JP2009143791A - Apparatus for generating hydrogen and fuel battery system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for generating hydrogen which can suppress an influence of a decrease in the reaction rate by a product and stably supply hydrogen, and to provide a fuel battery system which can generate a stable electric power in a fuel battery. <P>SOLUTION: The apparatus is provided with a first solution introduction passage through which a reaction solution is fed to a first hydrogen generating substance, a second solution introduction passage through which the reaction solution is fed to a second hydrogen generating substance, and a control valve which changes the feeding of the reaction solution from the first solution introduction passage to the second solution introduction passage, wherein even if the reaction is inhibited by adhesion of a product to the first hydrogen generating substance, control of the control valve changes the feeding of the reaction solution from the first solution introduction passage to the second solution introduction passage to feed the reaction solution to the second hydrogen generating substance, whereby a decrease in the reaction rate can be suppressed and hydrogen can stably be generated. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrogen generator, and further relates to a fuel cell system provided with such a hydrogen generator.

  A fuel cell is an electrochemical reaction in which a fuel fluid such as hydrogen gas or methanol is supplied to the anode side of a power generation unit having an anode and a cathode across a solid polymer electrolyte membrane, and an oxidizing fluid such as oxygen or air is supplied to the cathode side. To generate power.

  As a method of obtaining hydrogen with low energy when using hydrogen gas as a fuel, a method of hydrolyzing a metal hydride called chemical hydride is known. Examples of the chemical hydride include lithium borohydride, sodium borohydride, lithium aluminum hydride, and sodium aluminum hydride, which are a kind of metal hydride.

  When hydrolyzing a metal hydride to obtain hydrogen, products such as metal inclusions and bubbles generated by the reaction are present, and the product covers the metal hydride and inhibits contact between the metal hydride and water. . As a result, the reaction rate of the hydrogen generation reaction decreases, and the reaction eventually stops.

For this reason, the technique of removing a product by spraying the water supplied to a metal hydride at a high pressure is known. (For example, refer patent document 1) Since the product is removed by spraying the water supplied to a metal hydride at a high pressure, a decrease in reaction rate can be suppressed.
JP 2002-137903 A

  However, in the conventional technology, in order to maintain the hydrogen generation amount, a large amount of water must be supplied at a high pressure. Since a large amount of water is supplied, even after the supply of water is stopped, the hydrogen generation reaction continues to occur with the water supplied up to that point, and excessive hydrogen is generated. Therefore, hydrogen is generated when it is not necessary, and hydrogen is wasted.

  The present invention has been made in view of the above situation, and suppresses the influence of a decrease in reaction rate due to a product, and can generate a desired amount of hydrogen when necessary, thereby enabling a stable power supply. An object of the present invention is to provide a hydrogen generator and a fuel cell system.

  In order to achieve the above object, a first hydrogen generating apparatus of the present invention comprises a reaction vessel that contains a hydrogen generating substance and generates hydrogen by reacting the hydrogen generating substance with a reaction solution, and a reaction solution. A flowing solution channel, a solution feeding means for introducing the reaction solution into the solution channel, a first solution introduction channel for introducing the reaction solution into the first hydrogen generating material, and a second solution for the reaction. A second solution introduction path for introducing hydrogen into the hydrogen generating material, a hydrogen outlet path for discharging hydrogen generated in the reaction vessel, and one of the first solution introduction path and the second solution introduction path to the other. And a control valve for switching the liquid delivery of the reaction solution. The control valve switches the liquid delivery from the first solution introduction path to the second solution introduction path as the first hydrogen generating substance is consumed. And a switching unit.

  According to such a feature, the solution solution for reaction can be switched from the first solution introduction path to the second solution introduction path as the hydrogen generation substance is consumed, and the product adheres to the first hydrogen generation substance. Even when the hydrogen generation reaction is inhibited, the reaction solution is supplied to the second hydrogen generating material to which the product is not attached, so that the product inhibits the reaction and reduces the reaction rate. It is possible. Therefore, it is possible to stably generate a necessary amount of hydrogen without supplying extra water to the hydrogen generating material.

  In the second hydrogen generator of the present invention, the liquid feed switching unit is configured so that when the supply amount of the reaction solution to the first solution introduction path reaches a predetermined amount, The liquid feeding is switched to the solution introduction path.

  According to such a feature, when the reaction solution necessary for the reaction is supplied to the first hydrogen generating material, the reaction solution solution can be switched from the first solution introduction path to the second solution introduction path. Since the responsiveness of switching the solution introduction path for supplying the reaction solution is improved, a decrease in the reaction rate due to the inhibition of the product is suppressed, and a certain amount of hydrogen can be stably supplied.

  In the third hydrogen generator of the present invention, the control valve includes a pressing portion that presses the hydrogen generating material as the hydrogen generating material reacts, and the liquid feeding switching portion is pressed by the pressing portion as the hydrogen generating material decreases. The liquid feeding is switched from the first solution introduction path to the second solution introduction path.

  According to this feature, the hydrogen generating substance is pressed as it reacts, and the hydrogen generating substance can be pressed near the opening of the solution introduction path, so that the hydrogen generating substance is more likely to react with the reaction solution. In addition, the liquid feeding switching unit is pressed by the pressing unit along with the decrease of the hydrogen generating substance, and accordingly, the liquid feeding can be switched from the first solution introduction path to the second solution introduction path. Hydrogen can be generated.

  In the fourth hydrogen generator of the present invention, the liquid feed switching unit is switched to either a closed state in which the first solution introduction path is closed or an open state in which the first solution introduction path is opened. A valve body, a second valve body that switches between a closed state that closes the second solution introduction path and an open state that opens the second solution introduction path, and a first valve body and a second valve body And a rod portion that closes the first valve body and opens the second valve body in accordance with the displacement of the pressing portion.

  According to this feature, the first valve body and the second valve body, and the rod portion that connects the first valve body and the second valve body are provided, and the rod portion is pressed in accordance with the displacement of the pressing portion. Displacement of the 1 valve body and the 2nd valve body enables easy transfer of the solution for reaction from the first solution introduction path to the second solution introduction path, thus simplifying the structure and allowing efficient reaction It becomes possible to feed the solution for use.

  In the fifth hydrogen generator of the present invention, the control valve includes a pressure receiving displacement portion that is displaced in accordance with fluctuations in the reaction vessel, and the liquid feed switching portion is provided in the pressure receiving displacement portion that accompanies a decrease in the pressure in the reaction vessel. The liquid feeding is switched from the first solution introduction path to the second solution introduction path by the displacement.

  According to this feature, as the pressure in the reaction vessel decreases, that is, as the amount of hydrogen generated in the reaction vessel decreases, the reaction solution is fed from the first solution introduction path to the second solution introduction. Since it is possible to switch to a path, it becomes possible to supply a certain amount of hydrogen stably.

  In the sixth hydrogen generator of the present invention, the liquid feed switching unit is configured to open the first solution introduction path and close the second solution introduction path, and to close the first solution introduction path and close the second solution introduction path. The third valve body that is switched to one of the second states that open the solution introduction path and the third valve body are connected, and the third valve body is moved from the first state in accordance with the displacement of the pressure receiving displacement portion. And a connecting portion for switching to the second state.

  According to this feature, the third valve body and the connection portion connected to the third valve body are provided, and the connection portion moves due to the displacement of the pressure receiving displacement portion accompanying the decrease in pressure, and the third valve body is displaced to react. Since the solution supply solution can be easily switched from the first solution introduction path to the second solution introduction path, the structure is simplified and the reaction solution can be efficiently fed.

  A seventh hydrogen generating apparatus according to the present invention includes a partition portion that partitions between the first hydrogen generating material and the second hydrogen generating material.

  According to such a feature, it is possible to prevent the product generated by the reaction of the first hydrogen generating material from covering the second hydrogen generating material and inhibiting the reaction of the second hydrogen generating material. Even when the posture of the container changes, the reaction solution is not supplied to the unreacted hydrogen generating substance. Therefore, the reaction between the hydrogen generating substance and the reaction solution occurs efficiently, and more stable hydrogen supply can be achieved.

  In the fuel cell system of the present invention, the hydrogen outlet flow path of any one of the first to seventh hydrogen generators of the present invention is connected to the fuel electrode chamber of the fuel cell, and the generated hydrogen is supplied to the fuel electrode. It is characterized by that.

  According to such a feature, there is provided a fuel cell system that is provided with a hydrogen generator capable of stably supplying hydrogen while suppressing the influence of a reduction in reaction rate due to a product, and capable of generating stable power. Can do.

  Embodiments of the present invention will be described below with reference to the drawings.

(Embodiment 1)
1 is a schematic diagram of a hydrogen generator according to Embodiment 1. FIG.

  As shown in FIG. 1, the hydrogen generator 1 according to this embodiment includes a reaction vessel 2 as a reactor, and a plurality of hydrogen generating substances 9 as reactants of a hydrogen generation reaction are accommodated in the reaction vessel 2. Has been. A solution introduction path 7 is connected to each of the plurality of hydrogen generating substances.

  Although not shown, a reaction solution storage container is provided adjacent to the reaction container 2, and the reaction solution is stored in the container.

  The solution flow path 4 is provided with a solution feeding means 3, and the solution feeding means 3 controls the feeding and stopping of the reaction solution. The configuration of the solution delivery means 3 is not limited as long as the solution for reaction is introduced and circulated through the solution flow path 4. For example, a liquid feeding means to which a pumping mechanism such as a pump is applied can be used, and a liquid feeding amount controlled by the amount of hydrogen consumed (power consumption in the case of a fuel cell) is applied. In addition, liquid feeding means using a valve that is opened and closed using the internal pressure in the reaction vessel 2 can be used, and a device that generates hydrogen by feeding the liquid when the internal pressure of the reaction vessel 2 becomes low is applied. Is done.

  The reaction solution supplied by the solution delivery means 3 is sent to each solution introduction path 7 via a control valve 6 whose flow is controlled by the solution feed switching control unit 5 to react with each hydrogen generating substance, and to supply hydrogen. appear. Hydrogen generated in the reaction vessel 2 is supplied from the hydrogen outlet channel 10 to a hydrogen consumption unit (not shown).

  The detailed structure of the control valve 6 is shown in FIG.

As shown in FIG. 2, when the supply amount of the reaction solution to the first solution introduction path 21 reaches a predetermined amount, the control valve 6 sends the first solution introduction path 21 to the second solution introduction path 22. A liquid feed switching unit 24 for switching the liquid is provided (a). The reaction solution supplied from the first solution introduction path 21 reacts with the first hydrogen generating substance 28 disposed in the vicinity of the opening of the first solution introduction path 21 to generate hydrogen. When the liquid feed switching control unit 5 determines that a reaction solution corresponding to a predetermined amount has been supplied to the first hydrogen generating material, the liquid feed switching unit 24 supplies the reaction solution to the second solution introduction path 22. (B), the second hydrogen generating substance reacts with the reaction solution to generate hydrogen. By repeating this, the reaction solution is supplied to a plurality of hydrogen generating substances, and hydrogen is stably generated. In FIG. 2, the opening of the first solution introduction path 21 is on the right side with respect to the liquid feeding switching unit 24. However, the present invention is not limited to this position, and may be formed on the upper side, the left side, or the like of the liquid feed switching unit 24 as long as the reaction solution can be supplied to the first hydrogen generating substance 28. Absent.

  Although not shown in FIG. 1, the reaction vessel 2 may have a partition for partitioning each hydrogen generating material. Thereby, it is possible to prevent the product generated by the reaction of the first hydrogen generating material from covering the second hydrogen generating material and hindering the reaction of the second hydrogen generating material, and the posture of the reaction vessel is Even in the case of change, the reaction solution is not supplied to the unreacted hydrogen generating substance. Therefore, the reaction between the hydrogen generating substance and the reaction solution occurs efficiently, and more stable hydrogen supply is possible.

  Examples of the hydrogen generating substance include borohydride salt, aluminum hydroxide salt, sodium borohydride, lithium borohydride, lithium aluminum hydroxide and the like, and sodium borohydride is particularly preferable. Examples of the hydrogen generation catalyst include sulfuric acid, malic acid, and citric acid water, and malic acid is particularly preferable. These hydrogen generating substance and hydrogen generating catalyst are not particularly limited, and any hydrogen generating substance can be applied as long as it is a hydrolyzed metal hydride. Examples of the hydrogen generating catalyst include organic acids and inorganic acids. Alternatively, any hydrogen generation catalyst such as ruthenium is applicable. Further, any combination of a hydrogen generating material and a hydrogen generating catalyst, such as sodium hydrogen borohydride aqueous solution and malic acid as a hydrogen generating material, can be applied as long as they are substances that generate hydrogen by mixing. . Alternatively, hydrogen may be obtained by a reaction between a metal and a basic or acidic aqueous solution.

  Here, the predetermined amount of the supply amount of the reaction solution to the solution introduction path is a predetermined amount of the reaction solution supplied to each solution introduction path. As shown in FIG. 3, the hydrogen generation flow rate due to the reaction between the reaction solution and the hydrogen generating substance 9 is such that the reaction product generated by the hydrogen generation reaction inhibits the contact between the reaction solution and the hydrogen generating substance 9. descend. The supply amount of the reaction solution when the hydrogen generation flow rate is lower than the necessary hydrogen flow rate is defined as the reaction amount v0 of the reaction solution with the hydrogen generation substance.

  A specific flow of processing in the liquid feeding switching control unit 5 will be described with reference to FIG.

  In step 2, a solution introduction path for supplying the reaction solution is determined. Since the initial value is set to X = 1 in Step 1, the reaction solution is supplied to the solution introduction path 1. Next, in step 3, the supply amount of the reaction solution to the solution introduction path 1 is integrated to obtain v1. In step 4, the cumulative reaction solution amount v1 is compared with the reaction amount v0 of the hydrogen generating substance in the reaction solution. Here, v0 is a reaction between the reaction solution and the hydrogen generating substance 9 because the reaction between the reaction solution and the hydrogen generating substance 9 is inhibited by the reaction product generated by the hydrogen generating reaction shown in FIG. This is the supply amount v0 of the reaction solution at the time when the hydrogen generation flow rate due to the pressure decreases and falls below the required hydrogen flow rate. If the integrated reaction solution amount v1 does not reach the predetermined amount v0 (v1 <v0), the supply of the reaction solution to the solution introduction path 1 is continued, and the integration of the supply amount of the reaction solution in step 3 is continued. To do. If the cumulative reaction solution amount v1 has reached v0 (v1> v0), it is determined whether X has reached the solution introduction path number Z set in step 5. When the set number of solution introduction paths Z is reached, that is, when X = Z, the supply of the reaction solution is stopped. If the set number Z of solution introduction paths has not been reached, supply of the reaction solution to the solution introduction path 2 is started in step 6. At the same time, the value of X is incremented by 1, and the target for integrating the supply amount of the reaction solution in Step 3 is the supply amount v2 of the reaction solution to the solution introduction path 2. By repeating this, the reaction solution is supplied to all the set solution introduction path numbers Z.

  Therefore, a predetermined amount of the reaction solution can be supplied to each solution introduction path, and when the predetermined amount is reached, the reaction solution can be supplied to the next solution introduction path. For this reason, a necessary hydrogen flow rate can always be ensured.

(Embodiment 2)
In FIG. 5, the schematic of the hydrogen generator which concerns on Embodiment 2 is shown. Note that the same members as those in the first embodiment shown in FIG. In the hydrogen generator shown in FIGS. 5 and 1, the hydrogen generating substance 9 is divided into small parts in FIG. 1, but is different in that the hydrogen generating substance 9 is integrated in FIG. 5. Even when the hydrogen generating material is integrated as shown in FIG. 5, the reaction solution and the hydrogen generating material are supplied to supply the reaction solution from each solution introduction path to the hydrogen generating material in the vicinity of each opening. Thus, hydrogen can be stably supplied without inhibiting the above reaction and reducing the reaction rate.

(Embodiment 3)
FIG. 6 shows a schematic configuration of the hydrogen generator according to the third embodiment of the present invention.

  In addition, the same code | symbol is attached | subjected to the same member as 1st Embodiment shown in FIG. 1, and the overlapping description is abbreviate | omitted.

  The hydrogen generating apparatus shown in FIG. 6 includes a hydrogen generating material remaining amount detecting unit 11 that detects that the amount of the hydrogen generating material 9 has decreased and has reached a specified amount, and outputs a switching signal to the control valve 6. Upon receiving the switching signal, the control valve 6 switches the solution introduction path for supplying the reaction solution from the first solution introduction path to the second solution introduction path. As in the first embodiment, the hydrogen generating substance 9 is installed in small portions. Similarly, the amount of each hydrogen generating substance 9 is the amount of the hydrogen generating substance that can react with the supply amount v0 of the reaction solution in FIG.

  With this configuration, the remaining amount of each hydrogen generating substance 9 is detected, and when it is detected that the amount of the hydrogen generating substance 9 has reached a specified amount, a switching signal is output to the control valve 6, thereby Therefore, stable hydrogen can be supplied to each hydrogen generating material.

  In the third embodiment, the hydrogen generating material may be integrated as in the second embodiment.

(Embodiment 4)
FIG. 7 shows a configuration of a control valve according to the hydrogen generator according to the fourth embodiment of the present invention.

  A pressing portion 30 is provided that is pressed against the hydrogen generating material 28 by a pressing spring 29 and presses the hydrogen generating material 28 as the hydrogen generating material 28 is consumed.

  The liquid feeding switching unit 24 is switched to one of a rod part 33 that is pressed and operated by the pressing part 30, and a closed state that is fixed to the rod part 33 and closes the first solution introduction path 21 and an open state that opens. When the first valve body 31 is fixed to the rod portion 33 and the first valve body 31 is open, the second solution introduction path 22 is closed, and when the first valve body 31 is closed, the first valve body 31 is closed. And a second valve body 32 in an open state that opens the second solution introduction path 22.

  A specific operation state will be described in detail.

  The pressing portion 30 that is pressed against the hydrogen generating material 28 by the pressing spring 29 and is displaced as the hydrogen generating material 28 is consumed presses the rod portion 33 in the downward direction of the drawing as the hydrogen generating material 28 is consumed. The first valve body 31 and the second valve body 32 fixed to the rod portion 33 move downward in the drawing as the rod portion 33 moves.

  In FIG. 7A, the remaining amount of the hydrogen generating material 28 is sufficient, and the pressing portion 30 is located away from the rod portion 33. At this time, the rod portion 33 is pushed upward in the figure by the rod spring 25, and the first valve body 31 fixed to the rod portion 33 is in an open position where the first solution introduction path 21 is opened. The second valve body 32 is in a closed position that closes the second solution introduction path 22. For this reason, the reaction solution is supplied to the first solution introduction path 21. FIG. 7B shows a case where the remaining amount of the hydrogen generating substance 28 is reduced. At this time, the rod part 33 is pushed downward in the figure by the pressing part 30, and the first valve body 31 fixed to the rod part 33 moves to a closed position that closes the first solution introduction path 21, The second valve body 32 moves to an open position where the second solution introduction path 22 is opened. At this time, the feeding of the reaction liquid is switched from the first solution introduction path 21 to the second solution introduction path 22.

As a result, the first valve body, the second valve body, and the rod portion that connects the first valve body and the second valve body can be used to easily switch the liquid supply of the reaction solution. Further, since the hydrogen generating material can be pressed near the opening of the solution introduction path as it reacts, the hydrogen generating material easily reacts with the reaction solution. Therefore, stable hydrogen supply can be achieved with a simple structure that does not require a sensor or electrical control.
(Embodiment 5)
FIG. 8 shows the configuration of a control valve according to the hydrogen generator according to the fifth embodiment of the present invention.

  The control valve 50 according to this embodiment includes a liquid feed switching unit 55 and a drive unit 54.

  The liquid feed switching unit 55 is fixed to the connecting unit 51 and the connecting unit 51, opens the first solution introduction path 21 and closes the second solution introduction path 22, and the first solution introduction path 21. A third valve body 52 that switches to one of the second states in which the second solution introduction path 22 is opened and a connection spring 521 that is fixed to the third valve body.

  The drive unit 54 includes a pressure receiving displacement portion 57, a drive portion space 58 partitioned by the pressure receiving displacement portion 57 and the seal portion 53, and a stopper body 56 disposed so as to be pressed against the connecting portion 51.

  The control valve 50 is installed so that the upper surface of the pressure receiving displacement portion 57 in FIG. 8 receives the pressure in the reaction vessel 2 of the hydrogen generator. The pressure receiving displacement portion 57 is deformed by receiving a downward force due to the pressure in the reaction vessel 2, an upward force by which the connecting portion 51 is pushed up by the connecting spring 521, and an upward force due to the pressure in the drive portion space 58. This is a diaphragm having a so-called diaphragm structure. Moreover, the partition of a piston structure which moves to an up-down direction may be sufficient.

  A specific operation of the pressure receiving displacement portion 57 will be described in detail.

  The downward force due to the pressure in the reaction vessel 2 of the hydrogen generator is Fi, the upward force by which the connecting portion 51 is pushed up by the connecting spring 521 is Fs, and the upward force due to the pressure in the drive space 58 is Fa. Then, when Fi> Fs + Fa, the state shown in FIG. 8A is obtained, and when Fi <Fs + Fa, the state shown in FIG. 8B is obtained. The state of FIG. 8 (A) is the first state described above, and the state of FIG. 8 (B) is the second state described above.

  Therefore, the pressure value (switching operation pressure) in the reaction vessel 2 when switching from the state of FIG. 8 (A) to (B) can be adjusted by the strength of the coupling spring 521 and the pressure in the drive unit space 58. It is. Further, the structure in which the pressure receiving displacement portion 57 and the connecting portion 51 are connected and the connecting portion 33 is moved by using the upward force due to the pressure in the driving portion space 58 does not require the connecting spring 521. It is also possible. In this case, the switching operation pressure is set only by the pressure in the drive unit space 58.

  An enlarged view of the drive unit 54 is shown in FIG. A view of the drive unit 54 as viewed from the top in the AA plane is shown in FIG.

  The stopper body 56 is disposed so as to be pressed against the connecting portion 51 from the side surface. For example, as shown in FIG. 9B, the stopper body 56 may be pressed against the connecting portion 51 using a torsion spring 60 or the like. A cutout portion 59 is provided on the side surface of the connecting portion 51, and the pressure in the reaction vessel 2 is reduced to a state shown in FIG. 8B. That is, when the connecting portion 51 is pushed upward, the reaction solution At the same time that the liquid supply is switched from the first solution introduction path 21 to the second solution introduction path 22, the stopper body 56 is inserted into the notch 59, and the connecting portion 51 is fixed. As a result, the reaction solution is supplied to the second hydrogen generating material via the second solution introduction path, and the connecting portion 51 is fixed even when the hydrogen generation speed is recovered and the pressure in the reaction vessel 2 is increased. Therefore, the third valve body 52 connected to the connecting portion 51 moves downward, and the liquid supply to the second solution introduction path 22 is continued without opening the first solution introduction path 21 again. be able to.

  Next, a method for setting the pressure value in the reaction vessel 2 and the switching operation pressure when switching from the (A) state to the (B) state in FIG. 8 will be described.

  FIG. 10 shows an example of the transition of the internal pressure of the reaction vessel 2 during operation of the hydrogen generator.

  This is an example using a liquid feeding means for feeding a reaction solution when the pressure in the reaction vessel 2 is lowered to a set value (liquid feeding set pressure). In this case, the reaction solution is supplied once or more for one hydrogen generating substance. At this time, a pressure value lower than the liquid supply set pressure and higher than the minimum required pressure defined by the power generation characteristics of the fuel cell to be used is set as the switching operation pressure.

  The operation of switching the liquid feeding from the first solution introduction path 21 to the second solution introduction path 22 will be described.

  First, when a certain amount of reaction solution is supplied to the first hydrogen generating material via the first solution introduction path 21, hydrogen is generated and the pressure in the reaction vessel 2 rises. When the generated hydrogen is consumed, the pressure in the reaction vessel 2 decreases, but when the pressure decreases to the liquid feed set pressure, the pressure is reduced by supplying the reaction solution to the first hydrogen generating material again. Rise again. This operation is repeated to generate hydrogen from the first hydrogen generating material. Then, even if the reaction solution is supplied to the first hydrogen generating substance, the pressure in the reaction vessel 2 does not increase, and when the pressure decreases to the switching operation pressure, the state shown in FIG. . That is, the pressure receiving displacement portion 57 is displaced upward, and the third valve body 52 is moved from the first state in which the first solution introduction path 21 is opened and the second solution introduction path 22 is closed to the first solution introduction path. Then, the second solution introduction path 22 is opened and the second solution introduction path 22 is opened, and the reaction solution is sent to the second hydrogen generating material via the second solution introduction path 22 to recover the hydrogen generation speed. To do.

  By repeating this operation, liquid is sequentially fed to each of the plurality of hydrogen generating substances installed, and the pressure in the hydrogen generator can be continuously maintained near the liquid feeding set pressure. Moreover, a stable hydrogen supply can be achieved by a simple structure that does not require a reaction vessel sensor or electrical control.

  In the fifth embodiment, the hydrogen generating material may be integrated as in the second embodiment.

(Embodiment 6)
The fuel cell system will be described based on FIG.

  FIG. 11 shows a schematic configuration of a fuel cell system according to an embodiment of the present invention. In this embodiment, since the hydrogen generator 1 shown in FIG. 1 is applied, the same members as those shown in FIG.

  The fuel cell system shown in FIG. 11 is a system in which the hydrogen generator 1 shown in FIG. That is, the fuel cell 40 is provided with a fuel electrode chamber 42, and the fuel electrode chamber 42 constitutes a space in contact with the fuel electrode of the fuel cell 41. A hydrogen outlet channel 10 of the hydrogen generator 1 is connected to the fuel electrode chamber 42.

  The solution flow path 4 of the hydrogen generator 1 is connected to the solution container 43, and the reaction solution 44 in the solution container 43 is sent to the hydrogen generator 1 by the solution feeding means 3.

  The hydrogen generated in the hydrogen generator 1 is supplied from the hydrogen outlet channel 10 to the fuel electrode chamber 42 and consumed by the fuel cell reaction at the fuel electrode. The amount of hydrogen consumed at the fuel electrode of the fuel electrode chamber 42 is determined according to the output of the fuel cell 40.

  As the hydrogen generator, the hydrogen generators shown in FIGS. 5 and 6 and the hydrogen generator using the mechanisms shown in FIGS. 2, 7, and 8 can be applied.

  The fuel cell installation system described above is a fuel cell system including a hydrogen generator that suppresses the influence of a decrease in reaction rate due to a product and stably supplies hydrogen.

1 is a schematic configuration diagram of a hydrogen generator according to a first embodiment of the present invention. 1 is a schematic configuration diagram of a control valve according to a first embodiment of the present invention. It is a graph showing an example of the solution supply amount for reaction of this invention, and a hydrogen generation flow rate. It is a flowchart showing an example of the process in the liquid feeding switching control part of this invention. It is a schematic block diagram of the hydrogen generator which concerns on the 2nd Example of this invention. It is a schematic block diagram of the hydrogen generator which concerns on the example of 3rd Embodiment of this invention. It is a schematic block diagram of the control valve which concerns on the 4th Embodiment of this invention. It is a schematic block diagram of the control valve which concerns on the example of 5th Embodiment of this invention. It is an enlarged view of the control valve which concerns on the example of 5th Embodiment of this invention. It is a graph showing an example of the pressure in the reaction container of this invention. It is a schematic block diagram of the fuel cell system which concerns on the 6th Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydrogen generator 2 Reaction container 3 Solution liquid delivery means 4 Solution flow path 5 Liquid feed switching control part 6 Control valve 7 Solution introduction path 9, 28 Hydrogen generating substance 10 Hydrogen outlet flow path 11 Hydrogen generating substance residual quantity detection part 21 1st 1 solution introduction path 22 second solution introduction path 24 liquid feed switching section 25 rod spring 29 push spring 30 pressing section 31 first valve body 32 second valve body 33 rod section 40 fuel cell 41 fuel cell 42 fuel electrode chamber 43 Solution container 44 Reaction solution 50 Control valve 51 Connection portion 52 Third valve body 521 Connection spring 53 Seal portion 54 Drive portion 55 Liquid feed switching portion 56 Stopper body 57 Pressure receiving displacement portion 58 Drive portion space 59 Notch portion 60 Stopper push spring

Claims (8)

A hydrogen generating substance is contained, and a reaction vessel for generating hydrogen by reacting the hydrogen generating substance and a reaction solution;
A solution flow path for circulating the reaction solution;
Solution feeding means for introducing the reaction solution into the solution flow path;
A first solution introduction path for introducing the reaction solution into the first hydrogen generating material;
A second solution introduction path for introducing the reaction solution into the second hydrogen generating material;
A hydrogen outlet passage for discharging hydrogen generated in the reaction vessel;
A control valve for switching the feeding of the reaction solution from one of the first solution introduction path and the second solution introduction path to the other;
The control valve includes a liquid feed switching unit that switches the liquid feed from the first solution introduction path to the second solution introduction path as the first hydrogen generating substance is consumed. Generator.   The liquid feed switching unit feeds liquid from the first solution introduction path to the second solution introduction path when the supply amount of the reaction solution to the first solution introduction path reaches a predetermined amount. The hydrogen generator according to claim 1, wherein: The control valve includes a pressing portion that presses the hydrogen generating material as the hydrogen generating material reacts,
The liquid feeding switching unit is pressed by the pressing unit as the hydrogen generating material decreases, and switches the liquid feeding from the first solution introduction path to the second solution introduction path. The hydrogen generator described. The liquid feeding switching unit is
A first valve body that switches to one of a closed state that closes the first solution introduction path and an open state that opens the first solution introduction path;
A second valve body that switches to one of a closed state that closes the second solution introduction path and an open state that opens the second solution introduction path;
A rod portion that connects the first valve body and the second valve body, and closes the first valve body and displaces the second valve body in accordance with the displacement of the pressing portion; The hydrogen generator according to claim 3. The control valve includes a pressure receiving displacement portion that is displaced with a change in pressure in the reaction vessel,
The liquid feeding switching unit switches the liquid feeding from the first solution introduction path to the second solution introduction path according to the displacement of the pressure receiving displacement part as the pressure in the reaction vessel decreases. The hydrogen generator according to claim 1. The liquid feeding switching unit is
One of a first state in which the first solution introduction path is opened and the second solution introduction path is closed, and a second state in which the first solution introduction path is closed and the second solution introduction path is opened. A third valve body that switches to one state;
6. A connecting portion that is connected to the third valve body and switches the third valve body from the first state to the second state in accordance with the displacement of the pressure receiving displacement portion. Hydrogen generator.   The hydrogen generator according to any one of claims 1 to 6, further comprising a partition portion that partitions the first hydrogen generating material and the second hydrogen generating material.   8. The fuel cell, wherein the hydrogen outlet flow path of the hydrogen generator according to claim 1 is connected to a fuel electrode chamber of a fuel cell, and the generated hydrogen is supplied to the fuel electrode. system.

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