JP2009040625A - Hydrogen generating apparatus, fuel cell apparatus and hydrogen generating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen generating apparatus capable of supplying hydrogen while reliably suppressing outflow of reaction residues obtained by bringing a reactant into contact with an aqueous solution in a small space. <P>SOLUTION: A measurement section 7 detects the surface height of reaction residues 10, and when a control unit 9 judges that the increment of the reaction residues 10 exceeds a predetermined amount, a solution feeding means 4 is controlled so as to stop circulation of the aqueous solution, whereby hydrogen generation reaction is stopped and outflow of the reaction residues 10 is reliably suppressed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrogen generation apparatus and a hydrogen generation method for supplying hydrogen generated by a chemical reaction to a device that requires hydrogen, such as a fuel cell or a hydrogen engine, or a hydrogen storage container, and suppresses the influence of reaction residues. It is what I did.

  The present invention also relates to a fuel cell facility equipped with a hydrogen generator capable of supplying hydrogen while suppressing the influence of reaction residues.

  Due to the recent increase in energy problems and environmental problems, there is an increasing expectation for hydrogen as a clean fuel other than fossil fuels. However, hydrogen has problems in all aspects such as production, storage, transportation, and utilization technology, and development of handling technology is urgent.

  Examples of the power generation device using hydrogen include a fuel cell and an internal combustion engine (hereinafter, hydrogen engine). These power generators cover all types of industries such as regional distributed power sources, buildings, homes, automobiles, and portable devices. In either case, it is necessary to supply a predetermined amount of hydrogen promptly. In particular, in automobiles and portable devices, the generated power is efficiently sent to a device that consumes power because of the space for installing the power generation device. Therefore, it is required that the hydrogen supplier and the hydrogen generating material have a high hydrogen storage density and generate hydrogen with low energy.

  Conventionally, as a method of obtaining hydrogen with low energy, a method of hydrolyzing a complex hydride called chemical hydride is known. For example, lithium borohydride, sodium borohydride, lithium aluminum hydride, and sodium aluminum hydride, which are a kind of complex hydrides, are dissolved in an alkaline aqueous solution, and the aqueous solution is supplied to and contacted with a noble metal catalyst to perform a hydrogen generation reaction. There are known a method for causing a hydrogen generation reaction by supplying water or alcohol to a complex hydride (for example, see Patent Document 1).

  In this case, the reactants of the hydrogen generation reaction are a complex hydride and water, and the catalyst has an effect of a promoter that promotes the hydrogen generation reaction. When hydrogen is generated by causing a hydrogen generation reaction, products such as metal-containing materials and bubbles generated by the reaction are present, and flow resistance is present in the flow path. .

  For this reason, the obtained hydrogen is put into a separation means room together with a product such as bubbles, hydrogen and the product (reaction residue) are separated in the separation means room, and the hydrogen from which the product is separated is used as a fuel cell. The technique of supplying to consumption parts, such as these, is known (for example, refer patent document 2, patent document 3). Since the reaction residue can be separated by providing the separation means room, the reaction residue is prevented from flowing out, and the product is separated and hydrogen is supplied to the consumption unit without reducing the reaction efficiency. can do.

  However, in the conventional technique, the reaction residue can be separated and the influence of the reaction residue flowing to the outside can be suppressed. However, since the technique is provided with a separate separation chamber, a certain amount of space is required. This is necessary and hinders downsizing. In addition, unreacted complex hydride (fuel) may be included as a reaction residue. If unreacted fuel remains as a reaction residue, it will cause an increase in the volume of the reaction residue even after hydrogen generation is stopped. Therefore, it is necessary to secure a sufficient volume of the separation unit, which also hinders downsizing. Furthermore, in order to use it in a very small space such as a small device, the space of other devices such as a reaction vessel has to be sacrificed, and the function must be lowered.

JP 2003-206101 A JP 2002-154803 A JP 2005-225709 A

  The present invention has been made in view of the above situation, and a hydrogen generator capable of supplying hydrogen in a state where the outflow of the reaction residue obtained by bringing the reactant into contact with the aqueous solution in a small space is reliably suppressed, and An object is to provide a hydrogen generation method.

  In addition, the present invention has been made in view of the above situation, and hydrogen generation that can supply hydrogen in a state where the outflow of the reaction residue obtained by bringing the reactant into contact with the aqueous solution in a small space is reliably suppressed. It aims at providing the fuel cell equipment provided with the apparatus.

  In order to achieve the above object, a hydrogen generator of the present invention according to claim 1 comprises a reaction vessel that contains a reaction product, reacts the reaction product with an aqueous solution to produce hydrogen, and the aqueous solution contains the reaction solution. An aqueous solution supply unit that supplies the reaction vessel, a liquid feeding control unit that controls the flow of the aqueous solution in the aqueous solution supply unit, a discharge unit that discharges hydrogen generated in the reaction vessel, and a reaction inside the reaction vessel A reaction residue amount detection unit for detecting the amount of the residue, and when the amount of the reaction residue detected by the reaction residue amount detection unit exceeds a predetermined amount, And a stop control unit for making the stop state.

  In the present invention according to claim 1, when the reaction residue exceeds a predetermined amount, the flow of the aqueous solution can be stopped to stop the hydrogen generation reaction. For this reason, it becomes possible to supply hydrogen in a state where the outflow of the reaction residue obtained by bringing the reactant into contact with the aqueous solution in a small space is reliably suppressed.

  The hydrogen generator of the present invention according to claim 2 is the hydrogen generator according to claim 1, wherein the reaction residue amount detection unit floats on the reaction residue and the reaction residue has the predetermined amount. It has a sealing float which closes the discharge part when it becomes.

  In the present invention according to claim 2, since the sealing float blocks the discharge part and stops the discharge of hydrogen when the reaction residue reaches a predetermined amount, an increase in the reaction residue can be detected with a simple structure. Can do.

  Moreover, the hydrogen generator of the present invention according to claim 3 is the hydrogen generator according to claim 2, wherein the stop control part is the reaction vessel in a state where the discharge part is blocked by the sealing float. The flow of the aqueous solution in the liquid feeding control unit is stopped based on the internal pressure.

  In the present invention according to claim 3, in response to an increase in the internal pressure of the reaction vessel caused by the discharge portion being blocked by the sealing float, the liquid feeding control unit operates in a state where the flow of the aqueous solution is stopped, and the reaction The operation is stopped based on the increase in internal pressure when the residue increases.

  Moreover, the hydrogen generator of the present invention according to claim 4 is the hydrogen generator according to claim 3, wherein the liquid supply control unit is a liquid supply control unit that stops the flow of the aqueous solution by a stop signal, The stop control unit includes an internal pressure detection unit that detects an internal pressure of the reaction vessel, and an output unit that outputs the stop signal to the liquid feeding control unit based on a signal from the internal pressure detection unit. To do.

  In the present invention according to claim 4, a stop signal is output to the liquid feeding control unit based on the signal of the internal pressure detection unit, the flow of the aqueous solution is stopped, and based on the increase in internal pressure when the reaction residue increases. To stop operation reliably.

  The hydrogen generator of the present invention according to claim 5 is the hydrogen generator according to claim 1, wherein the liquid supply control unit is a liquid supply control unit that stops the flow of the aqueous solution by a stop signal, The stop control unit outputs the stop signal when the amount of the reaction residue detected by the reaction residue amount detection unit exceeds a predetermined amount.

  In the present invention according to claim 5, when the amount of the reaction residue exceeds a predetermined amount by the reaction residue amount detection unit, a stop signal is output to the liquid feed control unit, the flow of the aqueous solution is stopped, and the reaction residue Stop operation reliably based on the increase in objects.

  According to a sixth aspect of the present invention, there is provided the hydrogen generating apparatus according to the third aspect, wherein the liquid supply control unit is configured to stop the flow of the aqueous solution when a predetermined pressure is applied. It is a control part, The said stop control part was provided with the action part which makes the internal pressure of the said reaction container act on the said liquid feeding control part, It is characterized by the above-mentioned.

  In the present invention according to claim 6, the pressure based on the increase in the internal pressure of the reaction vessel due to the discharge part being blocked by the sealing float acts on the liquid feeding control part, the flow of the aqueous solution is stopped, and the reaction residue The operation is stopped in conjunction with the increase in internal pressure when things increase.

  The hydrogen generator of the present invention according to claim 7 is the hydrogen generator according to claim 1, wherein the stop control unit is configured to control the reaction residue based on a detection value of the reaction residue amount detection unit. An amount increase rate is calculated, and when the increase rate exceeds a predetermined increase rate, the flow of the aqueous solution in the liquid feeding control unit is stopped.

  In the present invention according to claim 7, since the hydrogen generation reaction is stopped by stopping the flow of the aqueous solution when the increase rate of the reaction residue exceeds a predetermined acceleration, the reaction residue is determined based on the increase rate of the reaction residue. Can be surely eliminated.

  The hydrogen generator of the present invention according to claim 8 is the hydrogen generator according to claim 1, wherein the stop control unit is configured to control the reaction residue based on the detection value of the reaction residue amount detection unit. The amount increase rate is calculated, and the predetermined amount corresponding to the increase rate is set.

  In the present invention according to claim 8, since the flow of the aqueous solution is stopped and the hydrogen generation reaction is stopped when a predetermined amount corresponding to the increasing rate of the reaction residue is exceeded, the reaction based on the increasing amount of the reaction residue is performed. The outflow of the residue can be surely eliminated.

  The hydrogen generator of the present invention according to claim 9 is the hydrogen generator according to claim 7 or claim 8, wherein the reaction residue amount detection unit detects the height of the surface of the reaction residue. It is a non-contact type sensor.

  In the present invention according to claim 9, the height of the surface of the reaction residue is detected by a non-contact sensor, and when the increase rate of the reaction residue exceeds a predetermined increase rate, the aqueous solution in the liquid feeding control unit is circulated. To stop the operation.

  A hydrogen generation apparatus according to a tenth aspect of the present invention is the hydrogen generation apparatus according to the seventh or eighth aspect, wherein the reaction residue amount detection unit includes a float floating on the reaction residue, a float of the float It comprises a displacement sensor for detecting the position.

  In the present invention according to claim 10, the increase amount of the reaction residue is obtained based on the displacement of the float detected by the displacement sensor, and the liquid feeding control is performed when it is detected that the reaction residue exceeds the predetermined amount. The circulation of the aqueous solution in the section is stopped and the operation is stopped.

  The hydrogen generator of the present invention according to claim 11 is the hydrogen generator according to claim 9 or claim 10, wherein the liquid supply controller stops the flow of the aqueous solution by a stop signal. The stop control unit outputs the stop signal to the liquid feeding control unit when the calculated increase speed exceeds a predetermined increase speed.

  In the present invention according to claim 11, when it is detected that the predetermined increase speed is exceeded, a stop signal is output to the liquid feeding control unit, the flow of the aqueous solution is stopped, and the operation is stopped.

  The hydrogen generator of the present invention according to claim 12 is the hydrogen generator according to claim 9 or claim 10, wherein the liquid feeding control unit allows the aqueous solution to flow when a predetermined pressure is applied. A liquid supply control unit that stops, the stop control unit configured to stop the hydrogen flow when the calculated increase rate exceeds the predetermined increase rate, and the hydrogen flow by the open / close unit. It is characterized by comprising an action part that causes the liquid feeding control part to act on the internal pressure of the reaction vessel as the predetermined internal pressure after being stopped.

  In the present invention according to claim 12, when the increase rate of the reaction residue exceeds a predetermined increase rate, the flow of hydrogen is stopped by the opening / closing part, and the pressure based on the increase in the internal pressure of the reaction vessel due to the stop of the hydrogen is supplied. Acting on the control unit, the flow of the aqueous solution is stopped, and the operation is stopped in conjunction with the increase of the internal pressure when the reaction residue increases.

  The hydrogen generator of the present invention according to claim 13 is the hydrogen generator according to claim 1, wherein the liquid feed control unit is configured to feed the aqueous solution stopped when a predetermined pressure is applied. An opening / closing unit that stops the flow of hydrogen when the amount of the reaction residue detected by the reaction residue amount detection unit exceeds a predetermined amount; After the hydrogen flow is stopped by the above, an action part is provided that causes the liquid feeding control part to act on the internal pressure of the reaction vessel as the predetermined internal pressure.

  In the present invention according to claim 13, when the amount of the reaction residue exceeds a predetermined amount, the flow of hydrogen is stopped by the opening / closing portion, and the pressure based on the increase in the internal pressure of the reaction vessel due to the stop of hydrogen is controlled by the liquid feeding control portion The flow of the aqueous solution is stopped, and the operation is stopped in conjunction with the increase of the internal pressure when the reaction residue increases.

  The hydrogen generator of the present invention according to claim 14 is the hydrogen generator according to claim 9 or claim 10, wherein the liquid supply controller stops the flow of the aqueous solution by a stop signal. The stop control unit is configured to stop the hydrogen flow when the calculated increase speed exceeds the predetermined increase speed, and after the hydrogen flow is stopped by the open / close unit, The liquid feeding control unit includes an output unit that outputs the stop signal.

  In the present invention according to claim 14, when it is detected that the increase rate of the reaction residue exceeds the predetermined increase rate, the flow of hydrogen is stopped by the opening / closing part, and the flow of hydrogen is stopped after the flow of hydrogen is stopped. A stop signal is output to the liquid control unit, the flow of the aqueous solution is stopped, and the operation is stopped.

  Moreover, the hydrogen generator of the present invention according to claim 15 is the hydrogen generator according to claim 1, wherein the liquid supply controller is a liquid supply controller that stops the flow of the aqueous solution by a stop signal, The stop control unit includes an open / close unit that stops the hydrogen flow when the amount of the reaction residue detected by the reaction residue amount detection unit exceeds a predetermined amount, and the hydrogen flow by the open / close unit. An output unit that outputs the stop signal to the liquid feeding control unit after being stopped is provided.

  In the present invention according to claim 15, when it is detected that the amount of the reaction residue has exceeded a predetermined amount, the flow of hydrogen is stopped by the opening / closing part, and the flow of hydrogen is stopped after the flow of hydrogen is stopped. A stop signal is output to the section, the flow of the aqueous solution is stopped, and the operation is stopped.

  The hydrogen generator of the present invention according to claim 16 is the hydrogen generator according to claim 1, wherein the predetermined amount of the reaction residue for stopping the flow of the aqueous solution is an allowable amount of the reaction residue. The maximum amount is set to a value obtained by subtracting the amount expected to increase the reaction residue after the flow of the aqueous solution is stopped.

  In the present invention according to claim 16, since the predetermined amount of the reaction residue is set in consideration of the amount that the reaction residue is expected to increase when the circulation of the aqueous solution is stopped, The outflow to the outside of the reaction vessel and the inhibition of the hydrogen generation reaction can be reliably eliminated.

  In order to achieve the above object, a fuel cell facility of the present invention according to claim 17 is characterized in that the discharge path of the hydrogen generator according to any one of claims 1 to 16 is an anode chamber of the fuel cell. The generated hydrogen is supplied to the negative electrode.

  In the present invention according to claim 17, a fuel cell comprising a hydrogen generator capable of supplying hydrogen in a state where the outflow of the reaction residue obtained by bringing the reactant into contact with the aqueous solution in a small space is reliably suppressed. It can be equipment.

  In addition, a hydrogen generation method according to claim 18 for achieving the above object is a container generated with an increase in a reaction residue when hydrogen is generated by bringing an aqueous solution into contact with a reaction product of a hydrogen generation reaction in the container. The supply of the aqueous solution is stopped based on the pressure change in the inside.

  In the present invention according to claim 18, hydrogen can be supplied in a state where the outflow of the reaction residue obtained by bringing the reactant into contact with the aqueous solution in a small space is reliably suppressed.

  The hydrogen generator and the hydrogen generation method of the present invention can supply hydrogen in a state where the outflow of the reaction residue obtained by bringing the reactant and the aqueous solution into contact with each other in a small space is reliably suppressed. Become a method.

  Further, the fuel cell equipment of the present invention is a fuel equipped with a hydrogen generator capable of supplying hydrogen in a state where the outflow of the reaction residue obtained by bringing the reactant and the aqueous solution into contact with each other in a small space is reliably suppressed. Battery equipment.

  A first embodiment will be described with reference to FIGS.

  FIG. 1 shows a schematic configuration of a hydrogen generator according to the first embodiment of the present invention, FIG. 2 shows a flow of a stop operation process, and FIG. 3 shows a change with time of the volume of a reaction residue.

  The hydrogen generator 1 includes a reaction vessel 2 as a reaction vessel, and a work 6 (for example, sodium borohydride: SBH) as a reaction product of a hydrogen generation reaction is accommodated in the reaction vessel 2 via a reaction unit 5. Has been. As the work 6, a metal hydride such as aluminum hydride salt, borohydride salt, lithium borohydride, lithium aluminum hydride, or the like can be used.

  A solution storage container (not shown) is provided adjacent to the reaction container 2, and an aqueous solution (for example, malic acid aqueous solution) of a hydrogen generation accelerator is stored in the container. As the accelerator, organic acids such as citric acid, inorganic acids such as hydrochloric acid and sulfuric acid, and the like can be used. Moreover, when making a reaction material into a solution, it is possible to use the solution which added hydroxide salt (sodium hydroxide, potassium hydroxide, etc.) to metal hydride, and was made into alkaline aqueous solution. In addition, a combination of a metal and a basic or acidic aqueous solution can be applied.

  A solution introduction path 3 (aqueous solution supply unit) is connected to the reaction vessel 2, and an aqueous solution is sent from the solution introduction path 3 to the reaction unit 5. When the aqueous solution is supplied from the solution introduction path 3 to the workpiece 6 through the reaction unit 5, the aqueous solution comes into contact with the workpiece 6 and reacts to generate hydrogen. The hydrogen produced in the reaction vessel 2 is supplied from the hydrogen outlet channel 8 (discharge unit) to the hydrogen consumption unit.

  The solution introduction path 3 is provided with a solution feeding means 4 (liquid feeding control unit), and the solution feeding means 4 controls the supply of the aqueous solution to the reaction unit 5. That is, the operation of the hydrogen generator is controlled. The configuration of the solution feeding means 4 is not limited as long as it controls the flow of the aqueous solution introduction path 3. For example, a liquid feeding means to which a pumping mechanism such as a pump is applied can be used, and a liquid whose amount is controlled by the amount of hydrogen consumed by the hydrogen consumption unit (power consumption in the case of a fuel cell) is applied. . In addition, a 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 vessel 2 is provided with a measuring unit 7 (reactant remaining amount detecting unit) for detecting the state (amount) of the reaction residue 10 in the inner space 11, and the measurement information of the measuring unit 7 is sent to the control unit 9. (Stop control unit). The measurement unit 7 can use an optical sensor that optically detects an object in a non-contact manner. For example, a non-contact side length sensor using a laser, an LED, an ultrasonic wave, or the like is applied.

  The surface height of the reaction residue 10 is detected by the measurement unit 7 and the detection information is input to the control unit 9. In the control unit 9, the increase rate is calculated by the change in the surface height of the reaction residue 10, and when the reaction residue 10 exceeds a predetermined amount exceeding the predetermined increase rate, the aqueous solution in the solution feeding means 4 is circulated. To stop. That is, when the volume of the reaction residue 10 is increased and the increase rate is increased, the reaction residue 10 may flow out to the hydrogen outlet channel 8 and the like, so the operation of the hydrogen generator 1 is stopped.

  The predetermined amount of the reaction residue 10 for stopping the flow of the aqueous solution is a threshold value of the amount when the aqueous solution is stopped (details will be described later), the outflow of the reaction residue 10 to the outside of the reaction vessel 2 and the like. The amount of the reaction residue 10 that does not hinder the hydrogen generation reaction (deterioration of the function of the hydrogen generator) or the reaction residue 10 in the empty space of the reaction vessel 2 with respect to the empty space, for example, Examples of the amount are as described above.

  It is also possible to stop the flow of the aqueous solution in the solution feeding means 4 regardless of the amount of the reaction residue 10 when the increase rate of the reaction residue 10 exceeds a predetermined increase rate.

  In the hydrogen generator 1 described above, hydrogen is generated by supplying an aqueous solution to the workpiece 6 of the reaction vessel 2, and the hydrogen generated in the reaction vessel 2 is supplied from a hydrogen outlet channel 8 to a hydrogen consuming unit such as a fuel cell. Supplied. As the reaction continues, the volume of the reaction residue 10 increases. If the increase rate of the reaction residue 10 is increased and the reaction residue 10 exceeds a predetermined amount, the reaction residue 10 may flow out to the hydrogen outlet channel 8 and the like. Is measured by the measuring unit 7. When the detection information of the measuring unit 7 is input to the control unit 9 and the control unit 9 determines that the reaction residue 10 has exceeded a predetermined increase rate, the flow of the aqueous solution in the solution feeding means 4 is stopped. Command is output.

  An example of a specific flow of processing in the control unit 9 will be described.

  As shown in FIG. 2, the amount S of the reaction residue 10 inside the reaction vessel 2 is measured in Step P1, and the increase rate Δt of the reaction residue 10 is calculated in Step P2. After the increase rate Δt is calculated, an increase amount v after stopping at the increase rate Δt of the reaction residue 10 is calculated in step P3.

  As shown in FIG. 3 showing the relationship of the volume (vertical axis) of the reaction residue 10 with respect to the operating time (horizontal axis) of the hydrogen generator 1, the increase rate Δt and the increase amount v after stopping (the amount of unreacted reactants) The amount predicted to increase) is grasped in advance, and the increase amount v at the increase speed Δt is calculated. For example, the increased amounts v1, v2, and v3 after the stop are calculated according to the increasing speeds Δt1, Δt2, and Δt3, respectively. Although three types of increase speed Δt are illustrated in FIG. 3 as an example, an increase amount v after stopping is sequentially calculated with respect to the calculated increase speed Δt.

The increase amount v after the stop is an allowable maximum amount (maximum amount) of the reaction residue Smax {the reaction residue flows out of the reaction vessel 2 or inhibits the hydrogen generation reaction (reduction of the function of the hydrogen generator 1). It is calculated based on the amount to be generated}. In step P4 of FIG. 2, a value obtained by subtracting the increase amount v for each increase rate Δt from the maximum amount Smax of the reaction residue is calculated as the threshold value St.
That is,
Threshold value St = maximum amount Smax−increase amount v (+ α)
Is calculated by

  Since the value obtained by subtracting the increase amount v at each increase rate Δt from the maximum amount Smax of the reaction residue is the threshold value St, even if the amount of unreacted reactants increases after the stop, the reaction residue is discharged to the outside of the reaction vessel. Inhibition of outflow and hydrogen generation reaction can be reliably eliminated.

  The threshold value St is preferably a value obtained by subtracting the increase amount v + α for each increase speed Δt from the maximum amount Smax with a margin α.

In the case of the increase rates Δt1, Δt2, and Δt3 shown in FIG. 3, the values obtained by subtracting the increase amounts v1 + α, v2 + α, and v3 + α for each increase rate Δt1, Δt2, and Δt3 from the maximum amount Smax of the reaction residue are the increase rates Δt1, Δt2, and The threshold values St1, St2, and St3 are set for each Δt3. That is,
Threshold value St1 = maximum amount Smax−increase amount (v1 + α)
Threshold value St2 = maximum amount Smax−increase amount (v2 + α)
Threshold value St3 = maximum amount Smax−increase amount (v3 + α)
It is said.

  After calculating the threshold value St in step P4, it is determined in step P5 whether or not the amount S of the reaction residue 10 exceeds the threshold value St. When it is determined in step P5 that the amount S of the reaction residue 10 does not exceed the threshold value St, the process proceeds to step P1 and measurement of the amount of the reaction residue 10 is continued. If it is determined in step P5 that the amount S of the reaction residue 10 exceeds the threshold value St, the solution generation is stopped in step P6 to stop the hydrogen generation reaction.

  Accordingly, the hydrogen generation reaction can be stopped by stopping the aqueous solution when the amount of the reaction residue 10 exceeds the threshold value St corresponding to the increase rate Δt. For this reason, it becomes possible to supply hydrogen in the state which suppressed outflow of the reaction residue 10 obtained by making the workpiece | work 6 and aqueous solution contact in a small space reliably. Further, when the reaction container 2 is filled with the reaction residue 10 as the use limit of the reaction container 2, the use limit (life) of the reaction container 2 can be accurately grasped.

  Another example of the specific flow of processing in the control unit 9 will be described based on FIGS. 4 and 5. FIG. 4 shows the flow of stop operation processing in another specific example, and FIG. 5 shows the change over time in the volume of the reaction residue in another specific example. This example is an example in which the increase rate region is divided into a Δt-L region where the increase rate is slow and a Δt-H region where the increase rate is fast, with the region of increase rate Δt2 of the reaction residue shown in FIG. is there.

  As shown in FIG. 4, the amount S of the reaction residue 10 inside the reaction vessel 2 is measured in Step P11, and the increase rate Δt of the reaction residue 10 is calculated in Step P12. After the increase speed Δt is calculated, it is determined in step P13 whether the increase speed is in the Δt-L region or the Δt-H region. When the increase rate is in the Δt-L region, the threshold value St2 shown in FIG. 5 (the threshold value in the region of the reaction residue increase rate Δt2) is applied, and when the increase rate is in the Δt-H region, The threshold value St3 shown in FIG. 5 is applied.

  If it is determined in step P13 that the increase rate is in the Δt−L region, it is determined in step P14 whether or not the amount S of the reaction residue 10 exceeds the threshold value St2. If it is determined in step P14 that the amount S of the reaction residue 10 does not exceed the threshold value St2, the process proceeds to step P11 and measurement of the amount of the reaction residue 10 is continued. If it is determined in step P14 that the amount S of the reaction residue 10 exceeds the threshold value St2, the solution generation is stopped in step P15 to stop the hydrogen generation reaction.

  If it is determined in step P13 that the increase rate is in the Δt-H region, it is determined in step P16 whether or not the amount S of the reaction residue 10 exceeds the threshold value St3. When it is determined in step P16 that the amount S of the reaction residue 10 does not exceed the threshold value St3, the process proceeds to step P11 and measurement of the amount of the reaction residue 10 is continued. If it is determined in step P16 that the amount S of the reaction residue 10 exceeds the threshold value St3, the solution generation is stopped in step P15 to stop the hydrogen generation reaction.

  Therefore, when the amount of the reaction residue 10 exceeds the threshold value in the region corresponding to the increasing rate, the aqueous solution can be stopped accurately to stop the hydrogen generation reaction. For this reason, it becomes possible to supply hydrogen accurately in a state where the outflow of the reaction residue 10 obtained by bringing the workpiece 6 and the aqueous solution into contact with each other in a small space is reliably suppressed.

  In the configuration shown in FIG. 1, when the solution feeding means 4 is configured to feed liquid when the internal pressure of the reaction vessel 2 becomes low, a pressure transmission path for directly acting the internal pressure of the reaction vessel 2 It is also possible to provide.

  A second embodiment example and a third embodiment example will be described with reference to FIGS.

  FIG. 6 shows a schematic configuration of a hydrogen generator according to the second embodiment of the present invention. FIG. 7 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 the 1st Embodiment shown in FIG. 1, and the overlapping description is abbreviate | omitted.

  A second embodiment will be described.

  In the hydrogen generator 31 shown in FIG. 6, the hydrogen outlet flow path 8 is provided with an opening / closing valve 12 (opening / closing part), and the opening / closing valve 12 is closed by a command from the control unit 9. That is, when it is determined by the control unit 9 that the increase rate of the reaction residue 10 is increased by the detection information of the measurement unit 7 and the reaction residue 10 exceeds the predetermined amount, a command to close the on-off valve 12 is output. The

  As the solution feeding means 4, a solution feeding means using a valve that is opened and closed using the internal pressure in the reaction vessel 2 is used. When the reaction residue 10 exceeds a predetermined amount and the on-off valve 12 is closed, the pressure in the reaction vessel 2 increases, and the pressure in the reaction vessel 2 is transferred to the solution feeding means 4 by the pressure transmission path 13 (action part). Works. When a high pressure acts on the solution feeding means 4, the solution feeding means 4 through which the aqueous solution is circulated is brought into a state where the solution feeding is stopped due to the pressure drop. Thereby, liquid feeding of aqueous solution stops and the hydrogen generator 31 is stopped.

  For this reason, when the reaction residue 10 exceeds a predetermined amount, the flow of hydrogen is stopped by the on-off valve 12, and the pressure based on the increase in the internal pressure of the reaction vessel 2 due to the stop of hydrogen acts on the solution feeding means 4. Then, the flow of the aqueous solution is stopped, and the operation can be stopped in conjunction with the increase of the internal pressure when the reaction residue 10 increases.

  It is also possible to increase the pressure in the reaction vessel 2 by closing the on-off valve 12 regardless of the amount of the reaction residue 10 while the increase rate of the reaction residue 10 is increased.

  A third embodiment will be described.

  The hydrogen generator 32 shown in FIG. 7 is provided with a pressure detector 17 (internal pressure detector) that detects the internal pressure (internal pressure) of the reaction vessel 2 with respect to the hydrogen generator 31 of FIG. When the reaction residue 10 exceeds a predetermined amount and the on-off valve 12 is closed, the pressure in the reaction vessel 2 increases and the pressure detector 17 detects an increase in pressure. The pressure signal of the pressure detection unit 17 is sent to the solution feeding unit 4 (output unit), and the solution feeding unit 4 is brought into a state of stopping the flow of the aqueous solution. Thereby, liquid feeding of aqueous solution stops and the hydrogen generator 32 is stopped.

  For this reason, when the reaction residue 10 exceeds a predetermined amount, the flow of hydrogen is stopped by the on-off valve 12, and an increase in the internal pressure of the reaction vessel 2 due to the stoppage of hydrogen is detected by the pressure detection unit 17, and the solution feed A stop signal is output to the means 4, the flow of the aqueous solution is stopped, and the operation can be stopped.

  A fourth embodiment and a fifth embodiment will be described with reference to FIGS.

  FIG. 8 shows a schematic configuration of a hydrogen generator according to the fourth embodiment of the present invention. FIG. 9 shows a schematic configuration of the hydrogen generator according to the fifth embodiment of the present invention. In addition, the same code | symbol is attached | subjected to the same member as the 1st Embodiment shown in FIG. 1, and the overlapping description is abbreviate | omitted.

  A fourth embodiment will be described.

  The hydrogen generator 33 shown in FIG. 8 includes a float 14 that floats on the reaction residue 10, and the position of the float 14 is detected by the measurement unit 7 (displacement sensor). The float 14 is guided directly under the measuring unit 7 by a guide. The detection information of the position of the float 14 is sent to the control unit 9, and it is determined whether or not the reaction residue 10 exceeds a predetermined amount by increasing the rate of increase of the reaction residue 10. When it is determined by the control unit 9 that the reaction residue 10 has exceeded a predetermined amount, a stop signal is output to the solution feeding means 4, the flow of the aqueous solution is stopped, and the hydrogen generator 33 is stopped.

  For this reason, when the position of the float 14 is detected, the surface of the reaction residue 10 can be accurately measured, the flow of the aqueous solution can be reliably stopped, and the operation can be stopped.

  A fifth embodiment will be described.

  The hydrogen generator 34 shown in FIG. 9 includes a float 51 floating on the reaction residue 10, and a variable resistance unit 52 is connected to the float 51. When the position of the float 51 is displaced, the resistance value of the variable resistance portion 52 changes accordingly, and information on the changing resistance value is sent to the control unit 9. In the control unit 9, it is determined whether or not the reaction residue 10 exceeds a predetermined amount due to the increase in the reaction residue 10 due to the change in resistance value (due to the displacement of the float 51). When it is determined by the control unit 9 that the reaction residue 10 has exceeded a predetermined amount, a stop signal is output to the solution feeding means 4, the flow of the aqueous solution is stopped, and the hydrogen generator 33 is stopped.

  For this reason, the change of the resistance value corresponding to the displacement of the float 51 is detected, so that the surface of the reaction residue 10 can be accurately measured, the flow of the aqueous solution is stopped reliably, and the operation is stopped. Can be made.

  In the above-described embodiment, the example in which the threshold value St is set based on the increase speed Δt and the increase amount v after stopping has been described, but the surface position of the reaction residue 10 (the amount of the reaction residue 10). The volume of the space in the reaction vessel 2 is detected, and the operation can be stopped (the aqueous solution is stopped) by the threshold value of the volume.

  That is, as shown in FIG. 10, the amount of the reaction residue 10 in the reaction vessel 2 is measured at step P21, and the space volume of the reaction vessel 2 is calculated at step P22. In step P23, it is determined whether or not the space volume is sufficient. If it is determined that the space volume is sufficient, the operation (reaction) is continued, and the process proceeds to step P21. When the reaction residue 10 becomes 2/3 or more, etc.), the hydrogen generation reaction is stopped (supply of the aqueous solution is stopped) in Step P24.

  Thereby, it becomes possible to supply the hydrogen in a state where the operation of the hydrogen generator is stopped by simple control and the outflow of the reaction residue 10 is reliably suppressed.

  A sixth embodiment and a seventh embodiment will be described with reference to FIGS. 11 and 12.

  FIG. 11 shows a schematic configuration of a hydrogen generator according to the sixth embodiment of the present invention. FIG. 12 shows a schematic configuration of the hydrogen generator according to the seventh embodiment of the present invention. The same members as those in the embodiment shown in FIG. 1, FIG. 6, and FIG.

  A sixth embodiment will be described.

  The hydrogen generator 35 shown in FIG. 11 is provided with a sealing float 61 floating on the reaction residue 10, and when the reaction residue 10 increases and the position of the sealing float 61 rises, that is, the reaction residue 10 When the amount exceeds a predetermined amount, the hydrogen outlet 16 of the hydrogen outlet channel 8 is blocked by the sealing float 61 so that the hydrogen flow is stopped. The sealing float 61 is guided directly under the hydrogen outlet 16 by a guide. Moreover, the pressure detection part 17 (internal pressure detection part) which detects the pressure (internal pressure) inside the reaction container 2 is provided.

  When the reaction residue 10 exceeds a predetermined amount and the hydrogen outlet 16 of the hydrogen outlet channel 8 is blocked by the sealing float 61, the pressure in the reaction vessel 2 increases, and the pressure detector 17 reduces the pressure. A rise is detected. The pressure signal of the pressure detection unit 17 is sent to the solution feeding unit 4 (output unit), and the solution feeding unit 4 is brought into a state of stopping the flow of the aqueous solution. As a result, the feeding of the aqueous solution is stopped and the hydrogen generator 35 is stopped.

  In the sixth embodiment, the sealing float 61 is a reaction residue amount detection unit that detects the amount of the reaction residue 10. Moreover, the sealing float 61 is a stop control unit that stops the reaction by stopping the flow of the aqueous solution due to the increase in pressure by stopping the flow of hydrogen and thereby stopping the flow of the aqueous solution.

  For this reason, when the amount of the reaction residue 10 exceeds a predetermined amount, the flow of hydrogen is stopped by the sealing float 61, and the increase in the internal pressure of the reaction vessel 2 due to the stop of hydrogen is detected by the pressure detection unit 17. A stop signal is output to the solution feeding means 4, the flow of the aqueous solution is stopped, and the operation can be stopped. As a result, the hydrogen generator 35 can be reliably stopped when the reaction residue 10 increases without using an expensive sensor or the like.

  A seventh embodiment will be described.

  The hydrogen generator 36 shown in FIG. 12 is provided with a sealing float 61 that floats on the reaction residue 10. When the reaction residue 10 increases and the position of the sealing float 61 rises, that is, the reaction residue 10 When the amount exceeds a predetermined amount, the hydrogen outlet 16 of the hydrogen outlet channel 8 is blocked by the sealing float 61 so that the hydrogen flow is stopped. The sealing float 61 is guided directly under the hydrogen outlet 16 by a guide.

  As the solution feeding means 4, a solution feeding means using a valve that is opened and closed using the internal pressure in the reaction vessel 2 is used. When the reaction residue 10 exceeds a predetermined amount and the hydrogen outlet 16 is blocked by the sealing float 61, the pressure in the reaction vessel 2 increases, and the pressure in the reaction vessel 2 is increased by the pressure transmission path 13 (action part). The pressure acts on the solution feeding means 4. When a high pressure acts on the solution feeding means 4, the solution feeding means 4 through which the aqueous solution flows is brought into a state where the liquid feeding is stopped. Thereby, liquid feeding of aqueous solution stops and the hydrogen generator 36 is stopped.

  For this reason, when the amount of the reaction residue 10 exceeds a predetermined amount, the flow of hydrogen is stopped by the sealing float 61, and the pressure based on the increase in the internal pressure of the reaction vessel 2 due to the stop of hydrogen is set to the solution feeding means 4. As a result, the flow of the aqueous solution is stopped, and the operation of the hydrogen generator 36 can be reliably stopped in conjunction with the increase in the internal pressure when the reaction residue 10 increases.

  In the seventh embodiment, the sealing float 61 is a reaction residue amount detection unit that detects the amount of the reaction residue 10. Moreover, the sealing float 61 is a stop control unit that stops the reaction by stopping the flow of the aqueous solution due to the increase in pressure by stopping the flow of hydrogen and thereby stopping the flow of the aqueous solution.

  It is also possible to float the reaction residue 10 and provide a switch that is pushed by the float when the amount of the reaction residue 10 exceeds a predetermined amount, and stop the flow of the aqueous solution by the switch signal. is there.

  The fuel cell facility will be described based on FIG.

  FIG. 13 shows a schematic configuration of a fuel cell facility according to an embodiment of the present invention. In the illustrated embodiment, the hydrogen generator 1 shown in FIG. 1 is applied. Therefore, the same members as those shown in FIG.

  The fuel cell facility shown in FIG. 13 is a facility in which the hydrogen generator 1 shown in FIG. That is, the fuel cell 18 includes a fuel electrode chamber 24, and the fuel electrode chamber 24 forms a space in contact with the negative electrode of the fuel cell 21. A hydrogen outlet flow path 8 of the hydrogen generator 1 is connected to the fuel electrode chamber 24.

  The solution introduction path 3 of the hydrogen generator 1 is connected to the solution container 25, and the aqueous solution 26 in the solution container 25 is sent to the reaction unit 5 by the solution feeding means 4.

  Hydrogen generated in the hydrogen generator 1 is supplied from the hydrogen outlet flow path 8 to the fuel electrode chamber 24 and consumed by the fuel cell reaction at the negative electrode. The amount of hydrogen consumed at the negative electrode of the fuel electrode chamber 24 is determined according to the output of the fuel cell 18.

  In addition, as a hydrogen generator, what was shown in FIG.6, FIG.7, FIG.8, FIG.9, FIG.11 and FIG.12 is also applicable.

  The fuel cell facility described above includes a fuel cell facility equipped with a hydrogen generator that can supply hydrogen in a state where the outflow of the reaction residue obtained by bringing the reactant and the aqueous solution into contact with each other in a small space is reliably suppressed; Become.

  INDUSTRIAL APPLICABILITY The present invention can be used in the industrial field of a hydrogen generator and a hydrogen generation method for supplying hydrogen generated by a chemical reaction to a device that requires hydrogen, such as a fuel cell or a hydrogen engine, or a hydrogen storage container.

  In addition, the present invention can be used in the industrial field of fuel cell equipment equipped with a hydrogen generator that can supply hydrogen while suppressing the influence of reaction residues.

1 is a schematic configuration diagram of a hydrogen generator according to a first embodiment of the present invention. It is a flowchart showing an example of a stop operation process. It is a graph showing an example of the time-dependent change of the volume of a reaction residue. It is a flowchart showing other examples of stop operation processing. It is a graph showing the other example of the time-dependent change of the volume of a reaction residue. 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 hydrogen generator which concerns on the example of 4th Embodiment of this invention. It is a schematic block diagram of the hydrogen generator which concerns on the example of 5th Embodiment of this invention. It is a flowchart of a stop operation process. It is a schematic block diagram of the hydrogen generator which concerns on the 6th Example of this invention. It is a schematic block diagram of the hydrogen generator which concerns on the example of 7th Embodiment of this invention. 1 is a schematic configuration diagram of a fuel cell facility according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 31, 32, 33, 34, 35, 36 Hydrogen generator 2 Reaction container 3 Solution introduction path 4 Solution feeding means 5 Reaction unit 6 Work 7 Measuring part 8 Hydrogen outlet flow path 9 Control unit 10 Reaction residue 11 Space DESCRIPTION OF SYMBOLS 12 On-off valve 13 Pressure transmission path 14, 51 Float 16 Hydrogen outlet 18 Fuel cell 21 Fuel cell 24 Fuel electrode 25 Solution container 26 Aqueous solution 52 Variable resistance part 61 Sealing float

Claims (18)

A reaction vessel containing a reactant and reacting the reactant with an aqueous solution to generate hydrogen;
An aqueous solution supply unit for supplying the aqueous solution to the reaction vessel;
A liquid feed control unit for controlling the flow of the aqueous solution in the aqueous solution supply unit;
A discharge part for discharging hydrogen generated in the reaction vessel;
A reaction residue amount detection unit for detecting the amount of reaction residue inside the reaction vessel;
A stop control unit that stops the flow of the aqueous solution in the liquid feeding control unit when the amount of the reaction residue detected by the reaction residue amount detection unit exceeds a predetermined amount. A hydrogen generator. The hydrogen generator according to claim 1,
The reaction residue amount detection unit has a sealing float that floats on the reaction residue and closes the discharge unit when the reaction residue reaches the predetermined amount. The hydrogen generator according to claim 2,
The stop control unit stops the flow of the aqueous solution in the liquid supply control unit based on the internal pressure of the reaction vessel in a state where the discharge unit is blocked by the sealing float. Generator. The hydrogen generator according to claim 3,
The liquid feeding control unit is a liquid feeding control unit that stops the flow of the aqueous solution by a stop signal,
The stop control unit
An internal pressure detector for detecting the internal pressure of the reaction vessel;
An hydrogen generation apparatus comprising: an output unit that outputs the stop signal to the liquid feeding control unit based on a signal from the internal pressure detection unit. The hydrogen generator according to claim 1,
The liquid feeding control unit is a liquid feeding control unit that stops the flow of the aqueous solution by a stop signal,
The stop control unit outputs the stop signal when the amount of the reaction residue detected by the reaction residue amount detection unit exceeds a predetermined amount. The hydrogen generator according to claim 3,
The liquid feeding control unit is a liquid feeding control unit that stops the circulation of the aqueous solution when a predetermined pressure acts,
The hydrogen generator according to claim 1, wherein the stop controller includes an action unit that causes the internal pressure of the reaction vessel to act on the liquid feed controller. The hydrogen generator according to claim 1,
The stop control unit calculates an increase rate of the amount of the reaction residue based on a detection value of the reaction residue amount detection unit, and the liquid feeding control unit when the increase rate exceeds a predetermined increase rate A hydrogen generator characterized by stopping the flow of the aqueous solution. The hydrogen generator according to claim 1,
The stop control unit calculates an increase rate of the amount of the reaction residue based on a detection value of the reaction residue amount detection unit, and sets the predetermined amount according to the increase rate. Hydrogen generator. In the hydrogen generator according to claim 7 or claim 8,
The reaction residue amount detection unit is a non-contact sensor that detects the height of the surface of the reaction residue. In the hydrogen generator according to claim 7 or claim 8,
The reaction residue amount detection unit includes a float floating on the reaction residue and a displacement sensor that detects a position of the float. In the hydrogen generator according to claim 9 or 10,
The liquid feeding control unit is a liquid feeding control unit that stops the flow of the aqueous solution by a stop signal,
The stop control unit outputs the stop signal to the liquid feeding control unit when the calculated increase rate exceeds a predetermined increase rate. In the hydrogen generator according to claim 9 or 10,
The liquid feeding control unit is a liquid feeding control unit that stops the circulation of the aqueous solution when a predetermined pressure acts,
The stop control unit
An opening / closing part for stopping the flow of the hydrogen when the calculated increase rate exceeds the predetermined increase rate;
A hydrogen generating apparatus, comprising: an action part that causes the liquid feeding control part to act on the internal pressure of the reaction vessel as the predetermined internal pressure after the hydrogen flow is stopped by the opening / closing part. The hydrogen generator according to claim 1,
The liquid feeding control unit is a liquid feeding control unit that stops the circulation of the aqueous solution when a predetermined pressure is applied.
The stop control unit
An open / close unit that stops the flow of hydrogen when the amount of the reaction residue detected by the reaction residue amount detection unit exceeds a predetermined amount;
A hydrogen generating apparatus comprising: an action part that causes the liquid supply control part to act on the internal pressure of the reaction vessel as the predetermined internal pressure after the hydrogen flow is stopped by the opening / closing part. In the hydrogen generator according to claim 9 or 10,
The liquid feeding control unit is a liquid feeding control unit that stops the flow of the aqueous solution by a stop signal,
The stop control unit
An opening / closing part for stopping the flow of the hydrogen when the calculated increase rate exceeds the predetermined increase rate;
An hydrogen generating apparatus comprising: an output unit that outputs the stop signal to the liquid feeding control unit after the hydrogen flow is stopped by the opening / closing unit. The hydrogen generator according to claim 1,
The liquid feeding control unit is a liquid feeding control unit that stops the flow of the aqueous solution by a stop signal,
The stop control unit
An open / close unit that stops the flow of hydrogen when the amount of the reaction residue detected by the reaction residue amount detection unit exceeds a predetermined amount;
An hydrogen generating apparatus comprising: an output unit that outputs the stop signal to the liquid feeding control unit after the hydrogen flow is stopped by the opening / closing unit. The hydrogen generator according to claim 1,
The predetermined amount of the reaction residue that stops the flow of the aqueous solution is an amount that is expected to increase the reaction residue after the flow of the aqueous solution is stopped from the allowable maximum amount of the reaction residue. A hydrogen generator characterized by being set to the amount of reduced value.   A fuel cell facility, wherein the discharge path of the hydrogen generator according to any one of claims 1 to 16 is connected to a fuel electrode chamber of a fuel cell, and the generated hydrogen is supplied to a negative electrode.   Hydrogen, characterized in that, when hydrogen is generated by bringing an aqueous solution into contact with the reaction product of the hydrogen generation reaction in the vessel, the supply of the aqueous solution is stopped based on a change in pressure in the vessel caused by an increase in the reaction residue. Occurrence method.

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