JP7079441B2 - Fuel cell system - Google Patents

Description

The present invention relates to a technique for enhancing stability and safety in a fuel cell system that generates electricity using hydrogen gas in a low pressure region as an energy source.

In recent years, power generation has been carried out using renewable energy, but there is a problem that the power output is unstable. In addition, engine-type generators are often used as emergency power sources in the event of a disaster, but there are problems with noise and exhaust gas. Therefore, fuel cells are attracting attention as a clean energy source.
However, when using a fuel cell, a hydrogen gas supply source is required.
In the case of a conventional hydrogen station for a fuel cell vehicle, a compressor is used to pre-fill the accumulator with high-pressure hydrogen gas, and the accumulator fills the fuel cell vehicle with hydrogen gas (for example). See Patent Document 1).
However, if a high-pressure cylinder is used as a hydrogen source, there is a problem that the installation location is restricted by laws and regulations because of the high risk. Therefore, the conventional hydrogen station has a problem that the cost for installation and operation is high.

If hydrogen gas in the low pressure range can be generated at the required location and supplied to the fuel cell, safety and convenience can be improved, but there is a problem that it costs a lot to generate hydrogen gas. rice field.

Therefore, a hydrogen production apparatus using hydrogen as a sheet-shaped aluminum as a hydrogen generating material by utilizing the reaction between water and aluminum is known (see, for example, Patent Document 2). According to this, hydrogen gas can be generated at low cost.
However, the hydrogen production apparatus disclosed in Patent Document 2 has a problem that the point of stably continuously generating hydrogen is not sufficiently disclosed. Further, it does not mean that a highly convenient fuel cell system is provided by integrating a hydrogen generator and a fuel cell.

Japanese Unexamined Patent Publication No. 2006-138332 Japanese Unexamined Patent Publication No. 2016-117620

In view of the above situation, the present invention is a fuel cell capable of continuously and quantitatively generating hydrogen gas, and stably and inexpensively using hydrogen gas in a low pressure region with high convenience and safety. The purpose is to provide a system.

In order to solve the above problems, the fuel cell system of the present invention is a fuel cell system including at least a hydrogen gas supply means capable of supplying hydrogen gas in a low pressure region and a fuel cell unit. The hydrogen gas supply means is composed of a hydrogen gas generation unit and a gas storage unit that stores the generated hydrogen gas. The hydrogen gas generating part is made of an aqueous solution of an alkaline earth metal hydroxide or an alkali metal hydroxide and an aluminum piece or a sheet of aluminum as raw materials, or an alkaline earth metal hydroxide or an alkali metal. A reaction vessel that uses hydroxide, aluminum pieces or sheet-like aluminum, and water as raw materials to mix the raw materials, and a supply that controls the supply of a part of the raw materials in order to continuously and quantitatively generate hydrogen gas. It has a control mechanism and an exchange mechanism for exchanging the reaction vessel with another reaction vessel.
In the fuel cell system of the present invention, the hydrogen gas supply means can supply hydrogen gas in a low pressure region, which improves safety. Here, the hydrogen gas in the low pressure region is a hydrogen gas of less than 2 MPa. Therefore, the hydrogen gas in the low pressure region may be, for example, hydrogen gas of less than 1 MPa, and in the case of a container for storing hydrogen gas in the low pressure region of less than 1 MPa, it does not fall under the pressure vessel in the High Pressure Gas Safety Law, so the restriction by the law is limited. You will not receive it.
Further, by providing the supply control mechanism in the hydrogen gas supply means, it becomes possible to stably generate hydrogen gas for a long time, and the fuel cell unit can be operated stably.

By providing an exchange mechanism, even if the reaction in one of the reaction vessels is completed, it is possible to discharge the residue and prepare new raw materials in the reaction vessel without stopping the operation of the fuel cell system. It can generate hydrogen gas in a stable manner.
The exchange mechanism may be, for example, a specification in which a reaction vessel arranged on a rotary table is rotated and exchanged, or may be switched by opening and closing a valve. Therefore, for example, in the case of an exchange mechanism that opens and closes a valve, not only a method of exchanging a reaction vessel but also a method of using a plurality of reaction vessels at the same time to generate a large amount of hydrogen gas is also possible. It is possible.

As the composition of the aqueous solution of the alkaline earth metal hydroxide or the alkali metal hydroxide, calcium hydroxide which is an alkaline earth metal hydroxide is suitable, but sodium hydroxide, potassium hydroxide and the like are suitable. Alkali metal-based hydroxides may be used.
As the aluminum piece or sheet-shaped aluminum, aluminum foil having a thickness of 10 to 14 μm is preferably cut into a rectangle having a side of 1 to 12 mm with a shredder or the like.
As the raw material, a residue discharged by a residue discharging means described later may be used.

In the fuel cell system of the present invention, the supply control mechanism preferably has a screw mechanism or a piston mechanism, and includes a first adjusting mechanism for adjusting the amount of aluminum pieces or sheet-shaped aluminum charged into the reaction vessel. ..
When the raw materials are mixed at once, a large amount of hydrogen gas is instantaneously generated, but the generated amount decreases in a short time thereafter, and it is difficult to stably generate hydrogen gas for a long time.
The supply control mechanism can not only adjust the amount of aluminum charged, but also the time interval of charging.
Therefore, by providing the first adjusting mechanism, it is possible to add aluminum pieces or sheet-shaped aluminum little by little to stably generate hydrogen gas for a long time.

In the fuel cell system of the present invention, the supply control mechanism is provided with a second adjusting mechanism for adjusting the amount of the aqueous solution of the alkaline earth metal hydroxide or the alkali metal hydroxide to be charged into the reaction vessel. Is preferable.
Here, the second adjusting mechanism can not only adjust the amount of the aqueous solution such as calcium hydroxide to be added, but also can adjust the time interval for adding the aqueous solution. As a result, hydrogen gas can be stably generated for a long time.
When an aqueous solution such as calcium hydroxide is added at regular intervals, the water temperature may decrease and the reaction rate may decrease. Therefore, in order to efficiently generate hydrogen gas, it is preferable to further provide a mechanism for further heating and charging an aqueous solution such as calcium hydroxide.

In the fuel cell system of the present invention, the supply control mechanism may include a third adjusting mechanism for adjusting the amount of water dropped in the reaction vessel.
In a relatively small fuel cell system that generates a power of about 100 W, as described above, either an alkaline earth metal hydroxide or an alkali metal hydroxide is mixed with an aluminum piece or a sheet of aluminum. It is also possible to adopt a method of dropping water. Since the method of dropping water is easier to adjust the amount of water added than the method of adding aluminum pieces or the like, it is possible to manufacture the device at low cost.

In the fuel cell system of the present invention, the exchange mechanism replaces the reaction vessel in which the chemical reaction by mixing the raw materials is completed with another reaction vessel containing the raw materials, and provides a residue discharge means for discharging the residue after the reaction. It is preferable to further prepare.
As a result, the residue can be discharged from the reaction vessel that is not used for the reaction, and the residue can be discharged without stopping the operation of the hydrogen gas supply means, and stable hydrogen gas can be generated. Become.

In the fuel cell system of the present invention, it is preferable that the hydrogen gas supply means and the fuel cell unit are connected and integrated.
By connecting and integrating the hydrogen gas supply means and the fuel cell unit, the fuel cell can be used without the need for a hydrogen station, which makes the system highly convenient.

In the fuel cell system of the present invention, it is preferable that the hydrogen gas supply means further includes an impurity removing mechanism for removing impurities such as water that cause performance deterioration.
By providing the impurity removal mechanism, high-purity hydrogen gas can be supplied to the fuel cell unit. It also helps prevent deterioration of the performance of the gas storage section and the like.

The impurity removing mechanism in the fuel cell system of the present invention may use a porous zeolite as an adsorbent and may include a regeneration unit that can be regenerated by increasing the temperature and changing the pressure. As the porous zeolite, for example, a molecular sieve can be used. The molecular sieve is a kind of zeolite, which adsorbs molecules into porous pores, and those molded into powder or pellets can be preferably used. In particular, it strongly adsorbs water molecules.
Here, the regeneration unit may be one that utilizes the heat generated during power generation in the fuel cell unit, or may be one that utilizes the heat generated during hydrogen production.

In the fuel cell system of the present invention, the gas storage unit may be a hydrogen storage alloy built-in container or a low-pressure hydrogen storage tank containing a hydrogen storage alloy.
Even if the hydrogen storage alloy is filled in a low pressure region of less than 1 MPa, for example, it is possible to store hydrogen at a pressure equivalent to 35 MPa, and the operating time of the fuel cell unit can be increased. In addition, space saving can be improved.

Here, as the hydrogen storage alloy, an already known hydrogen storage alloy can be used, for example, an alloy containing a transition element (nickel, cobalt, aluminum, etc.) having a catalytic effect on rare earth elements, niobium, and zirconium (such as nickel, cobalt, and aluminum). AB ₅ type), base alloys of transition elements such as titanium, manganese, zirconium, nickel (AB type ₂ ), magnesium base alloys (Mg alloys) and vanadium base alloys (V series alloys), titanium-iron metal compounds (Ti—Fe system) or the like can be used.

In the fuel cell system of the present invention, when the gas storage unit is a container with a built-in hydrogen storage alloy, exhaust heat from the fuel cell unit is exhausted when hydrogen gas is supplied from the container with a built-in hydrogen storage alloy to the fuel cell unit. , It may be used for releasing hydrogen gas from a container containing a hydrogen storage alloy.
By utilizing the waste heat from the fuel cell unit, hydrogen gas can be efficiently released.

In the fuel cell system of the present invention, when the gas storage unit is a container with a built-in hydrogen storage alloy, it is between the hydrogen gas generating unit and the container with a built-in hydrogen storage alloy, and between the container with a built-in hydrogen storage alloy and the fuel cell unit. It is preferable that a buffer tank for adjusting the supply amount of hydrogen gas is provided.
The hydrogen gas generation rate in the hydrogen gas generation section and the hydrogen gas storage rate in the hydrogen storage alloy built-in container, the hydrogen gas release rate in the hydrogen storage alloy built-in container, and the hydrogen gas usage rate in the fuel cell unit do not always match. Since it is not limited, the flow rate can be adjusted.

In the fuel cell system of the present invention, it is preferable that the hydrogen gas generating unit further includes a temperature control mechanism for controlling the temperature inside the reaction vessel.
The temperature control mechanism is for keeping the water or the aqueous solution in the reaction vessel or the raw material container at the optimum temperature for generating hydrogen gas when hydrogen is generated in the hydrogen gas generating unit. This makes it possible to safely and efficiently generate hydrogen gas.
The temperature control mechanism includes a heating means and a cooling means, and for example, the hydrogen outlet pipe of the reaction vessel is wound around a part of the pipe used for charging the raw material from the raw material container to the reaction vessel to heat the reaction vessel. It may be a means.

According to the fuel cell system of the present invention, hydrogen gas is continuously and quantitatively generated, and hydrogen gas in a low pressure region, which is highly convenient and highly safe, can be stably and inexpensively used for a fuel cell. be.

Functional block diagram of the fuel cell system of Example 1 System configuration diagram of the fuel cell system of the first embodiment Image of the hydrogen gas generator of Example 1 Explanatory drawing of the first adjustment mechanism of Example 1. Image of the fuel cell system of Example 1 Image of the hydrogen gas generator of Example 2 Image of the hydrogen gas generator of Example 3 System configuration diagram of the fuel cell system of Example 4 Cooling image of the container with built-in hydrogen storage alloy during hydrogen storage Heating image of the container with a built-in hydrogen storage alloy when releasing hydrogen Explanatory drawing of the first adjustment mechanism using a piston mechanism Explanatory drawing of the first adjustment mechanism using a screw mechanism Image of conventional hydrogen gas generator

Hereinafter, an example of the embodiment of the present invention will be described in detail with reference to the drawings. The scope of the present invention is not limited to the following examples and illustrated examples, and many changes and modifications can be made.

(Hydrogen gas generation method)
First, a method of generating hydrogen gas will be described. FIG. 13 shows an image diagram of a conventional hydrogen gas generator. As shown in FIG. 13, the hydrogen gas generator 33 includes a reaction vessel 60 and a raw material vessel 70. The reaction vessel 60 has a box shape provided with an openable / closable lid 60a at the top, and the inside of the reaction vessel 60 is provided with an aluminum foil 15a and calcium hydroxide 14. Water 13 is provided inside the raw material container 70.
As shown in FIG. 13, the conventional hydrogen gas generator has a structure in which water 13 is poured from the container 70 with the lid portion 60a open, the lid portion 60a is closed to cause a chemical reaction, and hydrogen gas is generated. .. A discharge hole 60b is provided on the side of the reaction vessel 60 so that the generated hydrogen gas can be discharged.
As described above, the principle of generating hydrogen gas using water 13, calcium hydroxide 14, and aluminum foil 15a is common in the following examples.

(About the aluminum used)
As for the aluminum to be used, first, hydrogen was generated using aluminum powder. As conditions, using 12 g of aluminum powder, 48 g of calcium hydroxide, and 216 mL of water, the reaction temperature was set to 10 ° C., 20 ° C., 40 ° C. and 60 ° C., and the amount of hydrogen gas generated was measured for 240 minutes. In the measurement, stirring was performed.
As a result of the measurement, the reaction rate was 53% when the reaction temperature was set to 10 ° C. The reaction rate when the reaction temperature is set to 20 ° C. is 51%, the reaction rate when the reaction temperature is set to 40 ° C. is 26%, and the reaction rate when the reaction temperature is set to 60 ° C. is small. The result was 9%.
In the measurement, it was found that when the reaction temperature was raised, the amount of hydrogen generated instantaneously increased and the time to reach the peak was shortened, but the reaction rate decreased. This tendency did not change even if the stirring method was improved. This is because in the case of aluminum powder having a reaction temperature of 60 ° C., only the surface of the particles reacts, and a layer (boehmite layer) that blocks water is formed as the second layer from the surface layer, and the reaction is stopped. be.

In the following examples, aluminum foil was used instead of aluminum powder. This is because the aluminum foil has a smaller surface area than the aluminum powder and it is easy to control the generation of hydrogen gas, so that it is suitable for continuously generating hydrogen gas for a long period of time.
In addition, in the case of aluminum powder, if it passes through a mesh sieve with a mesh size of 150 μm by 50% or more, there is a high risk of dust explosion, and it falls under the category of Class 2 dangerous goods under the Fire Service Act. , Aluminum foil does not fall under the category of Class 2 dangerous goods, and has the advantage of high safety. Therefore, a system using a hydrogen gas generator using aluminum foil can be installed and operated in a wide range of places.
Further, the thickness of the aluminum foil is 11 to 12 μm, which is the same thickness as a general aluminum foil used for home use, so that there is an advantage that it is easily available.
In the following examples, strip-shaped aluminum foil cut into a size of 2 mm × 6 to 10 mm in length and width is used.

FIG. 1 shows a functional block diagram of the fuel cell system of the first embodiment. As shown in FIG. 1, the fuel cell system 1 includes a hydrogen gas supply means 2 and a fuel cell unit 5, and the hydrogen gas supply means 2 and the fuel cell unit 5 are connected and integrated.
The hydrogen gas supply means 2 includes a hydrogen gas generation unit 3, an impurity removal mechanism 11, a temperature control mechanism 12, and a gas storage unit 4. The hydrogen gas generating section 3 is provided with a reaction vessel 6, a raw material vessel 7, a supply control mechanism 8, an exchange mechanism 9, and a residue discharging means 10.
In the fuel cell system 1, in the hydrogen gas generation unit 3, the temperature control mechanism 12 is used to adjust the temperature inside the reaction vessel 6 and the raw material vessel 7, while the supply control mechanism 8 is used to adjust the temperature from the raw material vessel 7 to the reaction vessel 6. Hydrogen gas is generated by putting the raw material into the fuel and chemically reacting it with the raw material previously placed in the reaction vessel.
The generated hydrogen gas is sent to the fuel cell unit 5 for power generation after impurities such as water are removed by the impurity removing mechanism 11 and the flow rate is adjusted in the gas storage unit 4.

FIG. 2 shows a system configuration diagram of the fuel cell system of the first embodiment. As shown in FIG. 2, the fuel cell system 1 includes a hydrogen gas generator 30, an impurity removing device 110, a temperature control device 120, a hydrogen gas cylinder 40, and a fuel cell unit 5. That is, the hydrogen gas generator 30 is provided as the hydrogen gas generator 3 shown in FIG. Further, an impurity removing device 110 is provided as the impurity removing mechanism 11, a temperature control device 120 is provided as the temperature control mechanism 12, and a hydrogen gas cylinder 40 is provided as the gas storage unit 4.

The temperature control device 120 is a device for keeping the water or the aqueous solution in the reaction vessel or the raw material container at the optimum temperature for generating hydrogen gas when hydrogen is generated in the hydrogen gas generator 30. This makes it possible to safely and efficiently generate hydrogen gas. Although the temperature control device 120 is externally attached to the hydrogen gas generator 30, it may be built in the hydrogen gas generator 30.

An impurity removing device 110 is provided between the hydrogen gas generator 30 and the hydrogen gas cylinder 40. The impurity removing device 110 plays a role of removing impurities such as water from the hydrogen gas generated in the hydrogen gas generating device 30 by zeolite (molecular sieve) and supplying high-purity hydrogen gas to the hydrogen gas cylinder 40.

In the fuel cell system 1, when supplying hydrogen gas to the fuel cell unit 5, hydrogen gas is generated in the hydrogen gas generator 30 while using the temperature control device 120, and after removing impurities by the impurity removing device 110, the hydrogen gas is removed. It is supplied to the fuel cell unit 5 via the hydrogen gas cylinder 40.
As described above, the fuel cell system 1 does not supply the hydrogen gas previously stored in the hydrogen gas cylinder to the fuel cell unit, but has a structure in which the hydrogen gas is generated and supplied at the place where the hydrogen gas is supplied. It is also possible to design it as a highly safe and mobile device. In addition, since it is a hydrogen generation source that does not generate carbon dioxide, it can be said that it is an environmentally friendly device.

Here, the specific structure of the hydrogen gas generator 30 will be described with reference to FIG.
FIG. 3 shows an image diagram of the hydrogen gas generator of the first embodiment. As shown in FIG. 3, the hydrogen gas generator 30 includes a reaction vessel (6a, 6b), a raw material vessel (7a, 7b), a first adjusting mechanism 8a, a second adjusting mechanism 8b, an exchange mechanism 9a, and a residue discharging means. 10 is provided. The first adjusting mechanism 8a and the second adjusting mechanism 8b are provided in the supply control mechanism 8 shown in FIG. For convenience of explanation, the outlet of the generated hydrogen gas is not shown.
A mixture of water 13 and calcium hydroxide 14 is contained in the raw material container 7a, and a cut aluminum foil 15 is contained in the raw material container 7b. When generating hydrogen gas, a mixture of water 13 and calcium hydroxide 14 and an aluminum foil 15 are put into a reaction vessel 6a to cause a chemical reaction to generate hydrogen gas. In that case, although not shown here, stirring is performed by a stirring device in order to promote a chemical reaction.

(Adjusting the amount of aluminum input)
As described above, the aluminum foil 15 has a smaller surface area than the aluminum powder, and it is easy to control the generation of hydrogen gas. However, even if the aluminum foil 15 is used in a large amount at one time, the amount of hydrogen gas generated temporarily increases. Although it increases, the generation of hydrogen gas ends in a short time. In order to stably supply hydrogen gas to the fuel cell unit 5, it is necessary to stably and continuously generate hydrogen gas. Therefore, the charging amount is adjusted by the first adjusting mechanism 8a, and the aluminum foil 15 is charged at regular intervals to continuously generate hydrogen gas.

(Aluminum input conditions)
The reaction vessel 6a used is a pressure-resistant vessel having a capacity of 33 L. As a premise, 480 g of calcium hydroxide 14 and 2000 mL of water at 80 ° C. are charged into the reaction vessel 6a, and then 40 g of aluminum foil 15 is charged to obtain 13 L / min required for power generation of a 1.1 kW fuel cell. I set the conditions to be used. As a result, after about 13 minutes, the reaction rate became 100% and the accumulated hydrogen generation amount became 58.8 L.

(About the first adjustment mechanism)
The first adjusting mechanism 8a used for charging the aluminum foil 15 at regular intervals will be described with reference to FIG.
4A and 4B are explanatory views of the first adjustment mechanism of the first embodiment, where FIG. 4 is an external view and FIG. 4 is a structural view. As shown in FIG. 4 (1), the first adjusting mechanism 8a includes a first adjusting mechanism main body 81, a piston portion (82, 83), and an aluminum input port 84. The piston portion 82 is provided with the piston 82a, and the piston portion 83 is provided with the piston 83a.
When the aluminum foil 15 is charged, the aluminum foil 15 is charged from the aluminum charging port 84, and the piston 82a is manually or automatically moved from the left to the right to move the aluminum foil 15 to the right. After that, the piston 83a is manually or automatically moved from the upper side to the lower side to move the aluminum foil 15 downward.

As shown in FIG. 4 (2), a valve 81a is provided inside the first adjusting mechanism main body 81. Due to the operation of the pistons (82a, 83a), the valve 81a moves from the upper side to the lower side, and the valve is opened. After the aluminum foil 15 is charged, the piston 83a is manually or automatically moved from the lower side to the upper side to return to the original state. Similarly, the piston 82a is manually or automatically moved from the right to the left to return to the original state. Since the valve 81a is provided inside the first adjusting mechanism main body 81, when the pistons (82a, 83a) are returned, the valve 81a moves from the lower side to the upper side, and the valve is closed. It has a structure that can prevent the leakage of generated hydrogen gas.

(Continuous generation of hydrogen gas by adjusting the amount of aluminum input)
Using the first adjusting mechanism 8a, the aluminum foil 15 was charged at regular intervals to continuously generate hydrogen gas.
First, 50 g of aluminum foil 15, 480 g of calcium hydroxide 14, and 2000 mL of water 13 at 80 ° C. were put into the reaction vessel 6a. Approximately 4 minutes after charging, 4.8 g of aluminum foil 15 was charged into the reaction vessel 6a 19 times every 40 seconds using the first adjusting mechanism 8a. As a result, it was found that the hydrogen generation flow rate of 13 L / min or more can be maintained for about 7 minutes and 30 seconds. The reaction rate was 90%, and the cumulative amount of hydrogen generated was 164.6 L.

(Continuous generation of hydrogen gas using calcium hydroxide and water input adjustment)
However, when aluminum is added at regular intervals, calcium hydroxide may be insufficient and the flow rate may decrease. Therefore, it was confirmed whether or not hydrogen gas can be generated more stably by adding not only aluminum but also calcium hydroxide and water at regular intervals.
Although not shown, the second adjusting mechanism 8b shown in FIG. 3 transfers calcium hydroxide and water to a sanitary pipe by a tubing pump.
First, 50 g of aluminum foil 15, 480 g of calcium hydroxide 14, and 1800 mL of water 13 at 80 ° C. were put into the reaction vessel 6a. Approximately 4 minutes after charging, 4.8 g of aluminum foil 15 was charged into the reaction vessel 6a 30 times every 40 seconds using the first adjusting mechanism 8a. In addition, about 4 minutes after the first raw material is charged, a mixture of 50 g of calcium hydroxide 14 and 200 mL of water 13 is charged into the reaction vessel 6a 15 times every 75 seconds using the second adjusting mechanism 8b. did.
As a result, it was found that the hydrogen generation flow rate was inferior to that of the case where only aluminum was charged at regular intervals.
However, the hydrogen generation time was about 20 minutes in the case of charging only aluminum at regular intervals, but it was about 22 minutes in this measurement, and it was found that the hydrogen generation time could be extended. The reaction rate in this measurement was 64%, and the cumulative hydrogen generation amount was 163 L.

In any of the above measurements, one reaction vessel 6a was used as the reaction vessel, but as shown in FIG. 3, the hydrogen gas generator 30 of this embodiment also provides the reaction vessel 6b. The hydrogen gas generator 30 is provided with an exchange mechanism 9a, and when the reaction in one of the reaction vessels 6a is completed, the exchange mechanism 9a switches to the reaction vessel 6b to operate the hydrogen gas generator 30. It is possible to continuously generate hydrogen gas without stopping.
That is, since the reacted residue remains inside the reaction vessel 6a at which the chemical reaction is completed, it is necessary to discharge the residue after the reaction by the residue discharging means 10 provided in the reaction vessel 6a. .. Further, as described above, even in the system in which the aluminum foil 15, the calcium hydroxide 14 and the water 13 are charged at regular intervals, it is necessary to provide a certain amount of calcium hydroxide 14 and the water 13 at the beginning of the reaction. Therefore, when the reaction in the reaction vessel 6a is completed, hydrogen gas can be continuously generated by immediately switching to the other reaction vessel 6b.
Similarly, when the reaction in the reaction vessel 6b is completed, the exchange mechanism 9a can switch to the reaction vessel 6a to continuously generate hydrogen gas without stopping the operation of the hydrogen gas generator 30. It is possible.
In this way, as soon as the generation of hydrogen gas in the reaction vessel is completed, the reaction vessel can be switched by the exchange mechanism 9a, and the reaction vessel that does not generate hydrogen gas can be treated with residues and new raw materials can be used. Since preparations and maintenance for hydrogen gas generation such as charging can be performed, safe and stable continuous generation of hydrogen gas becomes possible.

The exchange mechanism 9a can not only switch the reaction vessels (6a, 6b), but can also be provided with a function to be used in combination. By operating the reaction vessels (6a, 6b) at the same time, the reaction vessel (6a, 6b) can be operated in a shorter time. It is also possible to generate a large amount of hydrogen gas.

FIG. 5 shows an image diagram of the fuel cell system of the first embodiment. As shown in FIG. 5, the fuel cell system 1 is provided with a reaction vessel (6a, 6b), a raw material vessel (7a, 7b), a fuel cell unit 5, an impurity removing device 110, and the like, and generates hydrogen gas. It is a system in which a device and a fuel cell are integrated. Since hydrogen gas is generated at the place where hydrogen gas is needed and can be used immediately for fuel cells, it can be used as a power source for long-term backup by linking with a power source using renewable energy such as solar power generation and wind power generation. can. It also has the advantages of high safety and few laws and regulations.
The fuel cell system 1 is provided with devices other than the above, connecting members for each device, and the like, but they are omitted here.
For example, the communication function of the fuel cell makes it possible to grasp the status of the hydrogen generation system, that is, the operating status, the abnormality alarm, and the like on the net. In addition, an auxiliary battery is provided, and it is possible to supplement the power supply for a short time and the power supply while the fuel cell is completely started up.

FIG. 6 shows an image diagram of the hydrogen gas generator of the second embodiment. As shown in FIG. 6, the hydrogen gas generator 31 is provided with a reaction vessel (6c, 6d), a raw material vessel (7a, 7b), a first adjusting mechanism 8a, an exchange mechanism 9a, and a residue discharging means 10. .. For convenience of explanation, the discharge port of the generated hydrogen gas and the like are not shown.
A mixture of water 13 and calcium hydroxide 14 is contained in the reaction vessel 6c, and the aluminum foil 15 inside the raw material vessel 7b is put into the reaction vessel 6c to generate hydrogen gas.

Similar to the first embodiment, in order to stably and continuously generate hydrogen gas, the charging amount is adjusted by the first adjusting mechanism 8a, and the aluminum foil 15 is charged at regular intervals. The same applies to the fact that the reaction vessel 6c and the reaction vessel 6d can be immediately switched by the exchange mechanism 9a.
However, unlike the hydrogen gas generator 30 of the first embodiment, the hydrogen gas generator 31 of the second embodiment is not provided with the second adjusting mechanism 8b. The mixture of water 13 and calcium hydroxide 14 is charged in the reaction vessel 6d not used for the reaction, and by switching the reaction vessel (6c, 6d), hydrogen gas is continuously supplied without stopping the operation of the apparatus. It is a structure to generate. Therefore, there is an advantage that the installation cost can be reduced as compared with the hydrogen gas generator 30 in the first embodiment.

FIG. 7 shows an image diagram of the hydrogen gas generator of the third embodiment. As shown in FIG. 7, the hydrogen gas generator 32 is provided with a reaction vessel (6e, 6f), a raw material vessel 7a, a third adjusting mechanism 8c, and an exchange mechanism 9b.
The reaction vessel 6e contains a mixture of calcium hydroxide 14 and aluminum foil 15, and has a structure in which water 13 inside the raw material vessel 7a is dropped into the reaction vessel 6e to generate hydrogen gas. Similarly, the reaction vessel 6f also contains a mixture of calcium hydroxide 14 and aluminum foil 15. The shape of the aluminum foil 15 is the same as that of the first embodiment, but a strip-shaped aluminum foil may be used.

The reaction vessel (6e, 6f) is a removable fuel cartridge. Therefore, the structure of the exchange mechanism 9b is different from that of the exchange mechanism 9a in the hydrogen gas generator 30 of the first embodiment. That is, when the hydrogen gas generator 32 of the third embodiment is in operation, the reaction vessel that does not generate the hydrogen gas is filled with the raw material and the residue is discharged like the hydrogen gas generator 30 of the first embodiment. Instead, the reaction vessel is switched by exchanging the fuel cartridge previously filled with the aluminum foil 15 and the calcium hydroxide 14. Therefore, the reaction vessel (6e, 6f) is not provided with the residue discharging means 10. Similar to the exchange mechanism 9a, the exchange mechanism 9b can not only switch the reaction vessel (6e, 6f) but also have a function to be used in combination, and the reaction vessel (6e, 6f) can be operated at the same time. By doing so, it is possible to generate a large amount of hydrogen gas in a shorter time.

The hydrogen gas generator (30, 31) in the first or second embodiment is mainly used in a fuel cell system that requires an output of 500 W or more, whereas the hydrogen gas generator 32 in the present embodiment is used. Is mainly used in a relatively small fuel cell system having a maximum output of about 100 W. For example, compared to the first adjusting mechanism 8a for adjusting the input amount of the aluminum foil 15 in the hydrogen gas generator 31 of the second embodiment, the third adjusting the dropping amount of the water 13 in the hydrogen gas generator 32 of the present embodiment. Since the adjusting mechanism 8c only needs to adjust the flow rate, the structure is simple and the hydrogen gas generator 32 can be manufactured at low cost.

FIG. 8 shows a system configuration diagram of the fuel cell system of the fourth embodiment. As shown in FIG. 8, in the fuel cell system 100, a hydrogen storage alloy built-in container 41 is provided as a gas storage unit 4. Further, the hydrogen gas generated by the hydrogen gas generator 30 is once adjusted in flow rate in the buffer tank 16a before being stored in the hydrogen storage alloy built-in container 41, and is discharged from the hydrogen storage alloy built-in container 41 even after being discharged from the buffer. The flow rate is adjusted in the tank 16b and sent to the fuel cell unit 5. This is the hydrogen gas generation rate in the hydrogen gas generator 30, the hydrogen gas storage rate in the hydrogen storage alloy built-in container 41, the hydrogen gas release rate in the hydrogen storage alloy built-in container 41, and the use of hydrogen gas in the fuel cell unit. It is possible to adjust the flow rate when the speeds do not match.

Further, the fuel cell system 100 is provided with a heating / cooling unit 17 that utilizes the exhaust heat of the fuel cell unit 5. The heating / cooling unit 17 is used not only for cooling the heat generated from the fuel cell unit 5, but also for heating / cooling the hydrogen storage alloy built-in container 41. Specifically, when the container 41 containing a hydrogen storage alloy is filled with hydrogen gas, the heating / cooling unit 17 is used as a cooling means. On the other hand, when supplying hydrogen gas from the hydrogen storage alloy built-in container 41 to the fuel cell unit 5, the heating / cooling unit 17 is used as the heating means.

A mechanism for using the heating / cooling unit 17 as a heating means and a cooling means will be described with reference to FIGS. 9 and 10. For convenience of explanation, the buffer tanks (16a and 16b) are not shown in FIGS. 9 and 10.
FIG. 9 shows a cooling image diagram of a container containing a hydrogen storage alloy during hydrogen storage. As shown in FIG. 9, the heating / cooling unit 17 has a structure in which the coolant flows in the circulation direction indicated by the arrows (17a, 17b) inside the hydrogen storage alloy built-in container 41 and around the fuel cell unit 5. .. The same coolant is used as the coolant flowing in the heating / cooling unit 17 in any of the circulation directions indicated by the arrows (17a, 17b), and the flow path is changed by opening and closing a valve (not shown). can do.

Specifically, as shown in FIG. 9, when the hydrogen gas 18 is filled in the hydrogen storage alloy built-in container 41, it is necessary to cool the hydrogen storage alloy inside the hydrogen storage alloy built-in container 41 to reduce the pressure. In this case, the valve for passing around the fuel cell unit 5 is closed, and the coolant is circulated in the circulation direction indicated by the arrow 17a. When the heating / cooling unit 17 is operated with the valve closed, the coolant circulates and the hydrogen storage alloy in the container 41 containing the hydrogen storage alloy is cooled. When the hydrogen storage alloy in the hydrogen storage alloy built-in container 41 is cooled, the inside of the hydrogen storage alloy built-in container 41 is depressurized, and the hydrogen gas 18 is easily adsorbed by the hydrogen storage alloy. As a result, the hydrogen gas 18 is filled in the container 41 containing the hydrogen storage alloy.
Here, a constant temperature bath (not shown) is provided outside, and water at a constant temperature is allowed to flow from the constant temperature tank into a pipe that surrounds a part of the cooling liquid circulation pipe in the circulation direction indicated by the arrow 17a for cooling. It is also possible to control the temperature. For example, if the constant temperature bath can discharge water of two kinds of temperatures (50 ° C and 10 ° C), the temperature of the coolant rises if it is hot water at 50 ° C, and conversely if it is cold water at 10 ° C, the coolant The temperature of the will drop further. In this way, the cooling temperature can be controlled by flowing water having a constant temperature from the constant temperature bath.

FIG. 10 shows a heating image diagram of a container containing a hydrogen storage alloy at the time of hydrogen release. As shown in FIG. 10, when the hydrogen gas 18 is supplied from the hydrogen storage alloy built-in container 41 to the fuel cell unit 5, it is necessary to heat and boost the hydrogen storage alloy inside the hydrogen storage alloy built-in container 41. In this case, a valve for passing around the fuel cell unit 5 is opened so that the coolant circulates around the fuel cell unit 5 and inside the hydrogen storage alloy built-in container 41 in the circulation direction indicated by the arrow 17b. .. When the heating / cooling unit 17 is operated with the valve open, the coolant circulates not only in the hydrogen storage alloy inside the hydrogen storage alloy built-in container 41 but also around the fuel cell unit 5, so that the fuel cell unit 5 becomes The coolant absorbs the heat generated during operation, the temperature of the coolant rises, and it becomes a warm circulating fluid to heat the hydrogen storage alloy in the hydrogen storage alloy built-in container 41. When the hydrogen storage alloy in the hydrogen storage alloy built-in container 41 is heated, the pressure inside the hydrogen storage alloy built-in container 41 is increased, and the hydrogen gas 18 is easily released. As a result, the hydrogen gas 18 is supplied from the hydrogen storage alloy built-in container 41 to the fuel cell unit 5. According to the above configuration, the exhaust heat from the fuel cell unit 5 can be effectively used as a heating means for the hydrogen storage alloy in the hydrogen storage alloy built-in container 41.
Here, a radiator (a device that dissipates heat of the liquid) for adjusting the temperature of the circulating liquid, which is a part of the circulating liquid circulation pipe in the circulation direction shown by the arrow 17b and near the inlet of the container 41 containing the hydrogen storage alloy. May be provided. The temperature of the hydrogen storage alloy inside the hydrogen storage alloy built-in container 41 is adjusted, and the discharge rate of the hydrogen gas 18 is adjusted.

The heating / cooling function is easily performed by filling the hydrogen storage alloy built-in container 41 with the hydrogen gas 18 and switching the switch (not shown) for supplying the hydrogen gas 18 to the fuel cell unit 5. Is possible.

FIG. 11 shows an explanatory diagram of the first adjusting mechanism using the piston mechanism. As shown in FIG. 11, the first adjusting mechanism 8d is provided with the piston portion 85, and the piston portion 85a is provided inside the piston portion 85. The piston 85a is provided with two upper and lower sealing portions (85b, 85c), and the aluminum foil 15 charged from the aluminum charging port 86 is sandwiched between the sealing portion 85b and the sealing portion 85c, and the piston 85a is moved upward. By pushing down from the bottom, the structure is such that the reaction vessel is charged into 6 g while maintaining the airtightness.

FIG. 12 shows an explanatory diagram of the first adjusting mechanism using the screw mechanism. As shown in FIG. 12, the first adjusting mechanism 8e is provided with a screw portion 87, and the screw portion 87 is provided with a screw 87a and a handle 87b. When the handle 87b is automatically or manually rotated with the aluminum foil 15 charged from the aluminum charging port 88, the screw 87a rotates so that a certain amount can be stably charged into the reaction vessel 6 g. ing.

(Other examples)
(1) The impurity removing device 110 may be provided with an impurity removing function regenerating device, and may be configured to regenerate the function of the impurity removing device 110 by utilizing the heat generated during power generation in the fuel cell unit 5. In that case, the impurity removing device 110 is provided with an adsorption column and a regeneration column.
(2) The impurity removing device 110 may be provided with an impurity removing function regenerating device, and may be configured to regenerate the function of the impurity removing device 110 by utilizing the heat generated during hydrogen production. In that case, the impurity removing device 110 is provided with an adsorption column and a regeneration column.
(3) The impurity removing device 110 is provided with an impurity removing function regeneration device, and the function of the impurity removing device 110 using the heat generated during power generation in the fuel cell unit 5 and the heat generated during hydrogen production. It may be configured to reproduce. In that case, the impurity removing device 110 is provided with an adsorption column and a regeneration column.

The present invention can be used as a backup power source for power generation using natural energy. It can also be used as an emergency power source in the event of a disaster.

1 Fuel cell system 2 Hydrogen gas supply means 3 Hydrogen gas generator 4 Gas storage section 5 Fuel cell unit 6,6a-6g, 60 Reaction vessel 7,7a, 7b, 70 Raw material container 8 Supply control mechanism 8a, 8d, 8e 1 Adjustment mechanism 8b 2nd adjustment mechanism 8c 3rd adjustment mechanism 9, 9a, 9b Exchange mechanism 10 Residue discharge means 11 Purity removal mechanism 12 Temperature control mechanism 13 Water 14 Calcium hydroxide 15, 15a Aluminum foil 16a, 16b Buffer tank 17 addition Heating / cooling unit 17a, 17b Arrow 18 Hydrogen gas 30-33 Hydrogen gas generator 40 Hydrogen gas cylinder 41 Hydrogen storage alloy built-in container 60a Lid 60b Discharge port 81 First adjustment mechanism body 81a Valve 82, 83, 85 Piston part 82a, 83a , 85a Piston 85b, 85c Seal part 84,86,88 Aluminum inlet 87 Screw part 87a Screw 87b Handle 110 Purity remover 120 Temperature control device

Claims (12)

A fuel cell system including at least a hydrogen gas supply means and a fuel cell unit capable of supplying hydrogen gas in a low pressure region.
The hydrogen gas supply means is
It consists of a hydrogen gas generating part and a gas storage part that stores the generated hydrogen gas.
The hydrogen gas generating part is
Alkaline earth metal-based hydroxide or alkali metal-based hydroxide aqueous solution and aluminum pieces or sheet-like aluminum are used as raw materials.
Or,
Alkaline earth metal hydroxides or alkali metal hydroxides, aluminum pieces or sheet aluminum, and water are used as raw materials.
The reaction vessel for mixing the raw materials and the aluminum piece or sheet-like aluminum are moved by a screw mechanism or a piston mechanism to continuously and quantitatively generate hydrogen gas, and the amount charged into the reaction vessel is adjusted at regular intervals. A fuel cell system comprising a first adjusting mechanism of a supply control mechanism and an exchange mechanism for exchanging a reaction vessel with another reaction vessel. The fuel cell system according to claim 1 , wherein the supply control mechanism includes a second adjusting mechanism for adjusting the amount of the aqueous solution charged into the reaction vessel. The fuel cell system according to claim 1, wherein the supply control mechanism includes a third adjusting mechanism for adjusting the amount of water dropped in the reaction vessel. The exchange mechanism is further provided with a residue discharging means for replacing the reaction vessel in which the chemical reaction by mixing the raw materials is completed with another reaction vessel containing the raw materials and discharging the residue after the reaction. The fuel cell system according to any one of claims 1 to 3 . The fuel cell system according to any one of claims 1 to 4 , wherein the hydrogen gas supply means and the fuel cell unit are connected and integrated. The fuel cell system according to any one of claims 1 to 5 , wherein the hydrogen gas supply means further includes an impurity removing mechanism for removing impurities such as water that cause performance deterioration. The fuel cell system according to claim 6 , wherein the impurity removing mechanism uses porous zeolite as an adsorbent and includes a regeneration unit that can be regenerated by increasing temperature and changing pressure. The fuel cell system according to any one of claims 1 to 7 , wherein the gas storage unit is a container containing a hydrogen storage alloy. When supplying hydrogen gas from the container containing a hydrogen storage alloy to the fuel cell unit, the exhaust heat from the fuel cell unit is used to release hydrogen gas from the container containing the hydrogen storage alloy. The fuel cell system according to claim 8 . A buffer tank for adjusting the supply amount of hydrogen gas was provided between the hydrogen gas generating unit and the container containing the hydrogen storage alloy, and between the container containing the hydrogen storage alloy and the fuel cell unit. The fuel cell system according to claim 8 or 9 . The fuel cell system according to any one of claims 1 to 7 , wherein the gas storage unit is a hydrogen storage tank capable of storing hydrogen gas in a low pressure region. The fuel cell system according to any one of claims 1 to 11 , wherein the hydrogen gas generating unit further includes a temperature control mechanism for controlling the temperature inside the reaction vessel.

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