the reaction tank 7 in the recovery tank 8
The one in which the mixed solution and the reaction product are supplied can be smoothly transferred. It should be noted that the mixing tank 5, the recovery tank 8 or the tank 4 may be provided with a safety valve which is opened when the internal pressure exceeds a predetermined pressure.

○ In place of the structure in which the hydride container 2 and the liquid container 3 are provided in the tank 4 and the predetermined amount of the hydride 9 and the water are supplied to the mixing tank 5 by one metering valve 10, the hydride container is contained. The part 2 and the liquid storage part 3 may be separately provided, and the metering valve 10 may be configured to supply only the hydride 9 in a predetermined amount from the hydride storage part 2 to the mixing tank 5.

In the second embodiment, the liquid storage portion 3 is provided separately from the hydride storage portion 2, and the liquid storage portion 3 is provided as one unit so that water is supplied to the mixing tank 5 by a pump. Good.

In the second embodiment, instead of providing the mixing tanks 5 corresponding to the number of the hydride accommodation parts 2, one mixing tank 5 may be provided in a plurality of hydride accommodation parts 2. The mixing tank 5 may be one. In this case, mixing tank 5
The ratio occupied by the hydrogen generator becomes small, and the hydrogen generator 1 can be made compact.

The hydrogen source of the hydrogen supply pipe 18 may be replaced with the tank 4 and a hydrogen cylinder may be provided separately from the tank 4. The stirrer 21 is not limited to the static mixer, and a stirrer that positively drives the stirrer may be used. For example, a stirrer that rotates a rotating member that is arranged inside the mixing tank 5 by the attraction force of a magnet that is arranged outside the bottom of the mixing tank 5 and a stirrer that rotates a rotating shaft to which a propeller is fixed with a motor. Is used. In the case of a stirrer, an explosion-proof type is used.

The stirring means 21 does not necessarily have to be provided in the mixing tank 5, and a static mixer may be provided in the conduits 22a and 31. The high-pressure gas for increasing the pressure in the hydride container 2 is not limited to hydrogen but nitrogen or helium in order to smoothly feed the hydride 9 or the like contained in the hydride container 2 into the metering valve 10. Alternatively, an inert gas such as argon or neon or air may be used. However, when hydrogen is used as the hydrogen source of the fuel cell, when oxygen in the air is sent to the hydrogen electrode of the fuel cell together with hydrogen, there is a risk that problems such as a decrease in the activity of the catalyst may occur. It is preferred to use an inert gas, most preferably hydrogen. The same applies to the gas that smoothly discharges the hydride 9 to the mixing tank 5 side with the metering valve 10.

The gas-liquid separation device 32 may be omitted.
However, by positively separating the reaction product into gas and liquid by the gas-liquid separator 32, the reaction product NaBO ₂
It is possible to prevent the liquid droplets containing hydrogen from being sent together with hydrogen from the recovery tank 8 or the tank 4 used as the recovery tank to the fuel cell.

The reaction tank 7 is not necessarily configured to support the catalyst, and may be configured to accelerate the reaction by heating without using the catalyst. Since the hydrogen generation reaction is an exothermic reaction, the inside of the reaction tank 7 is heated by the heat generation as the reaction proceeds, so that it is not necessary to apply a large amount of heat unlike when hydrogen is taken out from the hydrogen storage alloy.

As a pressurizing means for pressurizing the hydride 9 stored in the hydride storage part 2, instead of using a filling gas, for example, a structure for mechanically pressing the hydride 9 is provided in the tank. Good.

As the liquid that reacts with the hydride 9 to generate hydrogen, alcohol or an aqueous solution containing hydrogen peroxide may be used. As the hydride 9, a substance other than sodium borohydride, such as lithium aluminum hydride or calcium hydride, may be used.

The invention (technical idea) understood from the above embodiment will be described below. (1) In the invention described in claim 7, the stirring means is a static mixer.

(2) In the invention described in claim 6,
The mixing chamber and the recovery tank are connected by a pipeline provided with a throttle valve and a check valve for restricting the movement of gas toward the mixing chamber.

(3) In the invention described in claim 2,
The mixing chamber is configured to be shared by a plurality of the hydride storage units. (4) In the invention according to claim 3, the tank has a mixing chamber at a lower portion thereof.

[0068]

As described in detail above, claims 1 to 8 are provided.
According to the invention described in (1), even if the hydrogen generation reaction is left for a long time without being carried out, a required amount of hydrogen can be generated when the hydrogen is required. Further, according to the invention described in claim 2, the volume occupied by the recovery tank can be significantly reduced, and the entire hydrogen generator can be downsized.

[Brief description of drawings]

FIG. 1 is a partially cutaway schematic side view of a hydrogen generator according to a first embodiment.

FIG. 2 is a schematic cross-sectional view showing a mixing tank and a metering valve.

FIG. 3 is a schematic sectional view of a metering valve.

FIG. 4 is a schematic plan view showing the arrangement of a reaction tank and a tank according to the second embodiment.

FIG. 5 is a partially cutaway schematic side view of the hydrogen generator.

FIG. 6 is a schematic cross-sectional view showing a metering valve of another embodiment.

FIG. 7 is a schematic side view of a hydrogen generator according to another embodiment.

FIG. 8 is a schematic side view of a hydrogen generator according to another embodiment.

FIG. 9 is a schematic side view of a hydrogen generator according to another embodiment.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Hydrogen generator, 2 ... Hydride accommodation part, 3 ... Liquid accommodation part, 4 ... Tank, 4a ... Partition wall, 5 ... Mixing tank as a mixing chamber, 7 ... Reaction tank, 8 ... Recovery tank, 9 ... Hydride 10,
... metering valve, 18 ... hydrogen supply pipe as hydrogen injection means, 21 ... stirring means, 33 ... pipe, 34 ... solenoid valve as valve.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Matsumoto             1 Toyota Town, Toyota City, Aichi Prefecture Toyota Auto             Car Co., Ltd. F term (reference) 5H027 AA02 BA13 BA14 KK21 MM01

Claims (8)

[Claims] 1. A hydrogen generator which mixes hydride that reacts with water or alcohol to generate hydrogen and water or alcohol, and sends the mixed solution to a reaction tank to cause reaction to generate hydrogen. The powdered hydride is used as the hydride, the hydride contained in the hydride container is supplied to the mixing chamber by a predetermined amount, and the mixed liquid mixed with water or alcohol is mixed in the mixing chamber. A hydrogen generator that sequentially transfers the reaction products to a reaction tank and collects the reaction products in a recovery tank. 2. A powdery hydride that reacts with water or alcohol to generate hydrogen and water or alcohol are mixed,
A hydrogen generator for sending the mixed solution to a reaction tank to react with it to generate hydrogen, wherein a plurality of hydride storage parts for storing the hydride are provided, and each hydride storage part and the reaction tank are valved. The product after the reaction is connected by a pipe line provided with a structure capable of recovering in an empty hydride storage unit, and the hydrides stored in the plurality of hydride storage units are sequentially added to the mixing chamber by a predetermined amount. It is supplied and the mixed liquid mixed with water or alcohol in the mixing chamber is sequentially transferred to the reaction tank, and the product after the reaction in the reaction tank is first recovered in a recovery tank, and then the hydride is used. A hydrogen generator in which the products after the reaction in the reaction tank are sequentially collected in the hydride storage portion that has been emptied. 3. The partition wall divides the hydride storage unit and a liquid storage unit that stores the hydride stored in the hydride storage unit and water or alcohol necessary for preparing the mixed liquid. The hydrogen generator according to claim 1 or 2, wherein the hydride and water or alcohol are contained in the tank. 4. A metering valve is provided in the middle of a path connecting the mixing chamber and the hydride container, and the metering valve is configured to supply the hydride in a predetermined amount to the mixing chamber. The hydrogen generator according to any one of claims 1 to 3. 5. The hydrogen generator according to claim 4, wherein a sensor for detecting the amount of liquid in the mixing chamber is provided, and the opening / closing control of the metering valve is performed based on the amount of liquid in the mixing chamber. 6. A hydrogen injection means for injecting hydrogen so as to send out the hydride to the mixing chamber side when the hydride measured by the measuring valve is supplied to the mixing chamber side. The hydrogen generator according to claim 4 or 5. 7. The stirring means for stirring the mixed liquid is provided in the mixing chamber or in a path connecting the mixing chamber and the reaction tank. The hydrogen generator described. 8. The pressurizing means for pressurizing the hydride contained in the hydride accommodation part is provided in the hydride accommodation part. Hydrogen generator.