JP2017105674A - Hydrogen generator and power generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen generator that can stably generate hydrogen even when a large amount of hydrogen generating agent is used (a case of a large capacity) and can prevent a pressure in a reactor from increasing too much, and a power generator using the same.SOLUTION: A hydrogen generator of the present invention includes a reactor 2 for storing a reaction liquid 1, a hydrogen generating agent housing part 4 for housing a solid hydrogen generating agent 3 for generating hydrogen by reacting with the reaction liquid 1, a hydrogen generating agent supply part 5 that is attached to the hydrogen generating agent housing part 4 and supplies intermittently the hydrogen generating agent 3 to the reaction liquid 1 by an operation of a driving mechanism 20, a reactor pressure detector 6 for detecting the pressure in the reactor 2, and a control means 7 that controls the pressure in the reactor 2 to pressure higher than a predetermined pressure by intermittently operating the driving mechanism 20 base on the reactor pressure detected by the reactor pressure detector 6.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hydrogen generator that generates hydrogen by supplying a solid hydrogen generating agent to a reaction solution in a reaction vessel that stores the reaction solution, and a power generation device using the same. The present invention is useful as a technique for generating power by supplying hydrogen to a fuel cell.

  For example, Patent Document 1 describes a method in which water, which is a reaction liquid, is added dropwise to a hydrogen generator in a reaction vessel by pressurization to generate hydrogen by the reaction between the two. However, in this method, particularly when a large amount of hydrogen generating agent is used, when the reaction proceeds, the reacted hydrogen generating agent absorbs water and a time lag occurs until the supplied water reaches the generating agent. And responsiveness decreases. Even when the supply of water is stopped, the absorbed water reacts with the generating agent, so that the responsiveness at the time of stoppage also tends to decrease.

  Further, in Patent Document 2, hydrogen generating agent powder and water as a reaction liquid are simultaneously supplied to a reaction vessel for generating hydrogen while being separately transported, and hydrogen is generated by the reaction between the two. Is described. However, in this method, there are problems that the structure of the apparatus is complicated because there are two transport mechanisms, and that the mixed state of the powder and water tends to be non-uniform, so that the reaction becomes non-uniform.

  On the other hand, Patent Document 3 proposes a hydrogen generator that generates hydrogen by supplying a particulate hydrogen generating agent to a reaction solution in a reaction vessel that stores the reaction solution. Also, in this apparatus, an opening is provided at the bottom of the powder supplier that contains the hydrogen generating agent, and the hydrogen generating agent is dropped into the reaction solution and supplied by an openable / closable plate valve provided in the opening. Yes. Further, it is described that the increase / decrease of the hydrogen generation amount is adjusted by the number of pellets (particles) to be dropped, and it can be understood that hydrogen is generated in a batch system.

JP 2009-1456 A JP2015-81221A JP 2003-221202 A

  However, since the hydrogen generator of Patent Document 3 generates hydrogen in a batch system, as described in the drawings, the temporal profile of the amount of generated hydrogen depends on the properties of the hydrogen generator particles. It is determined and it is difficult to control the amount of hydrogen generated according to the amount of hydrogen consumed by the fuel cell.

  Moreover, about the reaction container at the time of generating hydrogen, based on the occupational safety and health law, the pressure which can be used will be regulated according to the volume of the pressure container. Since hydrogen is generated in a batch system, it is difficult to prevent the pressure in the reaction vessel from rising too much.

  Accordingly, an object of the present invention is to provide a hydrogen generator capable of stably generating hydrogen even when a large amount of hydrogen generator is used (in the case of a large capacity) and preventing the reaction vessel pressure from rising excessively. Is to provide.

  Another object of the present invention is to use such a hydrogen generator, so that the reaction vessel can be used in a range not subject to the pressure vessel regulations of the Occupational Safety and Health Act, and power is generated by a fuel cell or the like. In such a case, an object of the present invention is to provide a power generator capable of stably generating a large amount of power.

The above object can be achieved by the present invention as follows.
That is, the hydrogen generator of the present invention includes a reaction vessel that stores a reaction liquid, and a hydrogen that is disposed in an upper space in the reaction container and contains a solid hydrogen generating agent that reacts with the reaction liquid to generate hydrogen. A generating agent storage unit, a hydrogen generating agent supply unit which is attached to the hydrogen generating agent storage unit and intermittently supplies the hydrogen generating agent to the reaction solution by operation of a drive mechanism; and in or in communication with the reaction vessel A reaction vessel pressure detector for detecting the pressure of the portion to be operated, and the reaction vessel pressure detected by the reaction vessel pressure detector, and intermittently operating the drive mechanism to reduce the pressure in the reaction vessel. And a control means for controlling the pressure to be equal to or higher than a predetermined pressure.

  According to the hydrogen generator of the present invention, since the solid hydrogen generating agent is supplied to the reaction liquid stored in the reaction vessel from the hydrogen generating agent storage unit disposed in the upper space, the supplied hydrogen generating agent reacts. Immediate contact with the liquid (hydroxide generated by the reaction is deposited at the bottom), and even when a large amount of hydrogen generating agent is used, the responsiveness at the start and stop of the reaction can be enhanced. At this time, the hydrogen generating agent can be intermittently supplied to the reaction solution by the hydrogen generating agent supply unit, and the pressure in the reaction vessel is set to a predetermined value by operating the drive mechanism of the hydrogen generating agent supply unit by the control means. It can be controlled above the pressure. For this reason, even when a large amount of hydrogen generator is used, hydrogen can be stably generated, and the pressure in the reaction vessel can be prevented from excessively rising. As a result, the reaction vessel can be made within a range not subject to the pressure vessel regulations of the Occupational Safety and Health Act, and when generating power with a fuel cell or the like, large-capacity power generation can be stably performed.

  In the above, it is preferable that the drive mechanism supplies a predetermined amount of the hydrogen generating agent in one operation by an air cylinder. By using an air cylinder (no electric parts are used), no sparks are generated by the electric system, so that hydrogen explosion can be prevented even if it is placed in the reaction vessel. Further, by supplying a predetermined amount of the hydrogen generating agent in one operation, it is possible to stably perform control by intermittent operation.

  Furthermore, a pressurized container connected to the air cylinder for supplying pressurized gas, a pressurized gas supply path for connecting the pressurized container and the reaction container, and the reaction container provided in the pressurized gas supply path And a check valve that allows the flow of pressurized gas into the pressurized container. In general, an air cylinder can be driven by a compressed air supply device or the like, but by adopting such a configuration, the air cylinder can be driven without a compressed air supply device or the like. That is, by connecting through a pressurized gas supply path including a pressurized container, a reaction container, and a check valve, hydrogen generated in the reaction container can be supplied to the pressurized container to increase the internal pressure. At this time, the check valve can prevent backflow, and the pressure in the pressurized container can be made equal to or higher than the pressure in the reaction container. Therefore, the air cylinder can be driven while returning hydrogen to the reaction container. .

  In the above, the hydrogen generating agent containing portion has an inclined surface that reduces a cross-sectional area toward the bottom portion, and an opening in the bottom portion, and the driving mechanism includes the air cylinder in which a cylinder is arranged in the vertical direction, And a valve member driven by the air cylinder. By having such an inclined surface and an opening, the hydrogen generating agent can be supplied by operating the air cylinder while gradually moving toward the bottom in the hydrogen generating agent accommodating portion. At this time, since the valve member is reciprocated up and down by the valve member driven by the air cylinder in which the cylinder is arranged in the vertical direction, vibration is transmitted vertically to the hydrogen generating agent. It can be moved smoothly (without clogging on the way).

  Further, the control by the control means includes control for operating the drive mechanism so as to supply a predetermined amount of the hydrogen generating agent at regular intervals when the reaction vessel pressure is lower than a set value. Is preferred. If the amount of the hydrogen generating agent supplied at one time is too large, the change in the hydrogen generation rate also becomes large, and it may be difficult to control the pressure constant. In this way, the hydrogen generating agent is spaced at regular intervals. By supplying the predetermined amount, it is possible to determine the control at the timing of performing the next operation while observing the passage of time, so that the pressure in the reaction vessel can be controlled more uniformly.

  On the other hand, a power generation device according to the present invention is characterized by including any of the hydrogen generation devices described above and a fuel cell that generates power using hydrogen supplied from the hydrogen generation device. According to the power generation device of the present invention, hydrogen is supplied to the fuel cell using the hydrogen generator having the above-described effects, so that the reaction vessel can be made within a range not subject to the pressure vessel regulation of the Industrial Safety and Health Act. In addition, when generating power with a fuel cell or the like, large-capacity power generation can be stably performed.

The schematic block diagram which shows an example of the electric power generating apparatus of this invention The flowchart which shows an example of control (electric power generation routine) in the electric power generating apparatus of this invention The flowchart which shows an example of control (the whole) in the electric power generating apparatus of this invention Graph showing results in Experimental Example 1 The schematic block diagram which shows the principal part of the other example of the electric power generating apparatus of this invention The schematic block diagram which shows the principal part of the other example of the electric power generating apparatus of this invention Graph showing results in Experimental Example 2

(Hydrogen generator)
As shown in FIG. 1, for example, the hydrogen generator of the present invention includes a reaction vessel 2 that stores a reaction liquid 1 and a hydrogen generator that contains a solid hydrogen generator 3 that reacts with the reaction liquid 1 to generate hydrogen. The storage unit 4 includes a hydrogen generation agent supply unit 5 which is attached to the hydrogen generation agent storage unit 4 and intermittently supplies the hydrogen generation agent 3 to the reaction liquid 1 by the operation of the drive mechanism 20.

  The reaction solution 1 may be anything that reacts with the hydrogen generator 3 to generate hydrogen, and neutral water, an aqueous acid solution, an aqueous alkaline solution, or the like is used. The hydrogen generating agent 3 will be described in detail later.

  As the reaction vessel 2, a sealed vessel is used, but when the reaction solution 1 or the hydrogen generating agent 3 is accommodated, one that can be opened and closed is preferable. In the present embodiment, an example of a reaction vessel 2 is shown in which a container body is constituted by a cylindrical portion 2a and a bottom surface portion 2b, and a lid member 2c that can be opened and closed is provided on the upper surface. Note that, as the reaction vessel 2, alkali may be generated by the reaction of the hydrogen generating agent 3, and therefore it is preferable to use a material having alkali resistance.

  The volume of the reaction vessel 2 is determined according to the reaction solution 1 and the hydrogen generating agent 3 to be charged. For example, the amount of the reaction solution 1 is preferably about 8 to 9 times the theoretical reaction amount with respect to the hydrogen generating agent 3. The volume of the reaction vessel 2 is preferably about 3 to 4 times the volume of the reaction solution 1.

  The lid member 2c of the reaction vessel 2 is provided with a discharge portion 2e for hydrogen H, and further provided with a safety valve 15 that opens when the pressure in the vessel exceeds a certain value. The cylindrical portion 2 a of the reaction vessel 2 is provided with an airtight connection portion 2 d for connecting a supply pipe 26 for compressed air C.

  Any safety valve 15 can be used as long as it releases gas at a pressure higher than a certain level. From the viewpoint of reducing the size and weight, it is preferable to use a valve such as a metal ball valve type, an umbrella type, a duckbill type, or the like as the safety valve 15. The set pressure of the safety valve 15 is determined according to the pressure resistance of the system, but is set to, for example, about 30 to 500 kPa (particularly 100 kPa).

  The hydrogen generating agent storage unit 4 is disposed in the upper space in the reaction vessel 2 and includes a drive mechanism 20 for supplying the hydrogen generating agent 3 to the reaction solution 1 intermittently. In the present embodiment, an example is shown in which the hydrogen generating agent storage unit 4 has a conical inclined surface 4a that reduces the cross-sectional area toward the bottom and an opening 4b at the bottom. The conical inclined surface 4 a is supported by four legs 4 c reaching the bottom surface 2 b of the reaction vessel 2.

  In the present embodiment, the drive mechanism 20 is provided at the tip of the rod of the air cylinder 22, the compressed air supplier 25 (compressor), the electromagnetic valves 24 a and 24 b, the air cylinder 22, the pipe 26 connecting them, and the air cylinder 22. The example which has the valve member 23 is shown. The drive mechanism 20 includes an air cylinder 22 in which a cylinder is arranged in the vertical direction, and a valve member 23 driven by the air cylinder 22.

  The compressed air supplier 25 is a device for supplying compressed air C for operating the air cylinder 22. In the present invention, it is preferable that the drive mechanism 20 further includes a buffer tank 28. In the illustrated example, the buffer tank 28 is provided outside the compressed air supply device 25, but the compressed air supply device 25 may include the buffer tank 28.

  The compressed air supply unit 25 is supplied with electric power to the compressed air supply unit 25, but is normally stopped in a state in which a pressure of a certain level or more is generated, so that almost no power supply is required. On the other hand, only when the pressure is lower than a certain level, it is operated by electric power and air is stored in the buffer tank 28. For this reason, power consumption can be greatly reduced by adopting the drive mechanism 20 including the compressed air supplier 25 having the buffer tank 28 and the air cylinder 22.

  The air cylinder 22 is fixed to the hydrogen generating agent storage unit 4 by a column 27. By fixing the air cylinder 22 to the hydrogen generating agent accommodating portion 4 through the support 27 in this manner, the hydrogen generating agent accommodating portion 4 having a conical inclined surface 4a when the air cylinder 22 is operated. Therefore, vibration is transmitted to the hydrogen generating agent 3, and the hydrogen generating agent 3 can be moved more smoothly (without clogging in the middle) toward the bottom. In the illustrated example, the air cylinder 22 has two systems of compressed air supply ports, and the compressed air supplied to the space communicating with one of them moves the piston to the side of the space communicating with the other, and conversely The air cylinder 22 is used to move the piston in the reverse direction by compressed air supplied to the space communicating with the other.

  The air cylinder 22 is operated by, for example, two three-way (three-port) electromagnetic valves 24a and 24b provided on the pipe 26 outside the reaction vessel 2, and the electric operation to one electromagnetic valve 24a is performed. The rod of the air cylinder 22 can be moved downward by communicating the primary side and the secondary side of the solenoid valve 24a with a signal to increase the pressure on the secondary side. At this time, the other solenoid valve 24b communicates with the secondary side and the tertiary side, and the pressure in the other space is released. Conversely, the rod of the air cylinder 22 is moved upward by connecting the primary side and the secondary side of the solenoid valve 24a to a high pressure on the secondary side by an electrical operation signal to the other solenoid valve 24b. Can be made. At this time, the other solenoid valve 24a is opened with the secondary side and the tertiary side communicating with each other. In this manner, the rod of the air cylinder 22 can be reciprocated.

  In performing such an operation, the solenoid valves 24a and 24b are configured such that when the operation signal is input, the primary side and the secondary side are communicated, and when there is no input, the secondary side and the tertiary side are communicated. What can open | release the next side (air cylinder 22 side) to air | atmosphere is preferable. Thereby, the operation signal during the opening time of the valve member 23 becomes unnecessary, and the power saving effect can be enhanced.

  The reciprocating motion width can be set to an appropriate width by the movable range adjustment mechanism of the air cylinder 22 or the like. The reciprocating speed can be adjusted with a throttle valve (not shown).

  In the present invention, since it is desirable that the valve member 23 provided at the tip of the rod moves downward for a certain time (for example, about 1 to 3 seconds), the operation signal causes the air cylinder 22 to move to the lower side for a certain time. It is preferable to operate. Such an operation for setting the predetermined opening time can be performed by a time difference between the operation signal to the electromagnetic valve 24a and the operation signal to the electromagnetic valve 24b.

  A predetermined amount of the hydrogen generating agent 3 can be supplied by one operation of the valve member 23 by the air cylinder 22. The amount at that time can be determined by the length of time of operation, the width of reciprocation, the size of the opening 4b, and the like. However, even if these are the same conditions, the amount of the hydrogen generating agent 3 supplied in one operation may differ depending on the amount of the hydrogen generating agent 3 remaining in the hydrogen generating agent storage unit 4. For this reason, it is also possible to reduce the change of the supplied hydrogen generating agent 3 by changing the opening time of one operation according to the remaining amount of the hydrogen generating agent 3. However, in the present invention, even if the amount of one supply is different, the pressure in the reaction vessel 2 can be kept almost constant by the control described later.

  Furthermore, the hydrogen generator of the present invention is detected by a reaction vessel pressure detector 6 for detecting the pressure in a reaction vessel 2 or a portion communicating with the reaction vessel 2 and a reaction vessel pressure detector 6 as shown in FIG. Control means 7 for controlling the pressure in the reaction vessel 2 to a predetermined pressure or higher by intermittently operating the drive mechanism 20 based on the reaction vessel pressure. In the present embodiment, an example in which the reaction container pressure detector 6 provided on the lid member 2c of the reaction container 2 is provided is shown.

  The reaction vessel pressure detector 6 is only required to be able to detect the pressure in the reaction vessel 2. In addition to measuring the pressure in the reaction vessel 2, the pressure in the path communicating with the reaction vessel 2 is measured. Is included. That is, in the present invention, the reaction vessel pressure detector 6 that directly or indirectly detects the pressure in the reaction vessel 2 is provided.

  As the reaction vessel pressure detector 6, a pressure sensor or the like that measures the gas pressure with a pressure-sensitive element through a diaphragm (stainless diaphragm, silicon diaphragm, etc.), converts it into an electrical signal, and the like can be used. Typical pressure sensors include semiconductor piezoresistive diffusion pressure sensors, capacitance pressure sensors, and the like.

  The control means 7 only needs to be able to output arithmetic operations and operation signals related to the above control. For example, a microcomputer unit, a program sequencer, a personal computer or the like can be used. Hereinafter, the control flow of this embodiment is demonstrated based on FIGS.

  FIG. 3 shows each routine from start to stop, but the control in the present invention is performed in the power generation routine (step S4) in a state where step S3 defined in the power generation preparation routine has been omitted. .

  As shown in FIG. 2, first, in step S11, data sampling and determination are performed. Examples of the target include reaction vessel pressure, and sampling can be performed many times (for example, 20 times / second) in a short time. It is also possible to calculate the average value by sampling a large number of times and use it as the reaction vessel pressure data at that time.

  In the present embodiment, an example is shown in which it is determined whether or not the reaction vessel pressure is less than a set value based on this data. If this is yes, the process proceeds to step S12, and if no, the process proceeds to step S15. As a set value of this reaction container pressure, 20-100 kPa is mentioned, for example, 40-80 kPa is more preferable from the relationship with the pressure container regulation of the occupational safety and health law, and 50-70 kPa is still more preferable.

  Step S12 is a process of sending an operation signal for communicating the primary side and the secondary side to the electromagnetic valve 24a. As a result, the rod of the air cylinder 22 can be moved downward to open the opening 4b of the hydrogen generating agent storage unit 4.

  Step S13 is processing for waiting time for the opening time. When the above-described preferable electromagnetic valves 24a and 24b are used, the state immediately after the operation signal is sent can be maintained without sending the operation signal to both. For this reason, in step S13, it becomes possible to maintain an open state only by processing as a waiting time. However, during this opening time, it is also possible to continue sending an operation signal for communicating the primary side and the secondary side to the electromagnetic valve 24a. By these processes, the opening 4b of the hydrogen generating agent storage unit 4 can be opened while the rod of the air cylinder 22 is moved downward.

  Step S14 is a process of sending an operation signal for communicating the primary side and the secondary side to the electromagnetic valve 24b. Thereby, the rod of the air cylinder 22 can be moved to the upper side, and the opening 4b of the hydrogen generating agent accommodation part 4 can be closed.

  By the processing from step S12 to step S14, the opening 4b of the hydrogen generating agent storage unit 4 can be opened for a predetermined time. Thereby, the predetermined amount of the hydrogen generating agent 3 can be supplied by one operation of the air cylinder 22. In addition, hydrogen generation can be started within a few seconds after the operation.

  Step S15 is a process for waiting time of the waiting time. Thereby, the closed state can be maintained for a predetermined time after one operation of the air cylinder 22. Although it depends on the hydrogen generation capacity of the hydrogen generator, the time for maintaining the closed state is, for example, 10 to 100 seconds, and preferably 20 to 80 seconds. When the predetermined standby time has elapsed, the process proceeds to step S16.

  In step S16, for example, it is determined whether or not to stop the operation based on an external input signal or an emergency stop signal. If no, the operation is continued and the process returns to step S11. In step S11, sampling is performed again, and when the reaction vessel pressure is less than the set value, the opening 4b of the hydrogen generating agent storage unit 4 is opened again in steps S12 to S14. By such control, the drive mechanism 20 can be intermittently operated, and thereby the pressure in the reaction vessel 2 can be controlled to be equal to or higher than a predetermined pressure. By stopping the operation in step S16, hydrogen generation can be stopped within about 3 minutes.

(Hydrogen generator)
As the hydrogen generating agent, it is possible to use a hydrogen generating material such as particulates alone (without embedding the resin), but from the viewpoint of controlling the reaction rate with the reaction liquid, the resin base material Those containing a particulate hydrogen generating substance are preferred. In that case, as the resin to be used, those other than the water-soluble resin are preferable from the viewpoint of appropriately adjusting the reaction.

  The solid hydrogen generator to be used may have any shape such as powder, granule (pulverized product), and lump (molded product). From the viewpoint of efficiently producing a product having a certain particle size, a predetermined amount is obtained after extrusion. Are preferably pulverized to a particle size of 2 and adjusted to a particle size by sieving. 1-10 mm is preferable and, as for the average particle diameter of such a granular material, 2-5 mm is more preferable.

  Examples of the hydrogen generating substance include calcium hydride, lithium hydride, potassium hydride, lithium aluminum hydride, sodium aluminum hydride, metal hydride such as magnesium hydride, metal such as aluminum, iron, magnesium, calcium, hydrogen Examples thereof include metal hydrogen complex compounds such as boron halide compounds. Of these, metal hydrides are preferable, and calcium hydride is particularly preferable. A plurality of metal hydride compounds, metals, and metal hydride complex compounds can be used in combination, or they can be used in combination.

That is, as the hydrogen generating agent, those containing granular calcium hydride (CaH ₂ ) in the base material of the resin excluding the water-soluble resin are particularly preferable. In this hydrogen generating agent, the granular calcium hydride is dispersed or embedded in the resin matrix, thereby suppressing the reactivity of the calcium hydride and improving the handleability during the reaction with water. The In addition, by using calcium hydride as a hydrogen generating substance, the reactivity with water and the like is increased, and the volume expansion coefficient of the reaction product (calcium hydroxide) generated when reacting with water and the like is increased. The action of collapsing the resin base material is increased, and the reaction with water and the like easily proceeds to the inside naturally.

  The content of the hydrogen generating material is preferably 60% by weight or more in the hydrogen generating agent, but from the viewpoint of causing the resin base material to collapse during the reaction while maintaining the shape retention, 60 to 90% in the hydrogen generating agent. It is preferable that it is weight%, and 70 to 85 weight% is more preferable.

  The average particle size of the particulate hydrogen generating substance is preferably 1 to 100 μm, more preferably 6 to 30 μm, and even more preferably 8 to 10 μm, from the viewpoint of appropriately controlling dispersibility in the resin and reaction.

  When another hydrogen generating substance is added to calcium hydride, the content of the hydrogen generating substance is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, and 0 to 5% by weight in the hydrogen generating agent. Is more preferable.

  As the resin, a resin other than the water-soluble resin is preferably used, and examples thereof include a thermosetting resin, a thermoplastic resin, and a heat resistant resin, and a thermosetting resin is preferable. By using a thermosetting resin, the resin base material generally tends to be brittle, the resin base material collapses more easily during the reaction, and the reaction easily proceeds naturally.

  Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylic resin, fluororesin, polyester, and polyamide. Examples of the heat resistant resin include aromatic polyimide, polyamide, and polyester.

  Examples of the thermosetting resin include epoxy resins, unsaturated polyester resins, phenol resins, amino resins, polyurethane resins, silicone resins, and thermosetting polyimide resins. Especially, an epoxy resin is preferable from a viewpoint that the resin base material has moderate disintegration during the hydrogen generation reaction. When the thermosetting resin is cured, a curing agent, a curing accelerator, or the like is appropriately used as necessary.

  The content of the resin is preferably less than 40% by weight, but is preferably 5 to 35% by weight in the hydrogen generator from the viewpoint of collapsing the resin base material during the reaction while maintaining the shape retention. -30% by weight is more preferred.

  The hydrogen generating agent to be used may contain other components such as a catalyst and a filler as optional components other than the above components. As the catalyst, an alkali compound such as sodium hydroxide, potassium hydroxide and calcium hydroxide is also effective in addition to the metal catalyst for the hydrogen generator.

  The hydrogen generating agent may have a porous structure, but a substantially solid structure is preferable. That is, in the hydrogen generating agent of the present invention, porosity (%) = pore volume / total volume × 100 is preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less.

(Power generation device)
As shown in FIG. 1, the power generation apparatus of the present invention includes the hydrogen generation apparatus of the present invention as described above and a fuel cell 13 that generates power with hydrogen H supplied from the hydrogen generation apparatus. In the present embodiment, an example in which the nitrogen concentrating device 14 for executing the nitrogen exhaust routine S2 is provided prior to the power generation routine S4 is shown.

  In the present embodiment, the hydrogen H supply path includes an ammonia removal device 11, a two-way (two-port) solenoid valve 17 for supplying and stopping, and a three-way (three-port) for switching the supply path. The electromagnetic valve 12 is provided.

  That is, in the present invention, it is preferable to provide the ammonia removing device 11 using an ammonia removing agent or the like in order to remove ammonia as an impurity from the generated hydrogen H. Specifically, a sheet-like ammonia removing agent filled in a container can be used. Such an ammonia removing agent is commercially available in the form of a sheet, but it is also possible to use one in which a granular adsorbent or the like is contained in a breathable bag.

  As the ammonia removing agent, for example, an adsorbent that adsorbs and removes ammonia in hydrogen (including chemical adsorption such as adsorption / decomposition and reaction adsorption), an absorbent that dissolves and removes ammonia, a reactant that removes ammonia by reaction, Examples include decomposition means for removing ammonia by decomposition (thermal decomposition, catalytic reaction decomposition, etc.), and it is preferable to provide an adsorbent that removes ammonia by physical adsorption or chemical adsorption.

  Among them, it is more preferable that the adsorbent is one that removes ammonia by physical adsorption or chemical adsorption, solid acid, activated carbon (excluding those corresponding to solid acids), zeolite (excluding those corresponding to solid acids), And at least one selected from the group consisting of molecular sieves. Among these, it is preferable to use a solid acid from the viewpoint of adsorption / removal ability of ammonia and a viewpoint capable of adsorption at a higher temperature.

  Examples of the solid acid include those in which the solid acid itself is granular, and those in which a solid acid or liquid acid is supported on a granular material, but those in which a metal salt is supported on activated carbon are from the viewpoint of cost and manufacturability. More preferred. Examples of the metal salt include sulfates, phosphates, chloride salts, and nitrates. As the metal forming the salt, a metal exhibiting acidity can be suitably used.

  As the activated carbon (including those corresponding to solid acids), GW48 / 100, GW-H48 / 100, GG10 / 20, 2GG, GLC10 / 32, 2GS, GW10 / 32, GW20 / 40, KLY10 / 32, KW10 / 32, KW20 / 42 (above, manufactured by Kuraray Chemical Co., Ltd.), SWWB agent (for alkali), WB agent, S agent (for acid) (above, manufactured by Anico Japan Co., Ltd.), 4T-B, 4T-C 4G-H, 4SA, 2GS, GW20 / 4042 (manufactured by Kuraray Chemical Co., Ltd.) and the like, and 4T-B, SWWB agent (for alkali), and WB agent are preferable.

  As zeolite, BX, HISIV, R-3 (above, union Showa Co., Ltd. product) etc. are mentioned, Preferably it is BX.

  Examples of the molecular sieve include Zeorum A-3 and Zeorum A-4 (above, manufactured by Tosoh Corporation), and Zeolum A-4 is preferable.

  As the fuel cell 13, any type of fuel cell can be used as long as it generates electricity with supplied hydrogen. For example, a solid polymer form (Polymer Electrolyte Fuel Cell), a solid oxide form (SOFC), a molten carbonate form (MCFC), or a phosphoric acid form (PAFC) can be used, which is suitable for the hydrogen generation method of the present invention. From the viewpoints of output, small size and low operating temperature, a polymer electrolyte fuel cell is preferable.

  The solid polymer fuel cell has any structure, the solid polymer electrolyte layer, the first electrode layer and the second electrode layer provided on both sides of the solid polymer electrolyte layer, and the electrode layers. The first conductive layer and the second conductive layer are disposed on the outer sides of the first conductive layer and the second conductive layer, respectively. The solid polymer electrolyte layer and the electrode layer are integrated to form a membrane electrode assembly (MEA). Further, the conductive layer has a flow path for collecting current from the electrode layer and supplying fuel to the electrode layer for reaction.

  The structure of the fuel cell 13 may be any of a stack structure, a structure in which single cells are connected, and a structure in which single cells are combined.

  In the case of a stack structure, unit cells are separated by a separator, and current is collected, and flow paths for supplying fuel are formed on both sides of the separator. The unit cells are electrically connected in series or in parallel, and the flow paths are mainly connected in parallel as gas supply.

  As a single cell used for a structure in which single cells are connected, a single cell may be provided with a flow path for each single cell. However, as described in Japanese Patent No. 4511610 (International Publication WO2009 / 145090), a solid cell A polymer electrolyte layer; a first electrode layer and a second electrode layer provided on both sides of the solid polymer electrolyte layer; and a first conductive layer and a second conductive layer respectively disposed further outside of the electrode layers; And a fuel cell in which these layers are integrated with a resin molded body obtained by insert molding.

  Further, as a structure in which single cells are combined, a structure in which a plurality of such fuel cells are integrated with a space forming member covering at least the anode side to provide a fuel gas supply space is preferable. In such a structure, it is preferable that a plurality of unit cells are electrically connected and insert-molded at the same time.

  The nitrogen concentrator 14 is a device for carrying out a nitrogen discharge routine S2 for concentrating and discharging nitrogen or the like, and includes a small and small capacity fuel cell. This fuel cell includes a hydrogen supply unit and a discharge unit communicating with the anode electrode side, and the discharge unit includes an electromagnetic valve. When hydrogen containing nitrogen or the like is supplied from the hydrogen supply unit at the time of start-up, hydrogen is consumed and nitrogen or the like is concentrated by generating power with the fuel cell. The degree of nitrogen concentration can be determined by detecting the power generation state of the fuel cell. When nitrogen is concentrated to some extent, the nitrogen valve is discharged from the discharge section by operating the solenoid valve. Thus, nitrogen and the like can be concentrated and selectively discharged.

  Next, steps S1 (start-up routine) to step S3 (power generation preparation routine) will be described with reference to FIG. In order to execute the processing by the startup routine, a detection cell for detecting a voltage connected to the gas discharge path of the fuel cell 13 and a circuit for detecting the output voltage of the fuel cell 13 are used (both not shown). ).

  In the present embodiment, in the state where the two-way (two-port) solenoid valve 17 is closed, the hydrogen generation described above is performed in the same manner as in the power generation routine by a start signal in step S1 (start routine). That is, steps S11 to S16 shown in FIG. 2 are executed. However, in step S11, when the pressure becomes a certain level or more, the electromagnetic valve 17 is opened, and the routine proceeds to the nitrogen exhaust routine in step S2. In Steps S2 to S3, Steps S11 to S16 shown in FIG. 2 are continuously executed in order to ensure a constant pressure.

  In the nitrogen discharge routine of step S2, hydrogen is supplied to the nitrogen concentrator 14 via the ammonia removing device 11 by the three-way (three-port) solenoid valve 12 with the solenoid valve 17 open. This hydrogen contains impurities derived from air, such as nitrogen and oxygen, present in the reaction vessel 2 at an early stage.

  In step S2, the fuel cell to which hydrogen containing nitrogen or the like is supplied from the hydrogen supply unit generates power, so that hydrogen is consumed and nitrogen or the like is concentrated. The degree of concentration of nitrogen, etc. can be automatically determined by detecting the power generation state by the fuel cell. When nitrogen is concentrated to some extent, nitrogen etc. is discharged from the discharge part by operating the solenoid valve. By discharging, nitrogen and the like can be concentrated and selectively discharged. By repeating this operation as necessary, almost all impurities in the system can be discharged out of the system. Whether or not the discharge of impurities has been completed can also be automatically determined by detecting the power generation state by the fuel cell. When the discharge of impurities is completed, the process proceeds to the power generation preparation routine in step S3.

  In step S <b> 3, the supply path is switched by the three-way (three-port) electromagnetic valve 12 so that hydrogen that has passed through the ammonia removing device 11 is supplied to the fuel cell 13. Thereby, step S4 which is a power generation routine can be executed.

In step S5 defined by the stop time routine, the operation is stopped in step S16 shown in FIG. Thereby, supply of the hydrogen generating agent 3 is stopped. At this time, the generated hydrogen is present in the reaction vessel 2 and the pressure is high, but the electromagnetic valve 17 is opened, and the power P generated by the power generation is a secondary battery (not shown). ) Is charged.
(Other embodiments)
(1) In the above-described embodiment, the air cylinder has two compressed air supply ports, and the compressed air supplied to the space communicating with one or the other of the air cylinders is used for the space communicating with the other or the other. Although an example of using an air cylinder that moves the piston to the side is shown, it is also possible to use a different type of air cylinder 22.

  For example, using an air cylinder with a single compressed air supply port, a signal for communicating (opening) the primary side and the secondary side of the solenoid valve with respect to the solenoid valve, and opening the secondary side With this signal, the valve member 23 can be opened and closed. It is also possible to continue to send an operation signal to the electromagnetic valve for a certain period of time, and to open the valve member 23 while increasing the secondary side of the electromagnetic valve a during that period.

  (2) In the above-described embodiment, an example in which an air cylinder is driven using a compressed air supply device is shown. However, in the present invention, an external power source such as a compressed air supply device is used as shown in FIG. It is possible to drive the air cylinder.

  In this example, the hydrogen generator of the present invention is further connected to an air cylinder 22 to supply a pressurized gas, and a pressurized gas supply path for connecting the pressurized container 31 and the reaction container 2. 32 and a check valve 33 that is provided in the pressurized gas supply path 32 and allows the pressurized gas to flow from the reaction vessel 2 to the pressurized vessel 31. The pressurized gas supply path 32 preferably has a pressure regulating valve 34 so that the pressure on the pressurized container 31 side is below a certain level (for example, 80 KPa or below).

  In this apparatus, in the power generation preparation routine (step S4), a process of initially pressurizing the inside of the pressurized container 31 is executed. At that time, the electromagnetic valve 17 for supplying hydrogen to the fuel cell 13 is closed, and the pressurized gas (hydrogen) is transferred from the reaction vessel 2 to the pressurized vessel 31 via the check valve 33 and the pressure regulating valve 34. Is supplied. At this time, supply is performed by the pressure adjusting valve 34 until the pressure in the pressurized container 31 becomes constant. When the pressure in the pressurized container 31 becomes equal to or higher than a certain level, the electromagnetic valve 17 is opened and a power generation routine (step S4) is executed.

  In the power generation routine, the operation of the air cylinder 22 is performed by, for example, two three-way (three-port) electromagnetic valves 24 a and 24 b provided in the pipe 26 outside the reaction vessel 2, and one of the electromagnetic valves 24 a The rod of the air cylinder 22 can be moved downward by connecting the primary side and the secondary side of the solenoid valve 24a with an electrical operation signal to increase the pressure on the secondary side. At this time, the other solenoid valve 24 b communicates with the secondary side and the tertiary side, and the pressure in the other space is opened to the reaction vessel 2. Conversely, the rod of the air cylinder 22 is moved upward by connecting the primary side and the secondary side of the solenoid valve 24a to a high pressure on the secondary side by an electrical operation signal to the other solenoid valve 24b. Can be made. At this time, the other solenoid valve 24a is opened to the reaction vessel 2 with the secondary side and the tertiary side communicating with each other. In this way, the rod of the air cylinder 22 can be reciprocated without discharging hydrogen to the outside.

  In a series of operations, the pressure in the initial pressurized container 31 gradually decreases, but in order to recover the pressure in the pressurized container 31, the power generation routine is temporarily interrupted, the electromagnetic valve 17 is closed, Similarly to the initial operation, a pressure recovery routine for supplying pressurized gas (hydrogen) from the reaction vessel 2 to the pressurized vessel 31 may be executed.

  (3) As a method of driving the air cylinder without using an external power source, the apparatus shown in FIG. 6 can be used.

  In this apparatus, a back pressure pressurization container 35 is connected to the upper space 22a of the piston of the air cylinder 22, and the upper space 22a is pressurized at a constant pressure. Instead of this configuration, an elastic body such as a spring can be used. On the other hand, the lower space 22b of the piston of the air cylinder 22 is open to the reaction vessel 2 through the supply port 22c.

  When the pressure in the reaction vessel 2 is above a certain level, the piston of the air cylinder 22 is moved upward and the valve member 23 is closed, but the hydrogen is consumed and the pressure in the reaction vessel 2 is above a certain level. In this case, the valve member 23 is temporarily opened, and the hydrogen generating agent can be intermittently supplied.

  That is, in this embodiment, the piston in the air cylinder 22 detects the pressure in the reaction vessel 2 (reaction vessel pressure detector), and the drive mechanism 20 is operated intermittently based on the detected reaction vessel pressure. Thus, the pressure in the reaction vessel 2 is controlled to be equal to or higher than a predetermined pressure.

  (4) In the above-described embodiment, the example of the drive mechanism including the air cylinder in which the cylinder is arranged in the vertical direction and the valve member driven by the air cylinder has been shown, but the cylinder is arranged in the lateral direction. The drive mechanism may include an air cylinder and a valve member that is driven laterally by the air cylinder. According to such a drive mechanism, the valve member 23 is temporarily opened by sliding the valve member, and the hydrogen generating agent can be supplied intermittently.

  (5) In the above-described embodiment, an example of a drive mechanism that supplies a predetermined amount of the hydrogen generating agent in one operation by an air cylinder has been described. However, a motor or the like using compressed air as a power source is used. It is also possible to drive a valve member, a screw type feeder or the like. It is also possible to use an externally arranged electric motor to hermetically seal the rotating shaft and drive a screw type feeder or the like from the outside.

  (6) Further, in order to make the hydrogen generating agent fall smoothly, it is possible to further provide a stirrer, a vibration applying device, etc. to the hydrogen generating agent supply section.

  Hereinafter, effects of the present invention will be described based on experimental examples.

Experimental example 1
The fuel cell output of the apparatus shown in FIG. 1 was connected to a lead storage battery (capacity 1 kWhr), and hydrogen generation and power generation were performed using a power generation apparatus in which the output of the lead storage battery was connected to an electronic load device. In the electronic load device, the discharge current was subjected to constant current control (CC control) so that the output from the lead storage battery was 200 W during power generation.

  As the fuel cell, a stack type fuel cell (output 200 W class) having a CV of 13.5 V was used. As a hydrogen generator, calcium hydride is contained in an epoxy resin at a concentration of 78% by weight, the uncured product is cured after extrusion (diameter 4 mm), and then pulverized and classified under a sieve having an aperture of 6.7 mm. The granular product (1900 g) was used.

  As a control method, when the pressure was less than 65 KPa, hydrogen was generated by controlling the dropping of the hydrogen generating agent into water (12 L) with a waiting time of 15 seconds at an opening time of 1 second.

  As a result, as shown in FIG. 4, in the state where the output to the electronic load device is controlled to approximately 200 W, the hydrogen pressure (pressure in the reaction vessel) is controlled in the range of about 60 to 70 KPa, and the fuel cell The power was able to be generated so that the output of the power supply was constant at about 170 W.

Experimental example 2
In the power generation apparatus shown in FIG. 1, the output of the fuel cell is connected to a lead storage battery (capacity 1 kWhr) using the power generation apparatus adopting the drive mechanism shown in FIG. 5, and the output of the lead storage battery is connected to an electronic load apparatus. Hydrogen generation and power generation were performed. In the electronic load device, the discharge current was subjected to constant current control (CC control) so that the output from the lead storage battery was 120 W during power generation.

  As the fuel cell, a stack type fuel cell (output 200 W class) having a CV of 13.5 V was used. The same hydrogen generator as in Experimental Example 1 was used.

  As a control method, when the difference between the pressure in the reaction vessel and the cylinder pressure is 20 KPa or more, control is performed to drop the hydrogen generating agent into water (6 L) with a waiting time of 10 seconds with an opening time of 2 seconds. As a result, hydrogen was generated.

  As a result, as shown in FIG. 7, the cylinder pressure slightly decreases, but the hydrogen consumption (pressure in the reaction vessel) fluctuates, but the amount of hydrogen consumed is kept almost constant (output is almost constant). ) Was able to generate electricity.

DESCRIPTION OF SYMBOLS 1 Reaction liquid 2 Reaction container 3 Hydrogen generating agent 4 Hydrogen generating agent accommodating part 5 Hydrogen generating agent supply part 6 Reaction container pressure detector 7 Control means 11 Ammonia removal apparatus 12 Electromagnetic valve 13 Fuel cell 14 Nitrogen concentrating apparatus 15 Safety valve 17 Electromagnetic valve DESCRIPTION OF SYMBOLS 20 Drive mechanism 22 Air cylinder 23 Valve member 24a Solenoid valve 24b Solenoid valve 25 Compressed air supply device 26 Piping 27 Strut 28 Buffer tank 31 Pressurization container 32 Pressurization gas supply path 33 Check valve 34 Pressure adjustment valve 35 Back pressure pressurization container

Claims (6)

A reaction vessel for storing the reaction solution;
A hydrogen generating agent storage unit that is disposed in an upper space in the reaction vessel and stores a solid hydrogen generating agent that reacts with the reaction solution to generate hydrogen;
A hydrogen generating agent supply unit that is attached to the hydrogen generating agent storage unit and intermittently supplies the hydrogen generating agent to the reaction solution by operation of a drive mechanism;
A reaction vessel pressure detector for detecting a pressure in the reaction vessel or a portion communicating with the reaction vessel;
Control means for controlling the pressure in the reaction vessel to a predetermined pressure or higher by intermittently operating the drive mechanism based on the reaction vessel pressure detected by the reaction vessel pressure detector;
A hydrogen generator comprising:   The hydrogen generating apparatus according to claim 1, wherein the driving mechanism supplies a predetermined amount of the hydrogen generating agent by one operation by an air cylinder.   Furthermore, a pressurized container connected to the air cylinder for supplying pressurized gas, a pressurized gas supply path for connecting the pressurized container and the reaction container, and the reaction container provided in the pressurized gas supply path The hydrogen generator of Claim 2 provided with the non-return valve which accept | permits inflow of the pressurized gas to the said pressurized container from. The hydrogen generating agent accommodating portion has an inclined surface that reduces a cross-sectional area toward the bottom portion, and an opening at the bottom portion,
4. The hydrogen generation apparatus according to claim 2, wherein the drive mechanism includes the air cylinder in which a cylinder is disposed in a vertical direction and a valve member driven by the air cylinder.   The control by the control means includes a control for operating the drive mechanism so as to supply a predetermined amount of the hydrogen generating agent at regular intervals when the reaction vessel pressure is equal to or lower than a set value. The hydrogen generator in any one of -4. A hydrogen generator according to any one of claims 1 to 5;
And a fuel cell that generates power using hydrogen supplied from the hydrogen generator.