JP5207441B2 - Hydrogen generator and fuel cell system - Google Patents

Description

  The present invention relates to, for example, a hydrogen generator that decomposes a metal hydride to generate hydrogen and a fuel cell system that uses hydrogen generated by the hydrogen generator as fuel.

  Due to the recent increase in energy problems, there is a demand for a power source with higher energy density and clean emissions. A fuel cell is a generator having an energy density several times that of an existing cell, has high energy efficiency, and is characterized by no or little nitrogen oxides and sulfur oxides contained in exhaust gas. Therefore, it can be said that it is a very effective device that meets the demand as a next-generation power supply device.

  In a fuel cell that obtains an electromotive force by an electrochemical reaction between hydrogen and oxygen, hydrogen is required as a fuel. An example of an apparatus for generating hydrogen gas includes, for example, a reaction vessel containing a reactant solid such as a metal hydride (borohydride salt) and a solution vessel containing a reaction solution such as water. When the pressure in the reaction vessel drops below the pressure in the solution vessel, the reaction solution in the solution vessel is sent to the reaction vessel and hydrogen is generated by the reaction between the metal hydride and the reaction solution (hydrogen generation reaction). There is a hydrogen generator to be used (for example, see Patent Document 1).

  In a hydrogen generator used in such a fuel cell or the like, it is necessary to detect the remaining amount of fuel (hydrogen). Since it is difficult to visually confirm the remaining amount of hydrogen (fuel) generated in the hydrogen generator, various methods other than visual inspection have been proposed. For example, there is one in which the pressure in a tank filled with a hydrogen storage alloy is detected, and the remaining amount of fuel is detected based on this pressure (see, for example, Patent Document 2).

JP 2006-160545 A JP 2007-80632 A

  For example, if the pressure in the reaction vessel is always detected in the apparatus of Patent Document 1, the remaining amount of fuel (hydrogen) may be obtained from the pressure, but the consumption used for detecting the pressure in the reaction vessel There is a problem that electric power is large. In a fuel cell using a hydrogen generator, if the remaining amount of fuel in the hydrogen generator is constantly detected, the power consumption used for the detection is large, and the amount of power used for the electronic device connected to the fuel cell is small. There is a problem that it will decrease.

  In order to suppress the power consumption used for fuel remaining amount detection (pressure detection), for example, it is conceivable to perform pressure detection at regular intervals. However, the pressure in the reaction vessel does not always change constantly. For example, in the apparatus of Patent Document 1, the pressure in the reaction vessel repeatedly decreases and increases, but the timing is not constant. For this reason, it is difficult to obtain an accurate fuel remaining amount if pressure is detected at regular intervals.

  Further, in the case of an apparatus that generates hydrogen by the hydrogen generation reaction described above, products other than hydrogen generated during the hydrogen generation reaction adhere to the reactant solid, and the amount of hydrogen generated, that is, depending on the degree of adhesion of this product, that is, There may be a change in the pressure in the reaction vessel. For this reason, there is a possibility that the remaining amount of fuel cannot be accurately obtained only by detecting the pressure in the reaction vessel.

  The present invention has been made in view of such circumstances, and provides a hydrogen generator and a fuel cell system capable of accurately grasping the remaining amount of fuel (remaining amount of hydrogen) with less power consumption. With the goal.

A first aspect of the present invention that solves the above problems includes a solution container that contains a reaction solution, a reaction container that contains a reactant solid that generates hydrogen by reaction with the reaction solution, and the solution container. A hydrogen generation apparatus having a liquid supply path communicating with the reaction container, wherein the reaction solution is supplied from the solution container to the reaction container when an internal pressure of the reaction container is equal to or lower than an internal pressure of the solution container A detection means for detecting the start and stop of the supply of the reaction solution from the solution container to the reaction container, and the length of the reaction solution supply period triggered by the detection by the detection means. Measuring means for measuring, and remaining amount calculating means for calculating the remaining amount of hydrogen generated by the reaction between the reactant solid and the reaction solution based on the measurement value by the measuring means, and the liquid feeding Provided on the road Open / close means that is a check valve that opens the liquid supply path and allows the reaction solution to be transferred from the reaction container to the reactant solution when the internal pressure of the container is equal to or lower than a predetermined pressure; and The opening / closing means also serves as the detecting means, and has a conductive portion and a contact portion that contact when the valve body constituting the check valve is in a closed state, and the conductive portion and the contact portion are electrically connected. The hydrogen generating apparatus is characterized in that the start and stop of liquid feeding of the reaction solution are detected from the state .

In the first aspect, since the remaining amount of hydrogen (remaining amount of fuel) is calculated from the length of the reaction solution feeding period, the power consumption required to acquire the remaining amount of fuel can be greatly reduced. . Further, by detecting the start and stop of liquid supply of the reaction solution, it is possible to further reduce the power consumption necessary for acquiring the remaining fuel amount. In addition, since electric power is not required for detecting the start and stop of liquid supply of the reaction solution, the amount of power consumption required to acquire the remaining amount of fuel can be further reduced.

  The second aspect of the present invention further includes a storage unit in which a table in which the length of the liquid feeding period and the remaining amount of hydrogen are associated with each other is stored in advance, and the remaining amount calculating unit is a measurement value by the measuring unit. The remaining amount of hydrogen is calculated from the table and the table.

  In the second aspect, the remaining fuel amount can be obtained more accurately and easily by referring to the table as described above.

  The third aspect of the present invention further includes a storage unit that stores the measurement value of the measurement unit, and the remaining amount calculation unit is stored in the storage unit with the latest measurement value by the measurement unit. The hydrogen generator according to the first or second aspect is characterized in that the hydrogen remaining amount is calculated based on a difference from a previous measurement value.

  In the third aspect, the remaining amount of fuel is calculated based on the amount of change in the length of the reaction solution feeding period. Thereby, the remaining amount of fuel can be calculated more accurately.

A fourth aspect of the present invention is the hydrogen generator according to any one of the first to third aspects, wherein the reaction solution is fed to the reaction vessel at a constant flow rate.

In the fourth aspect, since the change in the remaining amount of fuel is stable, the remaining amount of fuel can be obtained more accurately.

A fifth aspect of the present invention includes an anode chamber to which hydrogen is supplied, and the hydrogen generator according to any one of the first to fourth aspects is provided as means for supplying hydrogen to the anode chamber. In the fuel cell system.

In the fifth aspect, the power generation amount can be improved. In addition, since the remaining amount of fuel is accurately known, the fuel can be used to the end.

  The hydrogen generator of the present invention can determine the remaining amount of hydrogen (remaining amount of fuel) generated by hydrogen generation relatively easily and accurately. Moreover, the power consumption used when calculating | requiring the fuel remaining amount can be suppressed very little. Therefore, in the fuel cell system of the present invention, the power generation amount can be improved. Further, by accurately grasping the remaining amount of fuel, it becomes possible to use the fuel to the end, and the economic efficiency is improved.

  Hereinafter, the present invention will be described in detail based on embodiments.

(Embodiment 1)
FIG. 1 is a diagram showing a schematic configuration of a hydrogen generator according to Embodiment 1 of the present invention.

  As shown in FIG. 1, a hydrogen generator 10 according to this embodiment includes a reaction vessel 12 that stores a reactant solid 11 that is a hydrogen generating material, a solution vessel 14 that contains a reaction solution 13, and this solution. A liquid supply pipe 15 that is a liquid supply path for communicating the container 14 and the reaction container 12 is provided. Then, the reaction solution 13 in the solution container 14 is sent to the reactant solid 11 in the reaction container 12 through the liquid feeding tube 15, and the reactant solid 11 and the reaction solution 13 react (hydrogen generation reaction). By doing so, hydrogen as a fuel is generated.

Here, examples of the reactant solid (hydrogen generating substance) 11 held in the reaction vessel 12 include metal hydride compounds such as sodium borohydride, potassium borohydride, lithium aluminum hydroxide, and the like. In the form, sodium borohydride (NaBH ₄ ) is used. On the other hand, as the reaction solution supplied to the reactant solid, an aqueous solution of an accelerator, for example, an aqueous solution of malic acid, citric acid, succinic acid or the like is preferably used, but water can also be used. In this embodiment, malic acid aqueous solution is used. The reactant solid 11 and the reaction solution 13 are not particularly limited, and any reactant solid 11 can be applied as long as it is a hydrolyzable metal hydride. Any hydrogen generation catalyst such as acid and inorganic acid or ruthenium is applicable. Further, for example, malic acid powder that is a hydrogen generation catalyst may be held in the reaction vessel 12, and an aqueous solution of sodium borohydride that is a hydrogen generation material may be supplied to the reaction vessel 12 to cause a hydrogen generation reaction. Furthermore, a base metal can be used as the hydrogen generating material. In this case, the reaction solution 13 may be a basic or acidic aqueous solution or water.

  The reaction vessel 12 is connected to one end of a discharge pipe 16 for discharging the hydrogen generated by the reaction between the reactant solid 11 and the reaction solution 13 (hydrogen generation reaction) to the outside. Although the other end side of 16 is not shown in figure, it is connected to the electric power generation part etc. of a fuel cell, for example.

  The reaction solution 13 in the solution container 14 is always given a predetermined pressure by a pressurizing means (not shown). When the internal pressure of the reaction container 12 falls below the internal pressure of the solution container 14, the reaction solution 13 is fed from the solution container 14 into the reaction container 12 through the liquid feeding tube 15 at a constant flow rate. That is, the feed amount of the reaction solution 13 is controlled so that the amount of hydrogen generated in the reaction vessel 12 is always within a predetermined range. The liquid supply pipe 15 may be provided with opening / closing means such as a pressure adjusting valve that opens the flow path of the liquid supply pipe 15 when the internal pressure of the reaction container 12 becomes equal to or lower than the internal pressure of the solution container 14.

  Here, for example, when a certain amount of hydrogen is discharged from the reaction vessel 12 to the outside through the discharge pipe 16, the hydrogen generation reaction is intermittently performed, so that the reaction solution 13 is also intermittently accompanied by the hydrogen generation reaction. Then, the solution is sent to the reaction vessel 12. FIG. 2 is a graph showing changes in pressure in the reaction vessel and changes in the remaining amount of fuel (remaining amount of generated hydrogen) when such an intermittent hydrogen generation reaction is caused.

  In this embodiment, since hydrogen is discharged at a constant flow rate, the internal pressure of the reaction vessel 12 decreases with a constant gradient as the hydrogen is discharged, and the internal pressure of the reaction vessel 12 is the reference pressure as shown in FIG. In this embodiment, when the pressure falls below the internal pressure of the solution container 14, it starts to rise. That is, when the reaction solution 13 is sent to the reaction vessel 12 and hydrogen is generated by the hydrogen generation reaction, the internal pressure of the reaction vessel 12 starts to increase. When the internal pressure of the reaction vessel 12 exceeds the reference pressure, the feeding of the reaction solution 13 is stopped. Even after the liquid feeding is stopped, the hydrogen generation reaction is continued for a while, so that the internal pressure of the reaction vessel 12 continues to rise. When the hydrogen generation reaction is stopped, the internal pressure of the reaction vessel 12 again decreases with a constant gradient. As described above, the reaction solution 13 is intermittently fed, that is, in the period T1 to T4 in FIG. 2, and the internal pressure of the reaction vessel 12 repeatedly increases and decreases accordingly.

  When the reaction solution 13 is sent to the reaction vessel 12 and a hydrogen generation reaction occurs, the remaining amount of hydrogen (remaining fuel) generated by the hydrogen generation reaction gradually decreases. That is, while the hydrogen generation reaction is occurring, the remaining amount of fuel decreases with a predetermined gradient. Further, as the hydrogen generation reaction proceeds, the concentration of the reactant solid 11 gradually decreases, so the reaction rate of the hydrogen generation reaction decreases. For this reason, the time until the pressure in the reaction vessel 12 reaches the reference pressure gradually increases. For example, the lengths of the periods T1 to T4 in FIG. 2 are T1 <T2 <T3 <T4, and the time for feeding the reaction solution 13 is gradually increased.

  In this embodiment, since sodium borohydride is used as the reactant solid 11, a reaction product other than hydrogen is generated during the hydrogen generation reaction. This reaction product adheres to the surface of the reactant solid 11 and inhibits the hydrogen generation reaction. For this reason, although depending on the degree of adhesion of the reaction product, the reaction rate of the hydrogen generation reaction gradually decreases. That is, not only the decrease in the concentration of the reactant solid 11 but also the liquid feeding time of the reaction solution 13 may become longer gradually due to other factors.

  The present invention is characterized in that the remaining amount of fuel is calculated from the length of the reaction solution feeding period based on such knowledge. Specifically, a detection unit 17 as a detection unit that detects the start and stop of the supply of the reaction solution 13 is provided in the liquid supply tube 15, and the detection of the reaction solution is triggered by the detection by the detection unit 17. Measuring means 18 for measuring the length of the liquid period, and remaining amount calculating means 19 for calculating the remaining amount of fuel (remaining hydrogen amount) generated by the hydrogen generation reaction based on the measurement value by the measuring means 18.

  If the detection part 17 can detect the liquid feeding start and liquid feeding stop of the reaction solution 13, the structure will not be specifically limited. Specifically, for example, a pitot tube is arranged in the liquid feeding tube 15 and the liquid feeding start and the liquid feeding stop are detected by the pressure difference. Further, for example, a liquid feeding start and stop is made from an electromotive force generated by a conductive reaction solution 13 flowing through the liquid feeding pipe 15, which is composed of a pair of electromagnetic coils arranged with the liquid feeding pipe 15 interposed therebetween. May be detected. Further, the start and stop of liquid feeding may be detected from the time difference caused by the flow of ultrasonic waves propagating to the reaction solution 13 in the liquid feeding pipe 15.

  When the detection unit 17 detects the start of liquid feeding, the measurement unit 18 starts measuring time using the detection as a trigger. When the detection unit 17 detects liquid feeding stop, the measurement unit 18 stops measuring time using the detection as a trigger. . Thereby, the length of the liquid feeding period of the reaction solution 13 is measured.

  As described above, there is a relationship as shown in FIG. 2 between the length of the liquid feeding period of the reaction solution 13 and the remaining amount of fuel. In this embodiment, the length of the liquid feeding period is The storage unit 20 further stores in advance a table that associates the remaining fuel amount (remaining hydrogen amount). The remaining amount calculating unit 19 calculates the remaining amount of fuel from the measurement value obtained by the measuring unit 18 and the table stored in the storage unit 20. The table stored in the storage unit 20 is created taking into account, for example, a decrease in the reaction rate due to the reaction product resulting from the hydrogen generation reaction adhering to the reactant solid 11. In addition, since the reaction rate of the hydrogen generation reaction also changes depending on the flow rate of the reaction solution 13, this point needs to be taken into consideration when the flow rate of the reaction solution is not constant.

  Thus, by calculating the remaining amount of fuel from the length of the liquid feeding period of the reaction solution 13, the remaining amount of fuel can be acquired relatively easily and accurately. Moreover, since the measurement means 18 measures the length of the liquid feeding period of the reaction solution 13 using the detection of the detection unit 17 as a trigger, the power consumption by this measurement can be suppressed to an extremely low level. For example, compared with the case where the remaining amount of fuel is obtained by constantly measuring the internal pressure of the reaction vessel 12, the power consumption can be greatly reduced.

  In the present embodiment, the remaining amount calculation means 19 calculates the remaining amount of fuel from the length of the liquid feeding period, but the calculation method is not limited to this. For example, the length of each liquid delivery period measured by the measuring unit 18 is stored in the storage unit 20, and the remaining amount calculating unit 19 is stored in the storage unit 20 with the latest measured value by the measuring unit 18. The remaining fuel amount may be calculated based on the difference from the previous measured value. For example, taking the graph of FIG. 2 as an example, the remaining amount of fuel is calculated based on the difference between the length of the liquid feeding period T4 that is the latest measured value and the length of the liquid feeding period T3 that is the previous measured value. You may do it. Even if the remaining fuel amount is calculated in this way, the remaining fuel amount can be acquired relatively easily and accurately.

(Embodiment 2)
FIG. 3 is a cross-sectional view illustrating a schematic configuration of the hydrogen generator according to Embodiment 2, and FIG. 4 is a cross-sectional view illustrating a liquid feeding pipe portion of the hydrogen generator. The present embodiment is an example in which the detection means is changed, and the other configuration is the same as that of the first embodiment. For this reason, the same code | symbol is attached | subjected to the same member and the overlapping description is abbreviate | omitted.

  As shown in the figure, a check valve 21 as an opening / closing means is provided in the liquid feeding pipe 15 that connects the solution container 14 and the reaction container 12. Thereby, only the flow of the reaction solution 13 from the solution container 14 to the reaction container 12 is allowed, and the backflow from the reaction container 12 to the solution container 14 is prevented. In this embodiment, the check valve 21 is also an example of detecting means, and the start and stop of liquid feeding of the reaction solution 13 to the reaction container 12 are detected from the open / closed state of the check valve 21. doing. Specifically, as shown in FIG. 4, the check valve 21 according to the present embodiment is a cylinder made of an elastic member, for example, a rubber material such as butyl rubber or nitrile rubber, polyethylene terephthalate (PET), silicone, or the like. It is comprised by the shaped valve body 22. FIG. The valve body 22 is formed in a tapered shape in which the thickness of the flow path gradually decreases from one end side thereof, and the other end side opening 22a is formed in a slit shape. And the one end part side of the valve body 22 is fixed in the liquid feeding pipe | tube 15 so that the slit-shaped edge part side opening 22a may become the reaction container 12 side, and the non-return valve 21 is comprised.

  In the state where the reaction solution 13 is not fed, the check valve 21 has the other end side opening 22a of the valve body 22 closed as shown in FIG. When the reaction solution is fed to 12, the valve body 22 is elastically deformed by the flow and the other end side opening 22a is opened as shown in FIG. 4 (b). Note that the opening 22 a of the valve body 22 does not open in the flow from the reaction vessel 12 toward the solution vessel 14.

  A pair of conductive portions 23 and contact portions 24 made of a conductive material such as a metal material are provided at the edge of the opening 22a of the valve body 22, for example. The conductive portion 23 and the contact portion 24 are provided so as to be in contact with each other when the valve body 22 opening 22a is closed and to be separated when the opening 22a is opened. In addition, the conductive portion 23 and the contact portion 24 are connected to a pair of terminal portions 25 and 26 provided in the liquid feeding tube 15 by a wiring 27, respectively.

  For example, from the resistance value between these terminal portions 25 and 26, the start and stop of the feeding of the reaction solution 13 are detected by the conduction state between the conductive portion 23 and the contact portion 24. That is, the start of liquid feeding is detected by separating from the state in which the conductive portion 23 and the contact portion 24 are in contact with each other, and then the stop of liquid feeding is detected by the contact between the conductive portion 23 and the contact portion 24. Then, the measuring means 18 measures the length of the liquid feeding period of the reaction solution 13 triggered by the detection of the liquid feeding start and the liquid feeding stop, and the remaining amount calculating means 19 uses the measurement result and the table of the storage unit 20. Based on the above, the remaining fuel amount is calculated.

  In such a configuration of the present embodiment, since the detection of the liquid feeding start and the liquid feeding stop is clarified, the length of the liquid feeding period can be measured more accurately. Therefore, by calculating the fuel remaining amount based on the measurement result, it is possible to obtain a very accurate fuel remaining amount. In addition, since the configuration of the detection unit is simplified, it is possible to further reduce the amount of power consumption necessary for obtaining the remaining amount of fuel. Furthermore, by providing the check valve 21 in the liquid feeding pipe 15, the backflow of the reaction solution 13 from the reaction container 12 to the solution container 14 is prevented, and the liquid feeding stability of the reaction solution 13 is improved. You can also.

  In addition, although an example of the check valve was shown in FIG. 4, the structure of this check valve is not specifically limited. For example, as shown in FIG. 5, the check valve 21 </ b> A may be configured such that one end side of the valve body 22 </ b> A is rotatably supported by the valve shaft 28 in the liquid feeding pipe 15. In this example, the liquid feeding pipe 15 has a small diameter portion 15a and a large diameter portion 15b having an inner diameter larger than that of the small diameter portion 15a, and a valve body 22A is arranged at a boundary portion between the small diameter portion 15a and the large diameter portion 15b. Has been. The check valve 21A has an interference portion 15c that is a step at the boundary between the small diameter portion 15a and the large diameter portion 15b as shown in FIG. 5A when the reaction solution 13 is not being fed. When the reaction solution 13 is fed from the solution container 14 to the reaction container 12 as shown in FIG. The valve body 22A rotates about the valve shaft 28, and the flow path is opened.

  When such a check valve 21A is used, the valve body 22A itself is formed of a conductive material to form a conductive portion 23A. The end of the valve body 22A on the valve shaft 28 side is connected to one terminal portion 25A provided in the liquid feeding pipe 15, and the other terminal portion 26A is configured such that the valve body 22A which is the conductive portion 23A is an interference portion. It also serves as a contact portion 24A that is electrically connected in contact with 15c. Even in such a configuration, as described above, the start and stop of the feeding of the reaction solution 13 are detected from the contact state between the conductive portion 23A and the contact portion 24A.

(Embodiment 3)
FIG. 6 is a cross-sectional view showing a schematic configuration of the hydrogen generator according to Embodiment 3, and FIG. 7 is a cross-sectional view showing a liquid feed pipe portion. The present embodiment is an example in which the detection means is changed, and the other configuration is the same as that of the first embodiment. For this reason, the same code | symbol is attached | subjected to the same member and the overlapping description is abbreviate | omitted.

  In the present embodiment, as shown in the figure, a pressure adjusting valve 29 is provided in the liquid feeding pipe 15, and a switch member 30 is disposed in the vicinity of the pressure adjusting valve 29, and the detecting means is used for these pressure adjusting valves. 29 and an example of a switch member 30. In this example, the start and stop of the feeding of the reaction solution 13 are detected from the pressed state of the switch member 30 by the pressure regulating valve 29.

  The pressure regulating valve 29 includes a first pressure deforming portion 33 made of a flexible sheet and deformable in the thickness direction so as to close both sides in the thickness direction of the base 31 of the through portion 32 provided in the base 31. A second pressure deforming portion 34 is provided. A communication passage 35 communicating with the reaction vessel 12 is provided outside the first pressure deformation portion 33, and the first pressure deformation portion 33 receives the internal pressure of the reaction vessel 12 from the outside. On the other hand, the outside of the second pressure deforming portion 34 is open to the outside, and the second pressure deforming portion 34 receives atmospheric pressure from the outside.

  The space between the first and second pressure deformation portions 33 and 34 of the penetrating portion 32 is partitioned by a partition member 36 provided in the middle in the thickness direction of the base 31, and the first pressure deformation portion 33. The first flow path 37 and the second pressure deforming portion 34 side become the second flow path 38, respectively, extending in the plane direction of the base 31, and the first flow path 37 and the second flow path 38 is communicated with a through hole 39 provided in the partition member 36. The first flow path 37 and the second flow path 38 constitute a part of the liquid feeding pipe 15, the first flow path 37 communicates with the reaction vessel 12, and the second flow path 38 is It communicates with the solution container 14.

  Further, in the space between the first and second pressure deforming portions 33 and 34 of the penetrating portion 32, the first and second pressure deforming portions 33 and 34 are connected to the first and second pressure deforming portions 33 and 34. A valve member 40 that moves between two points in the vertical direction in the figure is provided together with the pressure deforming portions 33 and 34. The valve member 40 connects the first and second pressure deforming portions 33 and 34 and is provided on the first pressure deforming portion 33 side of the connecting portion 41 disposed through the through hole 39 and the connecting portion 41. And a valve portion 42 that can open and close the through hole 39.

  In the present embodiment, the switch member 30 is disposed adjacent to the pressure regulating valve 29 at a position facing the penetrating portion 32 of the pressure regulating valve 29. As will be described below, the switch member 30 is pressed when the valve member 40 of the pressure regulating valve 29 is in a predetermined position. Then, by electrically detecting whether or not the valve member 40 is pressing the switch member 30, the liquid feeding start and the liquid feeding stop of the reaction solution 13 are detected.

  Specifically, first, in a state where the internal pressure of the reaction vessel 12 received by the first pressure deformation section 33 is higher than the atmospheric pressure received by the second pressure deformation section 34, as shown in FIG. The second pressure deforming portions 33 and 34 together with the valve member 40 move upward in the figure, the valve portion 42 contacts the partition member 36, and the through hole 39 is closed, that is, the first flow path 37. And the communication between the second flow path 38 and the second flow path 38 are blocked. Further, the switch member 30 is pressed by the connecting portion 41 of the valve member 40.

  On the other hand, when the internal pressure of the reaction vessel 12 received by the first pressure deformation section 33 is lower than the atmospheric pressure received by the second pressure deformation section 34, as shown in FIG. The pressure deformation portions 33 and 34 are moved downward in the figure together with the valve member 40 so that the valve portion 42 is separated from the partition member 36 and the through-hole 39 is opened, that is, the first flow path 37 and the second flow passage. The flow path 38 is in communication with each other. Further, the connecting portion 41 of the valve member 40 is in a state separated from the switch member 30. In this state, the reaction solution 13 is fed from the solution container 14 to the reaction container 12 through the second flow path 38 and the first flow path 37 that are part of the liquid feed pipe 15. When the hydrogen generation reaction occurs due to the feeding of the reaction solution 13 and the internal pressure of the reaction vessel 12 becomes higher than the atmospheric pressure, the closed state is again established as described above. In the present embodiment, the second pressure deforming portion 34 is subjected to atmospheric pressure. However, for example, the second pressure deforming portion 34 is biased by a spring member or the like so that the reaction solution 13 is fed. The liquid pressure may be adjusted.

  As described above, in this embodiment, when the valve member 40 is separated from the switch member 30, the start of the liquid supply of the reaction solution 13 is detected, and when the valve member 40 presses the switch member 30, the liquid supply stop is detected. . Then, the measuring means 18 measures the length of the liquid feeding period of the reaction solution 13 triggered by the detection of the liquid feeding start and the liquid feeding stop, and the remaining amount calculating means 19 determines the remaining fuel amount based on the measurement result. calculate.

  In such a configuration of the present embodiment, no electric power is required for opening / closing control of the valve member 40. Since the start and stop of the feeding of the reaction solution 13 are detected depending on whether or not the switch member 30 is mechanically pressed by the valve member 40, no electric power is required for the detection. Therefore, it is possible to further reduce the amount of power consumption necessary for obtaining the remaining amount of fuel. In addition, since the switch member 30 is disposed outside the liquid feeding pipe 15, there is also an effect that corrosion of wiring and the like for sending an electric signal from the switch member 30 can be prevented.

(Embodiment 4)
FIG. 8 is a cross-sectional view showing a schematic configuration of a hydrogen generator according to Embodiment 4 of the present invention. In addition, this embodiment is an example which has arrange | positioned the solution container in reaction container, The same code | symbol is attached | subjected to the same member and the overlapping description is abbreviate | omitted.

  In the present embodiment, as shown in FIG. 8, a solution container 14A is provided in the reaction container 12A, and the reaction container 12A and the solution container 14A are connected by a liquid feeding pipe 15A arranged in the reaction container 12A. Has been. The liquid feeding pipe 15A is arranged so that the tip thereof faces the reactant solid 11 held in the reaction vessel 12A, and the reaction solution 13 fed through the liquid feeding pipe 15A is a reactant. The solid 11 is directly injected.

  14 A of solution containers which concern on this embodiment consist of a bag member of flexible materials, such as a resin material and rubber | gum, for example, The bottom part is being fixed in 12 A of reaction containers. Specific examples of the material for the solution container 14A include polypropylene, PET, silicone, silicone rubber, butyl rubber, and isoprene rubber. An urging member 43 made of, for example, a spring member is provided between the upper surface side of the solution container 14A and the upper wall surface of the reaction container 12A, and the urging member 43 urges the solution container 14A. . In addition, as a spring member which comprises the urging | biasing member 43, a constant load spring, a compression coil spring, etc. are used suitably, for example. Of course, the biasing member 43 is not limited to a spring member as long as it can bias the solution container 14A.

  As described above, the liquid feeding tube 15A is provided with the detection unit 17, and the measurement means 18 measures the length of the liquid feeding period of the reaction solution 13 using the detection of the detection unit 17 as a trigger, and the remaining amount. The calculation means 19 calculates the remaining fuel amount based on the measurement result and the table in the storage unit 20.

  In such a configuration of the present embodiment, the remaining amount of fuel can be acquired relatively easily and accurately as in the above-described embodiment. In the configuration of the present embodiment, as the reaction solution 13 in the solution container 14A is supplied to the reactant solid 11 in the reaction container 12A, the solution container 14A is urged by the urging force of the urging member 43. Volume decreases. For this reason, the volume of the reaction container 12A increases by the volume decrease of the solution container 14A. Therefore, there is no dead space, the area where hydrogen is generated in a small space can be increased, and space can be saved without reducing the amount of hydrogen generation. In addition, the amount of hydrogen generation can be increased without increasing the space.

(Embodiment 5)
FIG. 9 is a schematic configuration diagram showing an example of a fuel cell system according to Embodiment 5 of the present invention. In addition, the same part is attached | subjected to the same member and the overlapping description is abbreviate | omitted.

  The fuel cell system according to this embodiment shown in FIG. 9 is a system in which the hydrogen generator 10 shown in FIG. 1 is connected to a fuel cell. That is, the fuel cell 50 is provided with an anode chamber 51, and the anode chamber 51 constitutes a space in contact with the anode chamber of the fuel cell 52. The anode chamber is a space that temporarily holds hydrogen consumed by the anode. The anode chamber 51 and the reaction vessel 12 are connected by a discharge pipe 16, and hydrogen generated in the reaction vessel 12 is supplied to the anode chamber of the anode chamber 51. The hydrogen supplied to the anode chamber is consumed by the fuel cell reaction at the anode. The amount of hydrogen consumed at the anode is determined according to the output current of the fuel cell 50.

  In the fuel cell system having such a configuration, the remaining amount of fuel of the hydrogen generator 10 such as a fuel cartridge can be accurately grasped, and power consumption for detecting the remaining amount of fuel is suppressed. The power generation amount can be improved. In addition, the fuel can be used up to the end, and the economy is improved.

  As mentioned above, although each embodiment of this invention was described, this invention does not need to be limited to these embodiment. Moreover, it cannot be overemphasized that the structure of each above-mentioned embodiment may be combined.

It is sectional drawing which shows schematic structure of the hydrogen generator which concerns on Embodiment 1 of this invention. It is a graph which shows the relationship between time passage, fuel remaining amount, and the internal pressure of reaction container. It is sectional drawing which shows schematic structure of the hydrogen generator which concerns on Embodiment 2 of this invention. It is sectional drawing which shows the liquid feeding pipe part which concerns on Embodiment 2 of this invention. It is sectional drawing which shows the modification of the liquid feeding pipe part which concerns on Embodiment 2 of this invention. It is sectional drawing which shows schematic structure of the hydrogen generator which concerns on Embodiment 3 of this invention. It is sectional drawing which shows the liquid feeding pipe part which concerns on Embodiment 3 of this invention. It is sectional drawing which shows schematic structure of the hydrogen generator which concerns on Embodiment 4 of this invention. It is a schematic block diagram which shows an example of the fuel cell system which concerns on Embodiment 5 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Hydrogen generator 11 Reactant solid 12 Reaction container 13 Reaction solution 14 Solution container 15 Liquid supply pipe 16 Discharge pipe 17 Detection part 18 Measurement means 19 Remaining amount calculation means 20 Storage part 21 Check valve 22 Valve body 23 Conductive part 24 Contact Portions 25 and 26 Terminal portion 27 Wiring 28 Valve shaft 29 Pressure regulating valve 30 Switch member 31 Base body 32 Penetration portion 33 First pressure deformation portion 34 Second pressure deformation portion 35 Communication passage 36 Partition member 37 First flow passage 38 Second flow path 39 Through hole 40 Valve member 41 Connecting portion 42 Valve portion 43 Energizing member 50 Fuel cell

Claims (5)

A solution container in which a reaction solution is stored; a reaction container in which a reactant solid that generates hydrogen by reaction with the reaction solution is stored; and a liquid supply path that connects the solution container and the reaction container. A hydrogen generating apparatus in which the reaction solution is fed from the solution container to the reaction container when the internal pressure of the reaction container is equal to or lower than the internal pressure of the solution container,
Detection means for detecting the start and stop of the supply of the reaction solution from the solution container to the reaction container, and a measurement means for measuring the length of the reaction solution supply period triggered by detection by the detection means And a remaining amount calculating means for calculating the remaining amount of hydrogen generated by the reaction between the reactant solid and the reaction solution based on the measurement value by the measuring means ,
A check that is provided in the liquid feeding path and allows the liquid feeding of the reaction solution from the reaction container to the reactant solution by opening the liquid feeding path when the internal pressure of the reaction container is equal to or lower than a predetermined pressure. Having an opening and closing means that is a valve;
The opening / closing means also serves as the detection means, and has a conductive portion and a contact portion that contact when the valve body constituting the check valve is in a closed state. A hydrogen generating apparatus, wherein the start and stop of liquid supply of the reaction solution are detected from a conductive state . A table that associates the length of the liquid feeding period with the remaining amount of hydrogen is further stored in advance,
2. The hydrogen generation apparatus according to claim 1, wherein the remaining amount calculating unit calculates the hydrogen remaining amount from a measurement value obtained by the measuring unit and the table. A storage unit for storing a measurement value of the measurement unit;
2. The remaining amount calculating unit calculates the remaining hydrogen amount based on a difference between a latest measured value obtained by the measuring unit and a previous measured value stored in the storage unit. Or the hydrogen generator of 2. The hydrogen generating apparatus according to any one of claims 1 to 3 , wherein the reaction solution is sent to the reaction vessel at a constant flow rate. A fuel cell system comprising an anode chamber to which hydrogen is supplied and the hydrogen generator according to any one of claims 1 to 4 as means for supplying hydrogen to the anode chamber.

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