JP4822158B2 - HYDROGEN GENERATOR, FUEL CELL EQUIPMENT, AND HYDROGEN GENERATION METHOD - Google Patents

Description

  The present invention relates to a hydrogen generation apparatus and a hydrogen generation method for efficiently supplying hydrogen to an apparatus that requires hydrogen, such as a fuel cell or a hydrogen engine, and a hydrogen storage container.

  The present invention also relates to a fuel cell facility provided with a hydrogen generator capable of efficiently supplying hydrogen.

  Due to the recent increase in energy problems and environmental problems, there is a demand for a power source with higher energy density and clean emissions. Fuel cells and internal combustion engines (hydrogen engines) that generate electricity by generating hydrogen are generators that have several times the energy density of existing batteries, have high energy efficiency, and contain nitrogen oxides and sulfur oxides contained in exhaust gases. There is a feature that there is no or few. Therefore, it can be said that it is a very effective device meeting the demand as a next-generation power supply device.

  Power generation devices using hydrogen are targeted at all types of industries such as regional distributed power sources, buildings, household generations, 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. 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, in a hydrogen generator, it is considered to purify hydrogen efficiently and without waste by providing a separator (see, for example, Patent Document 2).

  That is, the hydrogen generator has a configuration in which a reactor and a separator are connected to a water tank via a pump and a valve. In the separator, impurities, water and hydrogen can be separated, and the supernatant water in the separator is reused. For this reason, the hydrogen purity produced | generated can be improved. In addition, the water tank volume can be reduced and the apparatus can be miniaturized by reusing water.

  However, the conventional hydrogen generator uses a pump as power to send water to the reactor, but consumes electric power for driving and controlling the pump, and in addition, there is a pump control unit, so the volume is large. It became large and unsuitable for downsizing and high capacity.

  Further, the metal hydride moved to the separator reacts with the water in the separator to generate hydrogen. It is preferable to react the entire amount of the metal hydride transferred to the separator quickly, but the reaction product has many bubbles and covers the surface of the metal hydride and hinders the reaction. It was difficult to control. In addition, since it is a technology that separately provides a room as a separating means, a space is required, and the size cannot be reduced.

  From the above, it has been a problem that there is no power in the water supply of the hydrogen generator, and in addition, it is easy to control hydrogen generation by removing bubbles and the like as reaction products without using a separator.

JP 2003-206101 A JP 2002-154803 A

  The present invention has been made in view of the above circumstances, and facilitates hydrogen generation control in a small space by passing the generated hydrogen and reaction product through an aqueous accelerator solution, and uses the pressure generated by hydrogen generation to reduce power. It is an object of the present invention to provide a hydrogen generation apparatus and a hydrogen generation method that can move a promoter aqueous solution without using it.

  Further, the present invention has been made in view of the above situation, by passing the generated hydrogen and reaction product through an aqueous accelerator solution to facilitate hydrogen generation control in a small space, and by using the pressure generated by hydrogen generation, It is an object of the present invention to provide a fuel cell facility equipped with a hydrogen generator that enables movement of an aqueous promoter solution without using electric power.

  In order to achieve the above object, a first aspect of the present invention includes a reactor that contains a solid reactant and generates hydrogen therein, and a storage chamber in the reactor that contains the solid reactant. A fluid chamber in which the volume of the storage chamber is variable in the storage chamber of the reactor; a solution reservoir that stores an aqueous solution of a promoter that generates hydrogen by contact with the solid reactant; the reactor; A fluid channel in communication with the solution reservoir and delivering hydrogen from the reactor to the solution reservoir, an end on the solution reservoir side contacting the promoter solution, the solution reservoir, and the solution reservoir A hydrogen flow path that communicates with the fluid chamber and delivers hydrogen from the solution reservoir to the fluid chamber of the reactor; and is provided in the solution reservoir and discharges the hydrogen delivered to the solution reservoir. A first hydrogen discharge passage, and the fluid chamber, A second hydrogen discharge path for discharging the delivered hydrogen, and a flow of the promoter aqueous solution in the fluid flow path by depressurization of the storage chamber through the fluid chamber due to generation and discharge of hydrogen, and the hydrogen flow path And a control means for controlling the flow of hydrogen in the first hydrogen discharge path and the second hydrogen discharge path, and for causing hydrogen to flow through the fluid flow path and bringing the reaction product into contact with the promoter aqueous solution. The hydrogen generator is characterized by the following.

  In the first aspect, the control means is controlled in accordance with the pressure fluctuation in the solution reservoir due to the generation and discharge of hydrogen, and the promoter aqueous solution is transferred to the solid reactant side of the hydrogen generation reaction through the fluid flow channel that is the aqueous solution flow channel. Moving, bringing the promoter aqueous solution into contact with the solid reactant to generate hydrogen, circulating the reaction product containing hydrogen generated through the fluid flow path, which is a circulation path, to the solution reservoir to contact the promoter aqueous solution, The product is removed by contacting with the aqueous promoter solution, and the hydrogen from which the product has been removed is discharged from the discharge path. As a result, without providing a room for removing the product, in addition, without a drive source for moving the fluid, hydrogen in a state where products such as bubbles and metal inclusions are removed in a small space. It can be discharged and supplied to the consumer.

  In order to achieve the above object, a second aspect of the present invention includes a reactor that contains a solid reactant and generates hydrogen therein, and a storage chamber in the reactor that contains the solid reactant. A fluid chamber in which the volume of the storage chamber is variable in the storage chamber of the reactor, a solution reservoir that stores an aqueous solution of a promoter that generates hydrogen by contact with the solid reactant, and the reactor A first fluid flow path that communicates between the storage chamber and the solution reservoir and supplies the aqueous solution of the accelerator from the solution reservoir to the solid reactant in the storage chamber; the storage chamber of the reactor; and the solution A second fluid flow path communicating with the reservoir and contacting the reaction product generated in the reactor with the promoter aqueous solution of the solution reservoir; and the solution reservoir and the fluid chamber of the reactor. And a hydrogen flow for sending hydrogen from the solution reservoir to the fluid chamber. And by depressurization of the storage chamber through the fluid chamber due to generation and discharge of hydrogen, the flow of the promoter aqueous solution in the first fluid channel, the hydrogen channel, the first hydrogen discharge channel, and the Control means for controlling the flow of hydrogen in the second hydrogen discharge passage, and for causing hydrogen to flow through the second fluid flow path and bringing the reaction product into contact with the promoter aqueous solution. In the generator.

  In the second aspect, the control means is controlled in accordance with the pressure fluctuation in the solution reservoir due to the generation and discharge of hydrogen, and the promoter aqueous solution is passed through the first fluid flow path that is the aqueous solution flow path, and the solid reaction product of the hydrogen generation reaction. To the side, the aqueous solution of the promoter is brought into contact with the solid reactant to generate hydrogen, and the reaction product containing hydrogen generated through the second fluid flow path, which is a circulation path, is circulated to the solution reservoir to promote the aqueous solution of the accelerator. The product is removed by contacting with the aqueous solution of the accelerator, and the product-removed hydrogen is discharged from the discharge passage. As a result, hydrogen in a state where products such as bubbles and metal inclusions are removed in a small space without providing a room for removing the product and without providing a drive source for fluid movement. It can be discharged and supplied to the consumer.

  In addition, a fluid channel connecting the reactor and the solution reservoir is generated in the first fluid channel and the reactor, which is an aqueous solution channel that supplies the promoter aqueous solution of the solution reservoir to the solid reactant of the reactor. The first fluid channel and the second fluid channel are constituted by two fluid channels of the second fluid channel, which is a circulation channel for circulating hydrogen through the solution reservoir and bringing the reaction product into contact with the promoter aqueous solution. The flow rate can be adjusted by changing the pipe diameter of the fluid channel of the fluid channel, and the amount of hydrogen can be easily controlled.

  According to a third aspect of the present invention, the hydrogen flow path is connected to an intermediate portion of the second hydrogen discharge path, and the first hydrogen is connected to the second hydrogen discharge path on the opposite side of the fluid chamber across the connection section. A discharge path is connected, and the control means is provided in the hydrogen flow path and a check valve that allows only the flow of hydrogen from the solution reservoir to the fluid chamber, and is provided in the second hydrogen discharge path. A pressure control valve that closes above a pressure; and a constant pressure shut-off valve that is provided in the first hydrogen discharge passage and has a valve body that closes when the pressure control valve is below the predetermined pressure when the pressure control valve is closed. Or it exists in the hydrogen generator as described in a 2nd aspect.

  In the third aspect, the check valve that allows only the flow of hydrogen from the solution reservoir to the fluid chamber prevents the backflow of hydrogen from the fluid chamber, sends the hydrogen in the solution reservoir to the fluid chamber, and the second hydrogen The pressure control valve provided in the discharge passage is closed above a predetermined pressure to control the inflow of hydrogen in the fluid chamber, and the constant pressure shut-off valve provided in the first hydrogen discharge passage is higher than the predetermined pressure at which the pressure control valve is closed. By closing below, by controlling the outflow and inflow of hydrogen in the liquid reservoir, the fluid chamber and the storage chamber are depressurized and the promoter aqueous solution in the solution container is provided without a drive source for fluid movement Can be fed to the solid reactant of the reactor.

  According to a fourth aspect of the present invention, the hydrogen flow path is connected to an intermediate portion of the second hydrogen discharge path, and the first hydrogen discharge path on the opposite side of the fluid chamber with the connection section interposed therebetween. A hydrogen discharge path is connected, and the control means is provided in the hydrogen flow path and allows only the flow of hydrogen from the solution reservoir to the fluid chamber; the first hydrogen discharge path; A three-way valve is provided at the connection portion of the second hydrogen discharge path, and the first hydrogen discharge path flows when the pressure exceeds a predetermined pressure, and the second hydrogen discharge path flows when the pressure falls below the predetermined pressure. It exists in the hydrogen generator as described in the 1st or 2nd aspect.

  In the fourth aspect, the check valve that allows only the flow of hydrogen from the solution reservoir to the fluid chamber prevents the backflow of hydrogen from the fluid chamber, and sends the hydrogen in the solution reservoir to the fluid chamber. A three-way valve provided at the connection between the discharge passage and the second hydrogen discharge passage circulates through the first hydrogen discharge passage which is the discharge passage on the solution container side when the pressure is higher than a predetermined pressure, and discharges hydrogen in the liquid reservoir. . On the other hand, when the pressure falls below a predetermined pressure, the second hydrogen discharge passage which is the discharge passage on the pressure chamber side is circulated to discharge hydrogen from the pressure chamber. By controlling the outflow and inflow of hydrogen in the liquid reservoir and the pressure chamber in this way, the fluid chamber and the storage chamber are depressurized, and the accelerator solution in the solution container is reacted without a drive source for fluid movement. The reactor can be fed to a solid reactant.

  According to a fifth aspect of the present invention, in the hydrogen generator according to the third aspect, the predetermined pressure of the constant pressure shut-off valve is controlled by a spring.

  In the fifth aspect, the movement of the aqueous accelerator solution can be suppressed by controlling the predetermined pressure with a spring.

  A sixth aspect of the present invention is the hydrogen generator according to the third aspect, wherein the set pressure of the pressure control valve is set to a valve opening pressure based on the internal pressure of the solution reservoir. It is in.

  In the sixth aspect, when the internal pressure of the solution reservoir decreases, that is, when the consumption of hydrogen proceeds, the aqueous accelerator solution can be circulated to the solid reactant side to generate hydrogen.

  According to a seventh aspect of the present invention, in the hydrogen generator according to the fourth aspect, the set pressure of the three-way valve is set to a valve opening pressure with reference to an internal pressure of the solution reservoir. is there.

  In the seventh aspect, when the internal pressure of the solution reservoir decreases, that is, when the consumption of hydrogen proceeds, hydrogen can be generated by flowing the aqueous accelerator solution to the solid reactant side.

  According to an eighth aspect of the present invention, in any one of the first to seventh aspects, the open end of the fluid flow path to the solution reservoir is disposed in the promoter aqueous solution. In the hydrogen generator described.

  In the eighth aspect, the product from the fluid flow path can be reliably brought into contact with the promoter aqueous solution.

  According to a ninth aspect of the present invention, the means for partitioning the fluid chamber and the storage chamber of the reactor and making the volume of the fluid chamber and the storage chamber variable is a deformation allowing member. The hydrogen generator according to the first or second aspect is provided.

  In the ninth aspect, the volume of the fluid chamber is changed according to the generation state and discharge state of hydrogen, and the pressure in the storage chamber can be changed.

  According to a tenth aspect of the present invention, the deformation allowing member that is a means for partitioning the fluid chamber and the storage chamber of the reactor and making the volume of the fluid chamber and the storage chamber variable is flexible. The hydrogen generator according to the ninth aspect is characterized by being a film of the above.

  In the tenth aspect, the volume of the fluid chamber is changed in accordance with the generation state and discharge state of hydrogen, and the pressure in the storage chamber can be changed.

  An eleventh aspect of the present invention is the hydrogen generator according to any one of the first to tenth aspects, wherein a filter is attached to a piping port of the fluid flow path through which the promoter aqueous solution moves. is there.

  In the eleventh aspect, the product can be prevented from being mixed into the reactor.

  According to a twelfth aspect of the present invention, the discharge path of the hydrogen generator according to any one of the first to eleventh aspects is connected to the fuel electrode of the fuel cell, and the generated hydrogen is supplied to the negative electrode chamber. The fuel cell equipment is featured.

  In the twelfth aspect, without providing a room for removing the product, hydrogen can be supplied to the consumption unit by discharging hydrogen in a state where products such as bubbles and metal-containing materials are removed in a small space. It can be set as the fuel cell equipment provided with the generator.

  The thirteenth aspect of the present invention for achieving the above object is that when hydrogen is generated by bringing an aqueous solution of an accelerator, which is an aqueous solution of an accelerator of a hydrogen generation reaction, into contact with a solid reactant of the hydrogen generation reaction, The generated pressurized pressure is generated to generate the generated pressurized pressure, and the partitioned chamber in the reactor containing the solid reactant is decompressed by the generated applied pressure and hydrogen discharge, thereby moving the aqueous solution of the accelerator, while And a product generated together with the aqueous accelerator solution to remove the product.

  In the thirteenth aspect, products such as bubbles and metal-containing materials are removed in a small space without providing a room for removing the products and without providing a drive source for fluid movement. The hydrogen in the state can be discharged and supplied to the consumption unit.

  In a fourteenth aspect of the present invention, when hydrogen is generated by bringing an aqueous solution of an accelerator, which is an aqueous solution of an accelerator for a hydrogen generation reaction, into contact with a solid reactant of the hydrogen generation reaction, an applied pressure is generated by the generation of hydrogen. The hydrogen generation method is characterized in that the aqueous solution of the accelerator is moved by reducing the pressure of the partitioned chamber in the reactor containing the solid reactant by the generated pressure and hydrogen discharge. .

  In the fourteenth aspect, without providing a drive source for fluid movement, hydrogen in a state where products such as bubbles and metal-containing materials are removed can be discharged and supplied to the consumption unit in a small space.

  According to a fifteenth aspect of the present invention, when hydrogen is generated by bringing an aqueous solution of an accelerator, which is an aqueous solution of an accelerator for a hydrogen generation reaction, into contact with a solid reactant of the hydrogen generation reaction, the product generated together with the hydrogen is promoted. A method for generating hydrogen is characterized in that the product is removed by contact with an aqueous solution.

  In the fifteenth aspect, hydrogen in a state where products such as bubbles and metal-containing materials are removed can be discharged and supplied to the consumption unit in a small space without providing a room for removing the products.

  A sixteenth aspect of the present invention is the hydrogen generation method according to the thirteenth or fourteenth aspect, wherein the hydrogen from which the reaction product has been removed is discharged by a generated pressure.

  In the sixteenth aspect, without providing a drive source for fluid movement, hydrogen in a state where products such as bubbles and metal-containing materials are removed can be discharged and supplied to the consumption unit in a small space.

  The hydrogen generating apparatus and the hydrogen generating method of the present invention include bubbles and metals from a reaction product obtained by contacting a solid reactant with an aqueous accelerator solution in a small space without providing a drive source for fluid movement. A hydrogen generation apparatus and a hydrogen generation method capable of supplying hydrogen in a state where a product such as a product is removed.

  In addition, the fuel cell facility of the present invention supplies hydrogen in a state where products such as bubbles and metal-containing materials are removed from a reaction product obtained by contacting a solid reactant and an aqueous accelerator solution in a small space. This is a fuel cell facility equipped with a hydrogen generator capable of

(Hydrogen generator according to the first embodiment)
A first embodiment will be described with reference to FIGS.

  FIG. 1 shows a schematic configuration of a hydrogen generator according to a first embodiment of the present invention, FIG. 2 shows a cross section of a constant pressure shut-off valve, FIGS. 3 and 4 show a cross section of a pressure control valve, and FIG. The flow of processing is shown.

  As shown in FIG. 1, the hydrogen generator 1 includes a reactor 2, and a work 3 as a solid reaction product of a hydrogen generating reaction is stored in a storage chamber 8 in the reactor 2. A solution container 4 serving as a solution reservoir is provided adjacent to the reactor 2, and an accelerator aqueous solution 5 that is an aqueous solution of a hydrogen generation accelerator is stored in the solution container 4.

  In this embodiment, sodium borohydride (SBH) was used for the work 3 and malic acid aqueous solution was used for the accelerator aqueous solution 5. The work 3 and the accelerator aqueous solution 5 will be described in detail later. In the present embodiment, the liquid supply pipe 13 is described as an example of the aqueous solution flow path. However, as the aqueous solution flow path, a hole for connecting the internal space to connect the reactor 2 and the solution container 4 is used. It is also possible to use grooves and lids.

  The reactor 2 and the solution container 4 are connected by a liquid feeding pipe 13 as a fluid flow path, and the promoter aqueous solution 5 in the solution container 4 is sent to the work 3 accommodated in the reactor 2. When the promoter aqueous solution 5 in the solution container 4 is supplied from the liquid feeding tube 13 to the workpiece 3 of the reactor 2, the promoter aqueous solution 5 comes into contact with the workpiece 3 and reacts to generate a reaction product such as hydrogen. . In addition, the liquid feeding pipe 13 sends the reaction product generated by the reaction in the reactor 2 to the solution container 4. The liquid feeding tube 13 is arranged at the end (open end) in the solution container 4 in the promoter aqueous solution 5, and the reaction product is in contact with the promoter aqueous solution 5, so that hydrogen in the reaction product is involved. Products such as foam and metal-containing materials are dissolved or precipitated in the aqueous accelerator solution 5 and removed from the hydrogen. This increases the purity of hydrogen, so that the chemical reaction proceeds smoothly.

  The reactor 2 is partitioned by a flexible elastic film 6 into a storage chamber 8 where the work 3 is stored and a reaction takes place, and a pressure chamber 7 in which the pressure varies as fluid enters and exits. When the elastic membrane 6 is deformed and moved upward due to the pressure chamber 7 being depressurized, the storage chamber 8 is depressurized, so that the promoter aqueous solution 5 in the solution container 4 moves to the reactor 2.

  The elastic membrane 6 may be, for example, a flexible bag-like member or a variable means having a syringe structure, and is not particularly limited as long as the volume of the pressure chamber 7 can be changed.

  The pressure chamber 7 in the reactor 2 and the solution container 4 are connected by a hydrogen conduit 14. The solution container 4 stores hydrogen from which bubbles and metal-containing materials have been removed. The stored hydrogen moves through the hydrogen conduit 14 to the pressure chamber 7. The hydrogen conduit 14 is provided with a check valve 10, which allows movement of the hydrogen from the solution container 4 only in the direction of the pressure chamber 7, and prevents backflow of hydrogen moving in the hydrogen conduit 14. As the hydrogen moves through the hydrogen conduit 14, the pressure chamber 7 is pressurized.

  The pressure chamber 7 in the reactor 2 has a pressure chamber side discharge passage 16 for discharging hydrogen stored in the pressure chamber 7, and the tip of the pressure chamber side discharge passage 16 (second hydrogen discharge passage) discharges from the regulator 12. It is connected to the unit 17, and the discharged hydrogen is connected to the hydrogen consumption unit. Further, the tip of a solution container side discharge path 15 (first hydrogen discharge path) for discharging hydrogen stored in the solution container 4 is connected to the pressure chamber side discharge path 16 and the path of the regulator 12.

  The solution container side discharge passage 15 (first hydrogen discharge passage) is provided with a constant pressure closing valve 9 for controlling the discharge of hydrogen stored in the solution container 4, and the hydrogen pressure stored in the solution container 4 is set to a predetermined pressure. When the above is reached, the constant pressure shut-off valve 9 is opened, and the hydrogen stored in the solution container 4 passes through the solution container side discharge path 15, passes through the connection portion with the pressure chamber side discharge path 16, and goes to the discharge section 17 through the regulator 12. And discharged. On the other hand, when the hydrogen pressure stored in the solution container 4 falls below a predetermined pressure, the constant pressure shut-off valve 9 is closed, the hydrogen that has been cut off the discharge path is stored in the solution container 4, and the solution container 4 is gradually added. Press. When the pressurization is continued and the internal pressure of the solution container 4 becomes a predetermined pressure or more, the constant pressure shut-off valve 9 is opened as described above, and hydrogen is discharged.

  The pressure chamber side discharge passage 16 (second hydrogen discharge passage) is provided with a pressure control valve 11 for controlling the discharge of hydrogen stored in the pressure chamber 7, and the hydrogen pressure stored in the solution container 4 has a predetermined pressure. When the pressure falls below, the pressure control valve 11 opens, and the hydrogen stored in the pressure chamber 7 passes through the pressure chamber side discharge passage 16 and is discharged to the discharge portion 17 via the regulator 12 through the connection portion with the solution container side discharge passage 15. Is done. Since the inside of the pressure chamber 7 is depressurized by the movement of hydrogen, the accommodating chamber 8 is depressurized by the elastic film 6 being deformed and moved upward. When the storage chamber 8 is depressurized, the promoter aqueous solution 5 in the solution container 4 moves to the reactor 2 and comes into contact with the workpiece 3 to generate hydrogen. On the contrary, when the hydrogen pressure stored in the solution container 4 becomes a predetermined pressure or more, the pressure control valve 11 is closed, and the hydrogen whose discharge path is cut off is stored in the pressure chamber 7, and the pressure chamber 7 is gradually increased. Press. Since the inside of the pressure chamber 7 continues to be pressurized and the elastic membrane 6 is deformed and moved downward to pressurize the storage chamber 8, the movement of the promoter aqueous solution 5 from the solution container 4 to the reactor 2 is stopped. When pressurization in the pressure chamber 7 continues and hydrogen in the solution container 4 is discharged through the constant pressure closing valve 9, the hydrogen pressure in the solution container 4 falls below a predetermined pressure, and the pressure control valve 11 opens.

  Although details will be described later, the predetermined pressure is set, for example, in relation to atmospheric pressure and hydrogen pressure (internal pressure of the solution container 4). That is, since the set pressure of the pressure control valve 11 is set to the valve opening pressure with reference to the internal pressure of the solution container 4, a broken line arrow is attached from the solution container 4 to the pressure control valve 11, and the state is shown in FIG. It was.

  The regulator 12 adjusts the amount of hydrogen discharged from both the pressure chamber 7 and the solution container 4 of the reactor 2. Although the regulator 12 can control the ratio of the hydrogen discharge amount between the pressure chamber 7 and the solution container 4, it is also possible to discharge hydrogen at a constant hydrogen pressure using a constant pressure valve.

  In the hydrogen generator 1 described above, hydrogen is generated by supplying the promoter aqueous solution 5 to the work 3 of the reactor 2, and hydrogen generated in the reactor 2 (hydrogen, bubbles entrained with hydrogen, etc.) is promoted. After coming into contact with the aqueous solution 5, the hydrogen is stored in the pressure chamber 7 from the hydrogen conduit 14, and is sent from the solution container side discharge path 15 to the hydrogen consuming part when the inside of the solution container 4 is at atmospheric pressure or higher. The movement of the promoter aqueous solution 5 and the movement of the generated hydrogen are performed by opening / closing control of the constant pressure closing valve 9 and the pressure control valve 11 by the pressure of hydrogen at the time of generation. For this reason, the power for production | generation of hydrogen and movement of hydrogen is not required, and the pump etc. for supplying the promoter aqueous solution 5 become unnecessary.

  The structure of the constant pressure shut-off valve 9 shown as a symbol in FIG. 1 will be described in detail based on FIG.

  As shown in FIG. 2, the constant pressure shut-off valve 9 includes a spring 19 and a pipe 21 that connect the fixed portion 18 and the valve body 20. The valve body 20 is urged to the pipe 21 by the spring 19 and is always closed by the urging force of the spring 19. When hydrogen having a pressure equal to or higher than a predetermined pressure flows through the pipe 21, the valve body 20 moves against the biasing force of the spring 19, and hydrogen flows through the pipe 21. In FIG. 1, the pipe 21 is the solution container side discharge path 15, and hydrogen in the solution container 4 flows therethrough. The pipe is made of a material whose shape can be changed, such as a resin tube, and the diameter of the pipe changes due to the balance of the spring by changing the amount of hydrogen flowing in the pipe, and the pipe 21 opens and closes. The upper and lower sides of the valve body are determined by the balance between the combined force of the spring force and the external pressure, the force that deflects the piping, and the pressure of the reaction solution. If the internal pressure of the solution container 4 is equal to or higher than the predetermined pressure, the reaction solution pressure is opened and the pipe 21 can be circulated. However, if the pressure is lower than the predetermined pressure, the pipe is closed by the biasing force of the spring and hydrogen cannot circulate. . By setting the biasing force of the spring to a pressure corresponding to the atmospheric pressure, the predetermined pressure is adjusted by the spring so as to balance the atmospheric pressure. Moreover, it can control to desired force with a spring.

  As described above, when the internal pressure of the solution container 4 is equal to or higher than the predetermined pressure (the urging force of the spring corresponding to the atmospheric pressure) by the constant pressure shut-off valve 9, hydrogen is discharged and the internal pressure of the solution container 4 is set to the predetermined pressure ( When the pressure is less than the biasing force of the spring corresponding to the atmospheric pressure, the closed state is reached, and hydrogen is stored in the solution container 4.

  The structure of the pressure control valve 11 shown as a symbol in FIG. 1 will be described in detail with reference to FIGS.

  First, in the pressure control valve 11 shown in FIG. 1, the pressure chamber side discharge passage 16 is connected in the left-right direction. FIG. 1 is a diagram for showing the arrangement relationship of devices as a gas or liquid transfer circuit. Therefore, it is not limited whether the pressure chamber side discharge path 16 is in the vertical direction or the horizontal direction. That is, the pressure chamber side discharge path 16 on the left side and the pressure chamber side discharge path 16 on the right side may be in the same direction with respect to the pressure control valve 11. The pressure control valve 11 shown in FIGS. 3 and 4 is an example in which the left pressure chamber side discharge path 16 and the right pressure chamber side discharge path 16 are in the same direction. FIG. 4 is a cross-sectional view showing the open state, and FIG. 4 is a cross-sectional view showing the closed state.

  As shown in FIGS. 3 and 4, the pressure control valve 11 has a base 22 on the outer peripheral portion. The base 22 serves as an outer frame for determining the overall size of the pressure control valve 11 as well as being connected to other equipment and piping used in a gas or liquid transfer circuit. The base 22 may be integrally formed with other equipment used in the transfer circuit.

  The base 22 is provided with a penetrating portion 23 penetrating in the thickness direction (vertical direction in the drawing) of the base. A first pressure deforming portion 24 is provided so as to close one opening 23a of the penetrating portion 23, and a second pressure deforming portion 25 is provided so as to close the other opening 23b. The 1st pressure deformation part 24 and the 2nd pressure deformation part 25 consist of a flexible sheet | seat, and can deform | transform in the thickness direction (up-down direction in a figure). A partition member 26 is provided in a space between the first pressure deforming portion 24 and the second pressure deforming portion 25 in the penetrating portion 23, and the partition member 26 is disposed in the middle in the thickness direction of the base body 22 and is subjected to the first pressure deformation. A space between the portion 24 and the second pressure deformation portion 25 is partitioned.

  A first flow path 27 is formed on the first pressure deforming portion 24 side by being partitioned by the partition member 26, and a second flow path 28 is formed on the second pressure deforming portion 25 side. The first flow path 27 and the second flow path 28 are each extended in the planar direction of the base body 22.

  The first flow path 27 is connected to, for example, the pressure chamber 7 side of the pressure chamber side discharge path 16, and the second flow path 28 is connected to, for example, the regulator 12 and the discharge unit 17 side of the pressure chamber side discharge path 16. ing. A through hole 29 is provided in the partition member 26, and the first flow path 27 and the second flow path 28 are communicated with each other through a communication path 30 formed by the through hole 29.

  A valve member 31 is provided in the space between the first pressure deforming portion 24 and the second pressure deforming portion 25 of the penetrating portion 23 so as to be movable in the vertical direction in the figure, and the valve member 31 is a valve penetrating the through hole 29. The rod 32 and the valve body 33 disposed on the second flow path 28 side are integrally provided. When the valve member 31 moves to the upper side in the drawing, the communication passage 30 is closed by the valve body 33 from the second flow path 28 side (see FIG. 4). A first pressure deformation portion 24 is connected to the end of the valve rod 32, and a second pressure deformation portion 25 is connected to the outer surface of the valve body 33. That is, the valve member 31 is supported by the first pressure deformation portion 24 and the second pressure deformation portion 25 so that the communication passage 30 can be opened and closed.

  The pressure control valve 11 receives, for example, a predetermined pressure such as atmospheric pressure on the outside of the first pressure deforming portion 24, and receives the hydrogen pressure of the solution container 4 (see FIG. 1) on the outside of the second pressure deforming portion 25. Are arranged as follows. That is, as indicated by a dotted line in FIG. 1, the outside of the second pressure deforming portion 25 and the solution container 4 are connected, and the hydrogen pressure of the solution container 4 (see FIG. 1) is received outside the second pressure deforming portion 25. Has been. Since the hydrogen pressure of the solution container 4 (see FIG. 1) is received on the outside of the second pressure deforming portion 24, a hydrogen pressure with little pressure fluctuation can be applied to the pressure control valve 11. It is also possible to receive the hydrogen pressure of the reactor 2 outside the second pressure deformation part 25.

  For this reason, when the hydrogen pressure in the solution container 4 is higher than the atmospheric pressure, the first pressure deforming portion 24 and the second pressure deforming portion 25 move together with the valve member 31 upward as shown in FIG. The passage 30 is closed by the valve body 33, and the first flow path 27 and the second flow path 28 are blocked. Therefore, when the hydrogen pressure in the solution container 4 (see FIG. 1) is high, the first flow path 27 and the second flow path 28 are blocked, and the hydrogen in the pressure chamber 7 is stored in the pressure chamber 7.

  When the consumption of hydrogen progresses and the hydrogen pressure in the solution container 4 becomes lower than the atmospheric pressure, the first pressure deformation portion 24 and the second pressure deformation portion 25 move downward in the figure together with the valve member 31 as shown in FIG. The valve body 33 is separated from the through hole 29 and the communication path 30 is opened, and the first flow path 27 and the second flow path 28 are in communication. Therefore, when the hydrogen pressure in the solution container 4 (see FIG. 1) becomes low, the first flow path 27 and the second flow path 28 communicate with each other and hydrogen in the pressure chamber 7 is discharged. The aqueous solution 5 is supplied to the reactor 2.

  In this way, the pressure control valve 11 is controlled to open and close in accordance with the consumption of hydrogen in the solution container 4 (see FIG. 1), and when necessary, the promoter aqueous solution 5 (see FIG. 1) is supplied to the reactor without using power. 2 can be supplied to generate hydrogen.

  The operation of the hydrogen generator 1 described above will be described with reference to FIGS. 1 and 5. The step numbers shown in the following description are the step numbers shown in FIG.

  The promoter aqueous solution 5 is supplied from the solution container 4 to the workpiece 3 of the reactor 2 through the liquid feeding tube 13 (step S1). When the hydrogen pressure in the solution container 4 is low, the pressure control valve 11 is open, and the constant pressure shut-off valve 9 is closed, the promoter aqueous solution 5 is supplied to the reactor 2, and the promoter aqueous solution 5 contacts the workpiece 3. Reaction occurs to generate hydrogen (step S2). Due to the increase in the internal pressure of the reactor 2, the generated reaction products such as hydrogen, products and bubbles move to the solution container 4 through the liquid feeding tube 13 (step S 3) (arrow b in FIG. 1). The promoter aqueous solution 5 in the solution container 4 and the reaction product come into contact with each other, the metal-containing material and bubbles are removed, and hydrogen is stored. The stored hydrogen passes through the hydrogen conduit 14 and is sent to the pressure chamber 7 (step S4) (arrow c in FIG. 1). When the hydrogen pressure in the solution container 4 becomes equal to or higher than the atmospheric pressure accompanying the generation of hydrogen, the constant pressure shut-off valve 9 is opened and the pressure control valve 11 is closed (step S5), and the hydrogen in the solution container 4 is discharged (step S6). (Arrow d → f in FIG. 1). When hydrogen is discharged and the hydrogen pressure in the solution container 4 falls below atmospheric pressure, the constant pressure shut-off valve 9 is closed (step S7), and when the pressure control valve 11 is opened, hydrogen in the pressure chamber 7 is discharged (step S8). (Arrow e → f in FIG. 1). As the hydrogen in the pressure chamber 7 is discharged, the pressure chamber 7 is depressurized and the elastic film 6 is deformed and moved upward (step S9), so that the storage chamber 8 is depressurized. When the storage chamber 8 is depressurized, the promoter aqueous solution 5 moves to the reactor 2 (step S10) (arrow a in FIG. 1).

  The hydrogen produced in the reactor 2 can come into contact with the promoter aqueous solution 5 together with the product and foam to separate the hydrogen and the product (foam). For this reason, without providing a means for separation (for example, a separation chamber or the like), it is possible to separate the product (bubbles) to eliminate a decrease in reaction efficiency and supply hydrogen to the consumption unit. And, by reducing the internal pressure of the reactor 2, the promoter aqueous solution 5 can be moved and the hydrogen, products, and bubbles can be moved, so that no power is required for movement and hydrogen is generated without power consumption. Can do.

  Therefore, it is provided with a means for separating bubbles and the like, in a state where the work 3 and the promoter aqueous solution 5 are brought into contact with each other in a small space, and products such as bubbles and metal-containing materials are removed from the obtained reaction product. A hydrogen generator capable of supplying hydrogen to the consumption unit is provided. And the movement of the promoter aqueous solution 5 and the reaction product containing hydrogen can be stably performed by reducing the internal pressure of the reactor 2 without using power.

  Here, the specific example of the workpiece | work 3 and the promoter aqueous solution 5 is demonstrated.

  Sodium borohydride (SBH) is used for the work 3 and malic acid aqueous solution is used for the accelerator aqueous solution 5. SBH is solid, and the form may be powder or tablet. The concentration of the malic acid aqueous solution is 5% or more and 60% or less, preferably 10% or more and 40% or less. Usually, a malic acid aqueous solution having a concentration of 25% is used. The hydrogen generation reaction is a reaction with SBH and malic acid aqueous water. Malic acid acts as a reaction accelerator.

  The example of the combination as the workpiece | work 3 and the promoter aqueous solution 5 is demonstrated.

  When a borohydride salt, an aluminum hydride salt, a solid or a basic solution is used as the work 3, an organic acid is 5% to 60% (10% to 40%), usually 25, as the promoter aqueous solution 5. % Concentration. Sodium, potassium and lithium are used as the salt of the work 3, and citric acid, malic acid and succinic acid are used as the organic acid of the accelerator aqueous solution 5.

  Further, when a borohydride salt, an aluminum hydride salt, a solid or a basic solution is used as the work 3, the metal chloride is used at a concentration of 1% to 20% as the promoter aqueous solution 5. When sodium, potassium, or lithium is used as the salt of the work 3, nickel, iron, or cobalt is usually used at a concentration of 12% as the promoter metal of the promoter aqueous solution 5.

  When metal chloride is used as the work 3, a basic solution of borohydride salt or aluminum hydride salt is used as the promoter aqueous solution 5 at a concentration of 1% to 20%, usually 12%. . Nickel, iron, and cobalt are used as the metal of the work 3, and sodium, potassium, and lithium are used as the salt of the accelerator aqueous solution 5.

  Further, when a metal whose oxidation-reduction potential is lower than that of hydrogen is used as the work 3, an acid is used as the promoter aqueous solution 5. Magnesium, aluminum, and iron are used as the metal of the work 3, and hydrochloric acid and sulfuric acid are used as the acid of the aqueous accelerator solution 5.

  When an amphoteric metal is used as the work 3, a basic aqueous solution is used as the accelerator aqueous solution 5. Aluminum, zinc, tin, and lead are used as the amphoteric metal of the work 3, and sodium hydroxide is used as the basic aqueous solution of the accelerator aqueous solution 5.

(Hydrogen generator according to the second embodiment)
A second embodiment will be described with reference to FIGS. In addition, the same code | symbol is attached | subjected to the same member as the member shown in FIG. 1, and the overlapping description is abbreviate | omitted.

  FIG. 6 shows a schematic configuration of the hydrogen generator according to the second embodiment of the present invention, FIGS. 7 and 8 show a cross section of the three-way valve, and FIG. 9 shows a flow of the hydrogen generation process.

  The hydrogen generator 34 includes a reactor 2 that stores the workpiece 3, a solution container 4 that stores the promoter aqueous solution 5, a liquid feeding pipe 13 that connects the reactor 2 and the solution container 4, and an elastic membrane 6 in the reactor 2. The pressure chamber 7 for storing hydrogen, the hydrogen conduit 14 for sending the hydrogen in the solution container 4 to the pressure chamber 7, the check valve 10 installed on the hydrogen conduit 14, and the solution container side discharge path 15 (first hydrogen discharge path). ), The pressure chamber side discharge path 16 (second hydrogen discharge path), the three-way valve 35, the regulator 12, and the discharge section installed at the connection section of both the solution container side discharge path 15 and the pressure chamber side discharge path 16 17.

  Similarly to the first embodiment, in the second embodiment, sodium borohydride (SBH) was used for the workpiece 3 and malic acid aqueous solution was used for the accelerator aqueous solution 5.

  The three-way valve 35 is a valve that works by combining both the constant pressure closing valve 9 and the pressure control valve 11 in the hydrogen generator 1 of FIG. 1 (first embodiment).

  As shown in FIG. 6, the hydrogen generator 34 is provided with a three-way valve 35 that controls the discharge of hydrogen stored in the pressure chamber 7 and the solution container 4, and the hydrogen pressure stored in the solution container 4 is atmospheric pressure. The three-way valve 35 shuts off the solution container side discharge path 15 and circulates through the pressure chamber side discharge path 16, and hydrogen stored in the pressure chamber 7 passes through the pressure chamber side discharge path 16 and is discharged to the solution container side. It is discharged to the discharge portion 17 via the regulator 12 through the connection portion with the path 15. Due to this movement of hydrogen, the pressure chamber 7 is depressurized and the elastic film 6 is deformed and moved upward, so that the storage chamber 8 is depressurized. When the storage chamber 8 is depressurized, the promoter aqueous solution 5 in the solution container 4 moves to the reactor 2 and comes into contact with the workpiece 3 to generate hydrogen. On the contrary, when the hydrogen pressure stored in the solution container 4 becomes equal to or higher than the predetermined pressure, the three-way valve 35 shuts off the pressure chamber side discharge path 16, and hydrogen that has been disconnected from the discharge path is stored in the pressure chamber 7. The pressure chamber 7 is pressurized. On the other hand, the solution container side discharge passage 15 flows and the hydrogen in the solution container 4 is discharged. Since the inside of the pressure chamber 7 continues to be pressurized and the elastic membrane 6 is deformed and moved downward to pressurize the storage chamber 8, the movement of the promoter aqueous solution 5 from the solution container 4 to the reactor 2 is stopped. When the hydrogen in the solution container 4 is discharged and the pressure in the solution container 4 is reduced so that the hydrogen pressure falls below a predetermined pressure, the three-way valve 35 again shuts off the solution container side discharge path 15 and the pressure chamber side discharge path. 16 is distributed.

  Although details will be described later, the predetermined pressure is set, for example, in relation to atmospheric pressure and hydrogen pressure (internal pressure of the solution container 4). In other words, since the set pressure of the three-way valve 35 is set based on the internal pressure of the solution container 4, a broken line arrow is attached from the solution container 4 to the three-way valve 35, and the state is shown in FIG.

  In the hydrogen generator 34 described above, hydrogen is generated by supplying the promoter aqueous solution 5 to the work 3 of the reactor 2, and hydrogen generated in the reactor 2 (hydrogen, bubbles entrained with hydrogen, etc.) is promoted. After coming into contact with the aqueous solution 5, the hydrogen is stored in the pressure chamber 7 from the hydrogen conduit 14, and when the internal pressure of the solution container 4 is high, it is sent from the solution container side discharge path 15 to the discharge unit 17 that is a hydrogen consumption unit. In the movement of the promoter aqueous solution 5 and the generated hydrogen, the three-way valve 35 controls the opening and closing of the solution container side discharge path 15 and the pressure chamber side discharge path 16 by the pressure of hydrogen at the time of generation. For this reason, the power for production | generation of hydrogen and movement of hydrogen is not required, and the pump etc. for supplying the promoter aqueous solution 5 become unnecessary.

  The structure of the three-way valve 35 shown as a symbol in FIG. 6 will be described in detail with reference to FIGS.

  First, in the three-way valve 35 shown in FIG. 6, the solution container side discharge path 15 is connected perpendicularly to the pressure chamber side discharge path 16, but FIG. 6 shows the arrangement relationship of equipment as a gas or liquid transfer circuit. Since it is a figure for showing, the connection direction of the flow paths of the pressure chamber side discharge path 16 and the solution container side discharge path 15 is not particularly limited. The three-way valve 35 shown in FIGS. 7 and 8 has the same arrangement as the flow path shown in FIG. 6. FIG. 7 shows the open state of the pressure chamber 7 (FIG. 6) of the three-way valve 35 and the solution container 4 (FIG. FIG. 8 is a cross-sectional view showing the closed state of the pressure chamber 7 and the open state of the solution container 4.

  The three-way valve 35 has a base body 38 on the outer peripheral portion. The base 38 serves as an outer frame for determining the overall size of the three-way valve 35 as well as being connected to other equipment and piping used in a gas or liquid transfer circuit. The base body 38 may be formed integrally with other equipment used in the transfer circuit.

  The three-way valve 35 includes a base body 38, a valve member 42, and a flexible film 37. A through portion 36 is provided in the base body 38, and an upper portion of the through portion 36 is closed with a flexible film 37. Since the through hole 45 on the solution container side is opened when the valve body 44 moves upward at the lower part of the through part 36, the through part 36 is opened, and when the valve body 44 moves downward, the through hole 45 on the solution container side. Is closed, so that the lower portion of the penetrating portion 36 is closed. Inside the substrate 38, a hydrogen conduit 39 on the pressure chamber side and a hydrogen conduit 40 on the solution container side penetrate in the plane direction, and a valve member 42 is disposed. The valve member 42 includes a valve rod 43 and a valve body 44, and the upper portion of the valve rod 43 is in contact with the base body 38 via a flexible film 37 that can be deformed in the thickness direction. It has become. The base body 38 is provided with a stopper 41 that has a penetrating portion having the same thickness as the hydrogen conduit 40 on the solution container side and supports the vertical movement of the valve body 44.

  The hydrogen conduit 39 on the pressure chamber side is connected to, for example, the pressure chamber side discharge passage 16 that is a flow path into which hydrogen from the pressure chamber 7 flows, and the hydrogen conduit 40 on the solution container side is, for example, a flow from which hydrogen is discharged. The solution container side through hole 45 is connected to a solution container side discharge path 15 through which hydrogen discharged from the solution container 4 flows. A through hole 45 is provided inside the base body 38, and a hydrogen conduit 39 on the pressure chamber side and a hydrogen conduit 40 on the solution container side are connected via a communication passage 46 formed by the through hole 45.

  The valve member 42 moves up and down via the flexible film 37, and the valve body 44 also moves up and down according to the valve member 42. When the valve body 44 moves downward, the bottom of the valve body 44 comes into contact with the bottom of the inner wall of the hydrogen conduit 40 on the solution container side and the bottom of the stopper 41, and the through portion 36 is closed. When the through portion 36 is closed, the solution container side through hole 45 is closed, and hydrogen is discharged from the pressure chamber side through the discharge path. When the valve body 44 moves upward, the upper part of the valve body 44 is caught by the upper inner wall part of the hydrogen conduit 40 on the solution container side and the upper part of the stopper 41, and the through part 36 is opened, and the through hole 45 on the solution container side is opened. The pressure chamber side discharge path 16 is closed and the hydrogen is discharged from the solution container side toward the discharge path.

  The hydrogen pressure in the solution container 4 from the lower part of the valve body 44 and the external pressure (for example, atmospheric pressure) are balanced from the outside of the flexible membrane. The hydrogen pressure in the pressure chamber pushes the flexible inner side and the upper part of the valve body, and therefore hardly affects the movement of the valve body.

  When the hydrogen pressure in the solution container 4 becomes equal to or higher than a predetermined pressure (atmospheric pressure), the valve body 44 is pushed upward due to the balance of force, and the through hole 47 on the solution container side opens, and conversely, the pressure chamber side penetrates. The hole 45 is closed, and hydrogen is discharged from the solution container 4 to the discharge portion 17 via the regulator 12 (state shown in FIG. 8). On the other hand, when the hydrogen evolution in the solution container 4 falls below a predetermined pressure (atmospheric pressure), the valve body 44 is pushed downward by force balance, and the through hole 47 on the solution container side is closed, and conversely, the pressure chamber side The through hole 45 is opened, and hydrogen flows from the pressure chamber side and is discharged to the discharge portion 17 via the regulator 12 (state of FIG. 7).

  As described above, the three-way valve 35 changes the pressure in the container by controlling the opening and closing of the flow passage when the hydrogen pressure in the solution container 4 becomes equal to or higher than a predetermined pressure (atmospheric pressure). A promoter aqueous solution 5 in the solution container 4 is supplied to the work 3 stored in the reactor 2.

  The operation of the hydrogen generator 34 described above will be described with reference to FIGS.

  The promoter aqueous solution 5 is supplied from the solution container 4 to the reactor 2 through the liquid feeding tube 13 (step S11). When the hydrogen pressure in the solution container 4 is low and the three-way valve 35 shuts off the solution container side discharge path 15 and causes the pressure chamber side discharge path 16 to flow, the promoter aqueous solution 5 is supplied to the reactor 2 and contacts the workpiece 3. Then, a reaction occurs to generate hydrogen (step S12). Due to the increase in the internal pressure of the reactor 2, the generated reaction products such as hydrogen, products and bubbles move to the solution container 4 through the liquid feeding tube 13 (step S 13) (arrow b in FIG. 6). The promoter aqueous solution 5 in the solution container 4 and the reaction product come into contact with each other, the metal-containing material and bubbles are removed, and hydrogen is stored. The stored hydrogen passes through the hydrogen conduit 14 and is sent to the pressure chamber 7 (step S14) (arrow c in FIG. 6). When the hydrogen pressure in the solution container 4 becomes equal to or higher than the atmospheric pressure due to the generation of hydrogen, the three-way valve 35 (step S15) flows through the solution container side discharge path 15 and shuts off the pressure chamber side discharge path 16. The hydrogen inside is discharged (step S16) (arrow d → f in FIG. 6). When the hydrogen is discharged and the hydrogen pressure in the solution container 4 falls below the atmospheric pressure, the three-way valve 35 (step S17) shuts off the solution container side discharge path 15 and causes the pressure chamber side discharge path 16 to flow. Hydrogen is discharged (step S18) (arrow e → f in FIG. 6). As the hydrogen in the pressure chamber 7 is discharged, the pressure chamber 7 is depressurized, and the elastic membrane 6 is deformed and moved upward (step S19), so that the storage chamber 8 is depressurized. When the storage chamber 8 is depressurized, the promoter aqueous solution 5 moves to the reactor 2 (step S20) (arrow a in FIG. 6).

  The hydrogen produced in the reactor 2 can come into contact with the promoter aqueous solution 5 together with the product and foam to separate the hydrogen and the product (foam). For this reason, without providing a means for separation (for example, a separation chamber or the like), it is possible to separate the product (bubbles) to eliminate a decrease in reaction efficiency and supply hydrogen to the consumption unit. And, by reducing the internal pressure of the reactor 2, the promoter aqueous solution 5 can be moved and the hydrogen, products, and bubbles can be moved, so that no power is required for movement and hydrogen is generated without power consumption. Can do.

  Therefore, it is provided with a means for separating bubbles and the like, in a state where the work 3 and the promoter aqueous solution 5 are brought into contact with each other in a small space, and products such as bubbles and metal-containing materials are removed from the obtained reaction product. A hydrogen generator capable of supplying hydrogen to the consumption unit is provided. And the movement of the promoter aqueous solution 5 and the reaction product containing hydrogen can be stably performed by reducing the internal pressure of the reactor 2 without using power.

  Here, a porous filter may be provided in at least one place in the pipe port of the conduit or in the middle tube. The porous filter is made of a metal foam, and by providing the porous filter, excessive movement of the metal hydride can be prevented. In addition, the reaction amount of the metal hydride in the solution container can be reduced, and there is an effect that the amount of hydrogen generation can be easily controlled.

(Hydrogen generator according to the third embodiment)
A third embodiment will be described based on FIG.

  FIG. 10 shows a schematic configuration of a hydrogen generator according to the third embodiment of the present invention. The same members as those shown in FIGS. 1 and 6 are denoted by the same reference numerals, and redundant description is omitted.

  The hydrogen generator 48 includes the liquid supply pipe 13 of the hydrogen generation apparatus 34 in FIG. 6 (second embodiment) as two liquid supply pipes 49 and 50, and check valves 51 and 50 respectively. 52 is provided. Further, the liquid feeding pipe 49 as the first fluid flow path sends the promoter aqueous solution 5 in the solution container 4 to the work 3 in the reactor 2, and the check valve 51 provided in the liquid feeding pipe 49 is a promoter aqueous solution. 5 is allowed to move only in the direction of the reactor 2 from the solution container 4 to prevent backflow. The opening end of the liquid feeding pipe 49 is arranged so as to be in contact with the work 3, and the accelerator aqueous solution is directly added to the work 3. On the other hand, the liquid feed pipe 50 feeds the reaction product generated in the reactor 2 to the solution container 4, and a check valve 52 provided in the liquid feed pipe 50 moves from the reaction product reactor 2 to the solution container 4. Only movement is allowed and backflow is prevented. The open end of the liquid feeding pipe 50 is arranged in the promoter aqueous solution 5 in the solution container 4, and the reaction product removes products such as bubbles and metal-containing materials from the hydrogen by the promoter aqueous solution 5. Further, the open end of the liquid feeding pipe 50 may not be brought into contact with the promoter aqueous solution 5 in the solution container 4. In the hydrogen generator 48, by providing two liquid feeding pipes 49 and 50, the pipe diameters of the liquid feeding pipes 49 and 50 can be changed so as to cope with the difference in the flow rates of the reaction product and the promoter aqueous solution 5. can do.

(Fuel cell facility according to the first embodiment)
FIG. 11 shows a schematic configuration of the fuel cell facility according to the first embodiment of the present invention. The fuel cell facility according to the first embodiment of the present invention will be described based on FIG.

  The fuel cell facility 53 according to the first embodiment described above can be made the fuel cell facility 53 by eliminating the regulator 12 of the hydrogen generator 1 and connecting the anode chamber 55 of the fuel cell 54 and the discharge unit 17.

  As shown in FIG. 11, the fuel cell facility 53 according to the first embodiment of the present invention is a facility in which the hydrogen generator 1 in the first embodiment shown in FIG. 1 is connected to the fuel cell 54. That is, the fuel cell 54 is provided with an anode chamber 55, and the anode chamber 55 constitutes a space in contact with the anode chamber of the fuel cell 56. The anode chamber is a space that temporarily holds hydrogen consumed by the anode.

  The anode chamber 55 and the reactor 2 are connected by a pressure chamber side discharge path 16 (second hydrogen discharge path), and hydrogen generated in the reactor 2 and the solution container 4 is supplied to the anode chamber of the anode chamber 55. The hydrogen supplied to the anode chamber is consumed by the fuel cell reaction at the anode. The amount of hydrogen consumed at the anode is determined according to the output of the fuel cell 54.

  The fuel cell facility 53 is a fuel according to the first embodiment of the present invention that includes the hydrogen generator 1 that can stably supply the promoter aqueous solution 5 and generate hydrogen without using a complicated mechanism or power. Battery equipment 53 can be obtained.

  FIG. 12 shows a schematic configuration of a fuel cell facility according to the second embodiment of the present invention. Based on FIG. 12, a fuel cell facility according to a second embodiment of the present invention will be described.

  The fuel cell facility 57 according to the second embodiment described above can be made the fuel cell facility 57 by eliminating the regulator 12 of the hydrogen generator 34 and connecting the anode chamber 55 of the fuel cell 54 and the discharge unit 17.

(Fuel cell facility according to the second embodiment)
As shown in FIG. 12, the fuel cell equipment 57 according to the second embodiment of the present invention is equipment in which the hydrogen generator 34 in the second embodiment shown in FIG. That is, the fuel cell 54 is provided with an anode chamber 55, and the anode chamber 55 constitutes a space in contact with the anode chamber of the fuel cell 56. The anode chamber is a space that temporarily holds hydrogen consumed by the anode.

  The anode chamber 55 and the reactor 2 are connected by the pressure chamber side discharge path 16 (second hydrogen discharge path), and hydrogen generated in the reactor 2 is supplied to the anode chamber of the anode chamber 55. The hydrogen supplied to the anode chamber is consumed by the fuel cell reaction at the anode. The amount of hydrogen consumed at the anode is determined according to the output of the fuel cell 54.

  The fuel cell facility 57 is a fuel according to the second embodiment of the present invention, which includes a hydrogen generator 34 that can stably supply the promoter aqueous solution 5 and generate hydrogen without using a complicated mechanism or power. Battery equipment 57 can be obtained.

(Fuel cell facility according to the third embodiment)
FIG. 13 shows a schematic configuration of a fuel cell facility according to the third embodiment of the present invention. Based on FIG. 13, a fuel cell facility according to a third embodiment of the present invention will be described.

  The fuel cell facility 58 according to the third embodiment described above can be configured as the fuel cell facility 58 by eliminating the regulator 12 of the hydrogen generator 48 and connecting the anode chamber 55 of the fuel cell 54 and the discharge unit 17.

  As shown in FIG. 13, the fuel cell facility 58 according to the third embodiment of the present invention is a facility in which the hydrogen generator 48 in the third embodiment shown in FIG. 10 is connected to the fuel cell 54. That is, the fuel cell 54 is provided with an anode chamber 55, and the anode chamber 55 constitutes a space in contact with the anode chamber of the fuel cell 56. The anode chamber is a space that temporarily holds hydrogen consumed by the anode.

  The anode chamber 55 and the reactor 2 are connected by the pressure chamber side discharge path 16 (second hydrogen discharge path), and hydrogen generated in the reactor 2 is supplied to the anode chamber of the anode chamber 55. The hydrogen supplied to the anode chamber is consumed by the fuel cell reaction at the anode. The amount of hydrogen consumed at the anode is determined according to the output of the fuel cell 54.

  The fuel cell facility 58 is a fuel according to a third embodiment of the present invention that includes a hydrogen generator 48 that can stably supply the promoter aqueous solution 5 and generate hydrogen without using a complicated mechanism or power. Battery equipment 58 can be obtained.

  The hydrogen generator of the present invention and the fuel cell equipment equipped with the hydrogen generator can generate hydrogen by moving the promoter aqueous solution 5 without power consumption without using power such as a pump. In addition, by bringing the reaction product into contact with the promoter aqueous solution 5 in the solution container 4, the time until the hydrogen generation reaction is stopped is shortened, and the amount of hydrogen can be easily controlled.

  The present invention, for example, consumes power in a particularly small flow path in addition to the industrial field of hydrogen generators that decompose metal hydrides to generate hydrogen and fuel cell equipment that uses hydrogen generated in the hydrogen generator as fuel. It can be used in various fields to be controlled without any problems.

It is a schematic block diagram of the hydrogen generator which concerns on 1st Embodiment of this invention. It is sectional drawing of a constant pressure closing valve. It is sectional drawing of a pressure control valve. It is sectional drawing of a pressure control valve. It is a flowchart of the hydrogen generator which concerns on 1st Embodiment of this invention. It is a schematic block diagram of the hydrogen generator which concerns on 2nd Embodiment of this invention. It is sectional drawing of a three-way valve. It is sectional drawing of a three-way valve. It is a flowchart of the hydrogen generator which concerns on 2nd Embodiment of this invention. It is a schematic block diagram of the hydrogen generator which concerns on 3rd Embodiment of this invention. It is explanatory drawing which shows schematic structure of the fuel cell equipment which concerns on 1st Embodiment of this invention. It is explanatory drawing which shows schematic structure of the fuel cell equipment which concerns on 2nd Embodiment of this invention. It is explanatory drawing which shows schematic structure of the fuel cell equipment which concerns on 3rd Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 34, 48 Hydrogen generator 2 Reactor 3 Workpiece | work 4 Solution container 5 Accelerator aqueous solution 6 Elastic film 7 Pressure chamber 8 Storage chamber 9 Constant pressure shut-off valve 10, 51, 52 Check valve 11 Pressure control valve 12 Regulator 13, 49 , 50 Liquid feed pipe 14 Hydrogen conduit 15 Solution container side discharge path (first hydrogen discharge path)
16 Pressure chamber side discharge path (second hydrogen discharge path)
17 Discharge part 18 Fixing part 19 Spring 20, 33, 44 Valve body 21 Piping 22, 38 Base 23, 36 Through part 24 First pressure deformation part 25 Second pressure deformation part 26 Partition member 27 First flow path 28 Second flow Path 29 Through-hole 30, 46 Communication path 31, 42 Valve member 32, 43 Valve rod 35 Three-way valve 37 Flexible membrane 39 Hydrogen conduit on the pressure chamber side 40 Hydrogen conduit on the solution container side 41 Stopper 45 Through-hole on the pressure chamber side Hole 47 Solution container side through hole 53, 57, 58 Fuel cell equipment 54 Fuel cell 55 Anode chamber 56 Fuel cell

Claims (16)

A reactor containing a solid reactant and generating hydrogen therein;
A storage chamber in the reactor for storing the solid reactant;
A fluid chamber in which the volume of the storage chamber is variable in the storage chamber of the reactor;
A solution reservoir containing an aqueous promoter solution that generates hydrogen upon contact with the solid reactant;
A fluid flow path in communication between the reactor and the solution reservoir, and for delivering hydrogen from the reactor to the solution reservoir, an end on the solution reservoir side contacting the promoter aqueous solution;
A hydrogen flow path that communicates the solution reservoir and the fluid chamber and delivers hydrogen from the solution reservoir to the fluid chamber of the reactor;
A first hydrogen discharge path which is provided in the solution reservoir and discharges hydrogen sent to the solution reservoir;
A second hydrogen discharge path provided in the fluid chamber for discharging the hydrogen delivered to the fluid chamber;
Due to the decompression of the storage chamber through the fluid chamber due to the generation and discharge of hydrogen, the flow of the promoter aqueous solution in the fluid flow path, the hydrogen flow path, the first hydrogen discharge path, and the second hydrogen discharge path Control means for controlling the flow of hydrogen and causing the reaction product to contact the aqueous accelerator solution by flowing hydrogen through the fluid flow path,
A hydrogen generator characterized by comprising: A reactor containing a solid reactant and generating hydrogen therein;
A storage chamber in the reactor for storing the solid reactant;
A fluid chamber in which the volume of the storage chamber is variable in the storage chamber of the reactor;
A solution reservoir containing an aqueous promoter solution that generates hydrogen upon contact with the solid reactant;
A first fluid flow path that communicates between the storage chamber of the reactor and the solution reservoir and that supplies an aqueous promoter solution from the solution reservoir to the solid reactant of the storage chamber;
A second fluid flow path connecting the storage chamber of the reactor and the solution reservoir, and contacting a reaction product generated in the reactor with the promoter aqueous solution of the solution reservoir;
A hydrogen flow path that communicates the solution reservoir and the fluid chamber of the reactor, and sends hydrogen from the solution reservoir to the fluid chamber;
Due to decompression of the storage chamber through the fluid chamber due to generation and discharge of hydrogen, the flow of the promoter aqueous solution in the first fluid channel, the hydrogen channel, the first hydrogen discharge channel, and the second Control means for controlling the flow of hydrogen in the hydrogen discharge passage, and for causing hydrogen to flow through the second fluid flow path to bring the reaction product into contact with the aqueous accelerator solution;
A hydrogen generator characterized by comprising: The hydrogen flow path is connected to an intermediate portion of the second hydrogen discharge path, the first hydrogen discharge path is connected to the second hydrogen discharge path on the opposite side of the fluid chamber across the connection portion,
The control means includes
A check valve that is provided in the hydrogen flow path and allows only the flow of hydrogen from the solution reservoir to the fluid chamber;
A pressure control valve provided in the second hydrogen discharge passage and closed at a predetermined pressure or higher;
3. The hydrogen according to claim 1, further comprising a constant pressure shut-off valve that is provided in the first hydrogen discharge passage and has a valve body that closes when the pressure control valve is below the predetermined pressure when the pressure control valve is closed. Generator. The hydrogen flow path is connected to a middle portion of the second hydrogen discharge path, and the first hydrogen discharge path is connected to the second hydrogen discharge path on the opposite side of the fluid chamber across the connection section,
The control means includes
The check valve provided in the hydrogen flow path and allowing only the flow of hydrogen from the solution reservoir to the fluid chamber;
The first hydrogen discharge path is provided at the connecting portion between the first hydrogen discharge path and the second hydrogen discharge path when the pressure exceeds a predetermined pressure, and the second hydrogen discharge path flows when the pressure falls below the predetermined pressure. The hydrogen generator according to claim 1, further comprising a three-way valve. The hydrogen generator according to claim 3, wherein a spring controls a predetermined pressure of the constant pressure shut-off valve. The hydrogen generation device according to claim 3, wherein the set pressure of the pressure control valve is set to a valve opening pressure with reference to an internal pressure of the solution reservoir. The hydrogen generator according to claim 4, wherein the set pressure of the three-way valve is set to a valve opening pressure with reference to an internal pressure of the solution reservoir. The hydrogen generating device according to any one of claims 1 to 7, wherein an opening end of the fluid channel to the solution reservoir is disposed in the promoter aqueous solution. The means for partitioning the fluid chamber and the storage chamber of the reactor and making the volumes of the fluid chamber and the storage chamber variable is a deformation-permitting member. The hydrogen generator described. The deformation allowing member, which is a means for partitioning the fluid chamber and the storage chamber of the reactor and making the volumes of the fluid chamber and the storage chamber variable, is a flexible film. The hydrogen generator according to claim 9. The hydrogen generator according to any one of claims 1 to 10, wherein a filter is attached to a piping port of the fluid flow path through which the aqueous accelerator solution moves.   A fuel cell facility, wherein the discharge path of the hydrogen generator according to any one of claims 1 to 11 is connected to a fuel electrode of a fuel cell, and the generated hydrogen is supplied to a negative electrode chamber.   When hydrogen is generated by bringing a promoter aqueous solution, which is an aqueous solution of a hydrogen generation reaction accelerator, into contact with the solid reactant of the hydrogen generation reaction, a pressure is generated by the generation of hydrogen to generate a generated pressure. The partitioned chamber in the reactor containing the solid reactant is depressurized by pressure and hydrogen discharge to move the aqueous solution of the accelerator while bringing the product generated together with hydrogen into contact with the aqueous solution of the promoter. A method for generating hydrogen, comprising removing.   When hydrogen is generated by bringing a promoter aqueous solution, which is an aqueous solution of a hydrogen generation reaction accelerator, into contact with the solid reactant of the hydrogen generation reaction, a pressure is generated by the generation of hydrogen to generate a generated pressure. A method for generating hydrogen, characterized in that an aqueous accelerator solution is moved by depressurizing a partitioned room in a reactor containing a solid reactant by pressure and hydrogen discharge.   When hydrogen is generated by bringing an aqueous solution of an accelerator, which is an aqueous solution of the hydrogen generation reaction, into contact with a solid reactant of the hydrogen generation reaction, the product generated together with the hydrogen is brought into contact with the aqueous solution of the accelerator to remove the product. A method for generating hydrogen, comprising: The hydrogen generation method according to claim 13 or 14, wherein the hydrogen from which the reaction product has been removed is discharged by a generation pressure.

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