JP4371746B2 - Hydrogen generation method and apparatus - Google Patents

Description

  The present invention relates to a hydrogen generation method and apparatus, and more particularly to a hydrogen generation method and apparatus for hydrolyzing a hydride in the presence of water to generate hydrogen.

  Hydrogen is considered to occupy an important position as a clean energy source in addition to an important chemical raw material used in the chemical industry and oil refining. It is proceeding in the direction. As a hydrogen source for easily obtaining hydrogen, a method of compressing and storing it in a container and a method of using a hydrogen storage alloy have been proposed. Many challenges remain.

  Therefore, a method for generating hydrogen by hydrolyzing an alkali metal hydride such as sodium hydride or an alkali earth metal hydride has recently attracted attention. However, these hydrides, such as sodium hydride, have the property that when they come into contact with water, they react violently to generate hydrogen, and therefore, by coating sodium hydride with a resin film and cutting this film, Although there is a method to control the generation, it is difficult to sufficiently control the amount of hydrogen generation, and a problem remains in terms of safety.

  There is also a method of generating hydrogen by hydrolyzing a complex metal hydride such as sodium borohydride. This method uses heated water and promotes the generation of hydrogen in the presence of an acidic aqueous solution or catalyst. These also control the amount of hydrogen generation and improve safety in the same way as described above. The problem remains.

  Under such a background, as a new method, a method of generating hydrogen in a short time by heating a hydrogen generating raw material in which two or more hydrides are mixed (see, for example, Patent Document 1) or the like. A method of hydrolyzing a complex metal hydride in the presence of a catalyst comprising a metal oxide, a metalloid oxide or a carbonaceous material and a noble metal (see, for example, Patent Documents 2 and 3), and hydrolytic reactivity. In the case of alkaline earth metal hydrides that are poor in acid, a method for promoting a hydrolysis reaction in an acidic aqueous solution (see, for example, Patent Document 4), or a catalyst comprising a metal oxide or a carbonaceous material in a complex metal hydride. In the presence of no substantial water in the presence, a method of heating to a relatively low temperature of 100 to 170 ° C. for thermal decomposition (see, for example, Patent Document 5) is a method for improving the amount of hydrogen generation. Proposed That. In addition to this, as a method of generating hydrogen from a metal hydride complex compound, a method (for example, see Patent Documents 6 and 7) that can improve the controllability of the generation amount and improve the stop response is proposed. .

JP 2001-253702 A JP 2001-199701 A JP 2001-342001 A JP 2002-80201 A JP 2002-137901 A JP 2003-146604 A JP 2003-146605 A

  However, although the conventional method described above can generate hydrogen in a short time, it is extremely difficult to reliably and easily control the amount of generation corresponding to the load, and during the reaction. Therefore, there is a problem that it is practically impossible to stop hydrogen generation quickly and easily with good response.

  As a result of paying attention to such problems, the present applicant can easily control the amount of hydrogen generation, and can also arbitrarily stop the generation of hydrogen as needed. In order to provide a device suitable for the implementation of the method, it was previously proposed as a prior application based on Japanese Patent Application No. 2002-224190. This prior application is based on the knowledge that when a hydride is hydrolyzed to generate hydrogen, the hydride reacts not only with liquid water but also with moisture in the air, that is, with water vapor. The basic constitutional point is that the above problem is solved by reacting with water molecules that are gently supplied through the water-repellent water vapor permeable material. .

  Therefore, the present invention further improves the controllability of the amount of hydrogen generated by further improving the invention according to the above-mentioned prior application, further improves the responsiveness and stability, and further prevents the generation of hydrogen during the reaction. A novel and practical method for generating hydrogen that makes it possible to stop quickly and easily with good responsiveness, and is particularly suitable as a hydrogen cartridge for a fuel cell for portable small and medium-sized equipment. An object of the present invention is to provide a hydrogen generator that is suitable for the implementation of the above.

  In order to achieve the above object, the present invention provides a hydrogen generation method for generating hydrogen by hydrolyzing a hydride 7 in a sealable main body container 1, wherein the hydride 7 layer and moisture W are combined. The impregnated water-absorbing material 8 is isolated by a water-permeable material 6 formed of a water-permeable film having a large number of fine pores through which a very small amount of moisture and water vapor can permeate. The water molecules that permeate the hydride 7 react with each other to generate hydrogen, and when the internal pressure of the water permeable material 6 and the water absorbing material 8 is increased according to a change in the internal pressure of the main body container 1 during the reaction. The amount of water molecules that permeate the moisture permeable material 6 is controlled by being detached and brought into contact when the internal pressure is reduced, thereby generating hydrogen in a configuration that controls the reaction between the hydride 7 and water molecules. It features a method That.

    The present invention also provides a hydrogen generation method for generating hydrogen by hydrolyzing the hydride 7 in the sealable main body container 1, wherein the layer of the hydride 7 and the water absorbing material 8 impregnated with water W are used. It is isolated by a moisture permeable material 6 formed of a moisture permeable membrane having a large number of fine pores through which a very small amount of moisture and water vapor can permeate, and a water-impermeable membrane 9 is planarized between the moisture permeable material 6 and the water absorbing material 8. The water permeable material 6 and the water absorbing material 8 are partly in direct contact with each other because the water impermeable film 9 is moved so that the water impermeable film 9 is not interposed. The water that passes through the moisture permeable material 6 through the contact point through the contact point is formed by allowing the contact point to be formed while being displaced in either a constant area state or an increasing area state. Hydrogen reacts with molecules and the hydride 7 In the reaction, the impermeable membrane 9 is not moved when the internal pressure is increased according to the change in the internal pressure of the main body container 1, and is moved when the internal pressure is decreased, so that the moisture permeable material 6 is permeated. A feature of the present invention is a hydrogen generation method having a configuration in which the amount of water molecules to be controlled is controlled to thereby control the reaction between the hydride 7 and water molecules.

    The present invention also provides three embodiments as a hydrogen generator for generating hydrogen by hydrolyzing the hydride 7, and the first apparatus includes a main container 1 having a hydrogen outlet 4 and a sealable main body container 1. A diaphragm 5 that is interposed in the main body container 1 and divides the inside of the vessel into a sealable hydrogen generating section 3 having a pressure adjusting section 2 and the hydrogen outlet 4; Moisture permeation formed from a moisture permeable membrane having a large number of fine pores to be obtained and divided into a hydrogen side chamber provided with a diaphragm 5 and a hydrogen side chamber provided with a hydrogen outlet 4 interposed in the hydrogen generating portion 3. A material 6, a layer of hydride 7 disposed in the hydrogen-side chamber in contact with the moisture-permeable material 6, and a movable body connected to the diaphragm 5 that can contact and separate from the moisture-permeable material 6. Water-absorbing material that is provided and impregnated with moisture W The hydride 7 reacts with water molecules that exit from the water absorbing material 8 and permeate the moisture permeable material 6 to generate hydrogen, and the internal pressure of the hydrogen generating unit 3 during the reaction Based on the operation of the diaphragm 5 that moves in the direction of contact with and away from the moisture permeable material 6 in response to the change, the water absorbing material 8 is separated from the moisture permeable material 6 when the internal pressure is increased, and is contacted when the internal pressure is reduced. The amount of water molecules that permeate the permeable material 6 is controlled, and thereby the amount of hydrogen generation is controlled.

    Next, in the second hydrogen generator according to the present invention, a sealable main body container 1 having a hydrogen outlet 4, and a pressure adjusting unit 2 and the hydrogen are interposed in the main body container 1. It is formed from a diaphragm 5 that is partitioned into a sealable hydrogen generator 3 having a lead-out port 4 and a water permeable membrane having a large number of fine holes through which a trace amount of moisture and water vapor can pass, and is interposed in the hydrogen generator 3. A water permeable material 6 that is divided into a water side chamber provided with a diaphragm 5 and a hydrogen side chamber provided with a hydrogen outlet 4 and is disposed in the hydrogen side chamber in contact with the water permeable material 6. A disk-shaped hydride 7 layer and a disk shape having the same diameter as that of the hydride 7 layer are formed. The moisture permeable material 6 is sandwiched between the hydride 7 layer and the same axis and rotated about the central axis. It is movably disposed in the water-side chamber and absorbs and retains moisture W. A notched circular shape comprising a material 8 and a water-impermeable thin film attached to the surface of the water-absorbing material 8 facing the moisture permeable material 6 and provided with a fan-shaped notch 10 extending from the center to the circumference. A water impermeable film 9 and a rotation driving means 11 that is connected to the water absorbing material 8 and rotates the water absorbing material 8 about its central axis in conjunction with the diaphragm 5. Hydrogen is generated by reacting the hydride 7 with the water molecule that has passed through the notch 10 corresponding to the direct contact portion between the water absorbing material 8 and the moisture permeable material 6 and the hydride 7. Based on the operation of the rotation drive means 11 interlocked with the diaphragm 5 that moves in response to the change in the internal pressure of the main body container 1 during the reaction, the rotation drive means 11 is deactivated when the internal pressure rises. Missing 10 When the internal pressure is lowered without being displaced, the rotational driving means 11 is operated to displace the notch 10 under a constant area state, thereby controlling the amount of water molecules that permeate the moisture permeable material 6, thereby the hydrogen. It is configured to control the reaction between the compound 7 and water molecules.

    Next, in the third hydrogen generating apparatus according to the present invention, the sealable main body container 1 having the hydrogen outlet 4 and the pressure regulating section 2 and the hydrogen guide are disposed inside the main body container 1. It is formed from a diaphragm 5 that is partitioned into a sealable hydrogen generator 3 having an outlet 4, and a moisture permeable membrane that has a large number of fine pores through which fine moisture and water vapor can permeate several water molecules or less. A moisture permeable material 6 interposed in the hydrogen generating section 3 and partitioned into a water side chamber provided with a diaphragm 6 and a hydrogen side chamber provided with a hydrogen outlet 4, and in contact with the moisture permeable material 6. A rectangular hydride 7 layer disposed in the hydrogen side chamber has a rectangular disk shape that is the same shape as the hydride 7 layer, and is joined to the hydride 7 layer with the moisture permeable material 6 interposed therebetween. Is disposed in the water side chamber, and absorbs and retains moisture W. A water-impermeable film 9 comprising a material 8 and a water-impermeable sheet thin film interposed between the layer of hydride 7 and the water-permeable material 6 so as to be movable in one direction parallel to one side of the square. A winding means 12 that winds up the water-impermeable film 9 in conjunction with the diaphragm 5 by a winding roll 13 provided close to one side of the water-absorbing material 8 and pulls it out. Then, the hydride 7 reacts with water molecules permeating the moisture permeable material 6 through the impermeable membrane non-intervening portion corresponding to the direct contact portion between the hydride 7 layer and the moisture permeable material 6. The impermeable membrane 9 is wound when the internal pressure is increased based on the operation of the winding means 12 interlocked with the diaphragm 5 that is displaced according to the change in the internal pressure of the main body container 1 during the reaction. Taken off when the internal pressure drops The amount of water molecules that permeate the moisture permeable material 6 is controlled by displacing the non-intervening portions under increasing area, thereby controlling the reaction between the hydride 7 and the water molecules. It is characterized by having the configuration as described above.

    As an aspect of the second and third hydrogen generators described above, the rotation drive means 11 is a spring force-rotation force conversion mechanism including a spring timer and a pendulum, and the diaphragm 5 stops its movement when the internal pressure increases, A configuration provided in association with the pendulum so as to allow the movement when the internal pressure is reduced is mentioned.

    As an aspect of the hydrogen generator according to the present invention, there is one in which a buffer material 14 is provided adjacent to the layer of the hydride 7 in the hydrogen side chamber, and the buffer material 14 has elasticity. In addition, it is preferable that an infinite number of communicating voids are provided so as to absorb the expanded portion of the hydride 7 while holding it and to allow the generated hydrogen to pass therethrough.

    Regarding the hydrogen generator according to the present invention described above, there may be mentioned one in which the hydride 7 is compartmentally molded into a polygonal shape such as a strip shape, a triangle shape, a square shape or a honeycomb shape.

  According to the hydrogen generation method of the present invention, hydride and water are not directly contacted and reacted as in the conventional method, but water molecules permeated through the moisture permeable material and hydride are reacted. The reaction is mild and therefore can be controlled easily by adjusting the amount of moisture that permeates. This greatly advances the practical application of hydrogen generation technology using hydrides, and at the same time promotes the practical application of small fuel cells using such hydrogen generation technology, and contributes greatly to the spread of clean energy. Be expected.

  The amount of generated hydrogen can also be easily controlled by adjusting the presence / absence of contact between the water-permeable material and the water-absorbing material or the contact area or one of the displacements of the contact point. Stoppage of hydrogen generation during the reaction, which was impossible in the hydrogen generation method by contact with hydride, can be reliably performed by disconnecting the water from the moisture permeable material. It is possible to generate hydrogen.

  In addition, since the internal pressure of the main body container can be stably held under a low pressure of 100 kPa or less, the pressure resistance of the container can be greatly reduced, and the size can be reduced by using a light and inexpensive material such as plastic. Therefore, when used as a hydrogen generator for a small fuel cell such as a mobile device, the hydrogen generator can be easily replaced by making it a small cartridge type that can be inserted into a mobile device or the like. It is extremely convenient to carry as a spare part.

  In addition, since the water required for the reaction is preliminarily absorbed and held in a water absorbent material such as a sponge, it is not only suitable as a top-and-bottom device that requires only a small amount of water absorption and whose posture is not specified. Since the water and moisture permeable material can be kept away from each other during transportation, the water absorbing material and the main body container are modularized in advance, and only the module of the used hydrogen generator is replaced. By doing so, it is expected that the hydrogen generator will be easily regenerated and contribute to resource saving.

  With regard to a specific configuration, by arranging a buffer material having elasticity and air permeability along the hydride in the hydrogen side chamber, swelling of the hydride generated during the reaction can be absorbed by the buffer material. The movement of the hydride during the reaction is prevented, and the hydrogen generation reaction can be performed stably.

  Further, in the hydrogen generator according to the present invention, when the hydride 7 is partitioned and formed into polygonal shapes such as strips, triangles, squares, and honeycombs by the partition walls 31, the hydride is caused by moisture bleeding in the lateral direction. Can prevent excessive reaction.

  Hereinafter, a hydrogen generation method and apparatus according to the present invention will be described in detail based on each embodiment shown in the drawings. FIG. 1 is a conceptual diagram of a front view of a hydrogen generator according to a first embodiment of the present invention, in which (a) shows an increase in internal pressure and (b) shows a decrease in internal pressure. In the illustrated hydrogen generating apparatus, reference numeral 1 denotes a cylindrical main body container, which is provided with a coupling portion at an intermediate portion. The main body container 1 is made of plastic, for example, nylon 66 and can be used as a hydrogen cartridge type container. It is formed to a size of about. A diaphragm 5 is fixed to the container cylinder wall with a diaphragm 5 interposed between the coupling portions in the main body container 1 as a partition member, and a pressure adjusting section 2 and a hydrogen outlet 4 are provided in the main body container 1. It is divided into two parts with the hydrogen generating part 3 which can be sealed.

  The operation state of the diaphragm 5 is shown in FIGS. 1A and 1B. The diaphragm membrane portion is moved to the pressure regulating portion 2 side in order to increase the volume of the hydrogen generating portion 3 as the internal pressure of the hydrogen generating portion 3 increases. On the contrary, the diaphragm membrane part is provided so as to be recessed into the generation part 3 side in order to reduce the volume of the hydrogen generation part 3 with the protrusion and the decrease in internal pressure. In FIG. 1, reference numeral 15 denotes an air hole penetrating the end wall on the pressure regulating unit 2 side of the main body container 1, and reference numeral 19 is provided on the end wall on the hydrogen generating unit 3 side of the main body container 1. It is a one-touch type connector fitted to the hydrogen outlet 4.

  A water permeable material 6 formed of a thin film body of a water permeable membrane is interposed at a substantially intermediate position in the cylinder axis direction of the hydrogen generating unit 3 as a partition member with its peripheral edge fixed to the container cylinder wall. Thus, the hydrogen generation unit 3 is divided into two chambers, a water side chamber provided with a diaphragm 5 and a hydrogen side chamber provided with a hydrogen outlet 4. The moisture permeable material 6 is a porous film having a large number of fine pores that can permeate only a small amount of moisture and water vapor. For example, a heat-resistant PTFE (polytetrafluoroethylene) porous thin film is used. As a kind of porous thin film, a desired one is appropriately selected from various permeable membranes described later.

  In the hydrogen generating unit 3 having the moisture permeable material 6 interposed, the hydrogen side chamber is provided with a layer of hydride 7 and a buffer material 14, while the water side chamber contains moisture (W). A water absorbing material 8 that is impregnated and held is disposed. The layer of the hydride 7 is, for example, a disk-shaped solidified hydride material such as calcium hydride (CaH2), which is placed in contact with the moisture permeable material 6 in the hydrogen side chamber. Further, the buffer material 14 is formed in a disk shape with ceramic wool, for example, in contact with the hydride 7. On the other hand, the water-absorbing material 8 is formed in a disc-like shape using a sponge or the like that can be held by impregnating a sufficient amount of water (W; water, acid, alcohol aqueous solution, etc.) in the water-side chamber. The hydrogen generator 3 is provided so as to be movable in the direction of the cylinder axis so as to be integrally connected to the diaphragm 5 and to be able to contact and separate from the moisture permeable material 6. The buffer material 14 is a member having elasticity that can expand and contract in the axial direction and having an infinite number of communicating voids, while absorbing the expansion due to the hydrolysis action of the hydride 7. As long as it is held so as not to be misaligned and does not obstruct the passage of the generated hydrogen, an appropriate material is applied. Further, in FIG. 1, reference numeral 16 is a restraining spring for adjusting the set pressure of the diaphragm 5, reference numeral 18 is a connecting rod for mechanically connecting the diaphragm 5 and the water absorbing material 8, and reference numeral 17 is The spring adjustment knob.

  Next, an operation mode of the hydrogen generator according to the first embodiment will be described. A cartridge-type hydrogen generator in which a layer of unreacted hydride 7 and a water-absorbing material 8 impregnated with water (W) in an amount corresponding to the required amount of hydrogen generation is stored is a water-absorbing material 8. Fine moisture and water vapor discharged from the gas permeate the moisture permeable material 6 and enter the hydrogen side chamber, reach the layer of hydride 7 and react with the hydride 7 to generate hydrogen. In this case, it is possible to suppress a rapid reaction through the moisture permeable material 6 and to gradually generate hydrogen over a long period of time. When the internal pressure rises above the set pressure of the diaphragm 5, FIG. As shown in FIG. 4, the water absorbing material 8 moves to a position away from the moisture permeable material 6 in conjunction with the protrusion of the diaphragm 5, so that the reaction stops and the hydrogen generation stops.

  Specifically, with respect to the mode when the load is connected, the water absorbing material 8 is changed to a diaphragm as the internal pressure of the cartridge main body container 1 changes depending on the amount of hydrogen used in the fuel cell connected to the hydrogen outlet 4 by a communication pipe (not shown). When the consumption is high, the internal pressure is reduced to 60 kPa or less and the water absorbing material 8 reaches the moisture permeable material 6. When the consumption is low, the internal pressure is increased to 60 kPa or more. The water absorbing material 8 is moved away from the water permeable material 6, thereby automatically controlling the amount of hydrogen generated, and stably maintaining the required amount of hydrogen while maintaining the internal pressure of the cartridge body container 1 within a certain range. Can be generated. Of course, when the consumption stops during the hydrogen generation operation, the water absorption material 8 quickly leaves the moisture permeable material 6 as the internal pressure rises, so that the hydrogen generation can be stopped quickly.

  By the way, compared to conventional cylinder type or meta-high type hydrogen cartridges, etc., the hydrogen generator according to the present invention can greatly reduce the pressure resistance of the container, so the container material is a lightweight and inexpensive material such as synthetic resin. In addition, since it is not necessary to provide an auxiliary machine such as a pressure reducing valve on the supply line, it can greatly contribute to simplification and miniaturization of the entire fuel cell system.

  In addition, in the above-mentioned hydrogen generator, the moisture permeability of the moisture permeable material 6 is insufficient, and when the moisture (W) sufficient to correspond to the consumption of hydrogen cannot be permeated over the necessary time, the reaction is performed. The water permeation rate of the membrane can be improved by dissolving about 1 wt% of the surfactant in the moisture, or applying the surfactant to the moisture permeable material itself to make it hydrophilic.

  From this, the water permeable material originally does not require water repellency, and it is sufficient to simply use a membrane having a sufficiently small pore diameter. However, the temperature during the reaction (up to a little less than 200 ° C. for a short time) and the post-reaction An example of a membrane having moderately fine pores that can withstand strong alkalinity is a 10 μ-thick PTFE membrane subjected to a hydrophilic treatment.

  Here, the hydride 7 used in the present invention will be described. The hydride 7 includes lithium aluminum hydride (LiAlH4), lithium borohydride (LiBH4), sodium aluminum hydride (NaAlH4), sodium borohydride (NaBH4), potassium aluminum hydride (KAlH4), boron hydride. Potassium (KBH4), Magnesium borohydride (Mg (BH4) 2), Calcium borohydride (Ca (BH4) 2), Barium borohydride (Ba (BH4) 2), Strontium borohydride (Sr (BH4) 2) Iron borohydride (Fe (BH4) 2), lithium hydride (LiH), sodium hydride (NaH), potassium hydride (KH), barium hydride (BaH2), magnesium hydride (MgH2), 1 selected from the group consisting of calcium hydride (CaH2), strontium hydride (SrH2), and aluminum hydride (AlH3) Examples of the above are powders, particles, granules, pellets, plates, and honeycombs, which are suitably formed. For the purpose of increasing the surface area and increasing the reactivity, powders, particles, or granules Is preferred.

  The moisture permeable material 6 used in the present invention will be described. The moisture permeable material 6 is selected from the group of polytetrafluoroethylene resin, polyethylene resin, polypropylene resin, polystyrene resin, polycarbonate resin, polyamide resin, polyester resin, fluorine resin, silicon resin, acetal resin, acrylic resin, and melamine resin. Examples thereof include those formed from one or more kinds of synthetic resins or paper, and having continuous micropores through which a minute amount of moisture and water vapor can permeate.

Next, Example 1 of the hydrogen generator according to the first embodiment of the present invention will be described with reference to FIG. This apparatus includes a prototype cartridge [container material: plastic, size: 40 ml (about a single dry cell), weight: 50 g, hydrogen generation amount: 2 liters / 35 minutes, hydride (CaH ₂ ) loading amount: 1.8 g, Moisture permeable material membrane diameter: 20 mm] was prototyped and subjected to a load test (hydrogen generation operation), and the operating time characteristics of internal pressure A, gas outlet temperature B, power generation output C, and external side surface temperature D at that time were measured. . The result is as shown in FIG. As is apparent from this result, stable power generation was possible with an output of 3.5 W for 35 minutes at a reaction rate of 100% of the charged CaH ₂ . Further, the internal pressure changed at 100 kPa or less (FC withstand pressure of 100 kPa). The gas temperature also remained at a level that did not affect FC. On the other hand, the plastic container main body was not deformed by heat generation, and the external surface temperature of the container main body coated with a heat insulating material (polyethylene foam) was kept at 60 ° C. or less so that it was not heated even when touched. As described above, the hydrogen generator according to the first embodiment of the present invention is an apparatus that can be practically used as a low-power hydrogen cartridge for small devices such as PDAs.

  FIG. 3 shows a plan view of a state where the upper casing of the hydrogen generator according to the second embodiment of the present invention is detached, and FIG. 4 shows the direction of the arrow along the line AA in FIG. A cross-sectional view in the direction of the arrow along the line BB is shown in (b). FIG. 5 shows a cross-sectional view in the direction of the arrow along the line CC in FIG. In the illustrated hydrogen generation apparatus, the apparatus is similar to the apparatus shown in FIG. 1, and corresponding members are denoted by the same reference numerals. The main body container 1 is formed in a hexagonal flat plate that can be hermetically sealed by vertically and vertically joining a hexagonal upper casing 20 and a lower casing 21 having 2 perpendicular corners and 4 obtuse corners.

  The main body container 1 is divided into a pressure-regulating part 2 that occupies a part of the space and a sealable hydrogen generator 3 that occupies a large part of space by a diaphragm 5 that is horizontally installed near a right-angled corner in the container. The The hydrogen generation unit 3 includes a water-permeable material 6 installed horizontally on the obtuse corner side, a sealed water-side chamber (lower chamber) provided with a diaphragm 5, and a sealed hydrogen-side chamber (upper side chamber) provided with a hydrogen outlet 4. It is divided into two rooms.

  In the hydrogen generation unit 3 having the moisture permeable material 6 interposed, the hydrogen side chamber is provided with a layer of a hydride 7 and a buffer material 14 respectively, while the water side chamber contains moisture (W). The water-absorbing material 8, impervious film 9 and rotation driving means 11 which are impregnated and held are respectively disposed. The layer of the hydride 7 is formed by solidifying a hydride particulate raw material into a disk shape, which is in contact with the moisture permeable material 6 and mounted horizontally. The cushioning material 14, which is also formed in a disk shape, is mounted horizontally on the hydride 7 layer.

  The water-absorbing material 8 is formed in a disk shape having the same diameter as the layer of the hydride 7 and is mounted on a turntable 22 provided below the moisture-permeable material 6 in the water side chamber so as to be horizontally rotatable around the central longitudinal axis. The water-absorbing material 8 is horizontally driven around the central longitudinal axis coaxially with the layer of the hydride 7 while lightly contacting the moisture-permeable material 6 with the upper surface by the rotational drive of the rotary table 22. It has come to be. On the other hand, the water-impermeable film 9 is made of a water-impermeable film such as an aluminum sheet, and is integrally attached to the upper surface of the water-absorbing material 8 facing the water-permeable material 6 to form a surface film. As shown in FIG. 3, the water-impermeable film 9 has a fan-shaped notch 10 (for example, a central angle of 20 degrees) extending from the center to the circumference, and has a certain area. It functions so that the surface of the water absorbing material can be exposed only at the notch 10 and the water absorbing material 8 itself can be brought into direct contact with the moisture permeable material 6.

  The rotation driving means 11 is disposed adjacent to the turntable 22 in such a manner that the start / stop operation side is connected to the diaphragm 5 and the rotation output side is connected to a pulley 23 provided coaxially with the turntable 22. This rotation drive means 11 is composed of a spring force-rotation force conversion mechanism, and includes a spring timer 24, a pulley / spring winding knob 25, a pendulum 26, and a pendulum stop hook 27 as constituent elements, which are open for a long time. “Spring spring” is used as an example of a suitable apparatus. That is, the support portion of the pendulum stop hook 27 on the start / stop operation side is axially coupled to the center of the membrane of the diaphragm 5 by the connecting rod 29, and the protruding / recessing operation of the diaphragm 5 is stopped by the connecting rod 29. A belt 30 is stretched between the pulley 23 and the mainspring winding knob 25 on the rotational output side and the pulley 23 while being provided directly to the hook 27 to stop and start the movement of the pendulum 26. It is provided so that the rotational power of the mainspring winding knob 25 is transmitted to the pulley 23 via the gear belt 30 as a rotational motion. In FIG. 4B, reference numeral 28 denotes a pendulum stopper knob which is attached to the connecting rod 29 and can be operated from outside the main body container 1.

  Next, the mode of operation of the hydrogen generator according to the second embodiment will be described. A cartridge-type hydrogen generator in which a layer of unreacted hydride 7 and a water-absorbing material 8 impregnated and retained with an amount of water (W) corresponding to a required amount of hydrogen generation is stored is a water-absorbing material 8. Fine water and water vapor discharged from the water penetrates the water permeable material 6 through the notch 10 of the impermeable membrane 9 and enters the hydrogen side chamber, reaches the layer of hydride 7 and reacts with the hydride 7 to form hydrogen. Is generated. In this case, the water in the water absorbing material 8 flows smoothly to the notch 10 due to the action of capillary action or dyeing, etc., and by suppressing the rapid reaction by being through the water permeable material 6, Hydrogen can be generated gradually. Since the pendulum 26 continues the pendulum motion in conjunction with the recess of the diaphragm 5 until the internal pressure rises above the set pressure of the diaphragm 5, the water absorbing material 8 and the notch 10 of the water-impermeable film 9 are integrated. To continue the hydrolysis reaction. When the internal pressure rises above the set pressure of the diaphragm 5, the pendulum stop hook 27 operates so as to stop the movement of the pendulum 26 in conjunction with the protrusion of the diaphragm 5, so that the water absorbing material 8 and the water-impermeable film The notch 10 of 9 is not displaced by the stop, the reaction stops and the hydrogen generation stops.

  Specifically, with respect to the mode when the load is connected, the diaphragm 5 protrudes as the internal pressure of the cartridge main body container 1 changes depending on the amount of hydrogen used in the fuel cell connected to the hydrogen outlet 4 by a communication pipe (not shown). When the protrusion is moved and the consumption is large, the internal pressure drops to, for example, 60 kPa or less, the pendulum stopper hook 27 interlocked with the diaphragm 5 is released and the pendulum 26 can be moved to cut out the water absorbing material 8 and the impermeable membrane 9 10 rotates and hydrogen generation continues. On the other hand, when the consumption is low, the internal pressure rises to, for example, 60 kPa or more, and the pendulum locking hook 27 interlocked with the diaphragm 5 stops the movement of the pendulum 26. Thus, the amount of hydrogen generated is automatically controlled, and the required amount of hydrogen is stably generated while maintaining the internal pressure of the cartridge body container 1 within a certain range. Rukoto can. Of course, when the consumption stops during the hydrogen generation operation, the hydrogen generation can be quickly stopped as the internal pressure increases.

  In the hydrogen generator of this embodiment, a hydrogen generator capable of supporting a large output by enlarging the diameter of the hydride layer 7 and the water absorbing material 8, and a long-term compatible hydrogen generator by slowing the rotation speed. Can do. On the other hand, in the layer of hydride 7 formed in a disk shape, a hydride 7 in which the required hydride 7 is formed by filling a particulate hydride into a disk receptor in which a large number of partitions having a honeycomb shape are formed in advance is used. In the case of this example, when the rotation of the water-absorbing material 8 is stopped, the moisture that has entered from the location of the notch 10 in the layer of the hydride 7 spreads in the lateral direction. It is possible to surely avoid a situation in which the reaction proceeds due to spreading, which is preferable in terms of leading to accurate on-off control. Of course, it is possible to use a small motor such as a step motor instead of the above-described spring force-rotational force conversion mechanism as the rotation driving means 11, but in this case, an auxiliary battery for driving the motor is considered. There is a need.

Next, Example 2 of the hydrogen generator according to the second embodiment of the present invention will be described with reference to FIG. This apparatus basically has the same structure as that shown in FIGS. 3 to 5 [hydrogen generation amount: 2.5 liters / 45 minutes, hydride (CaH ₂ ) loading amount: 2.0 g, moisture permeation An apparatus with a material film diameter of 40 mm] was prototyped and subjected to a load test (hydrogen generation operation). The operating time characteristics of the internal pressure A and the power generation output C at that time were measured. The result is as shown in FIG. As is apparent from this result, stable power generation was possible with an output of 3.5 W for 45 minutes at a reaction rate of 100% of the charged CaH ₂ . The internal pressure was maintained around 60 kPa (FC withstand pressure of 100 kPa). In the second half of the reaction, the pressure fluctuation range did not change. As described above, the hydrogen generator according to the second embodiment of the present invention is a flat-plate type medium output hydrogen cartridge that can be used for medium-sized devices such as notebook computers.

  FIG. 7 shows the structure of the main part of the hydrogen generator according to the third embodiment of the present invention in (a) in the state immediately before the hydrogen generation operation, and (b) in the state in the middle of the hydrogen generation operation. Each is shown by a conceptual diagram of a slope. FIG. 8 is a perspective view showing a modified example of the water absorbing material 7 in the hydrogen generator shown in FIG. 7, and FIG. 9 is a separate view showing the stacking mode of the component members in the hydrogen generator shown in FIG. An explanatory diagram is shown respectively. FIG. 7 schematically shows the basic structure of the hydrogen generator 3 in the hydrogen generator, and the main body container, the pressure regulator, the diaphragm, and the spring force-rotational force conversion as the drive means for this device. Since the components of the mechanism are essentially the same as those provided in the hydrogen generator according to the second embodiment shown in FIGS. 3 to 5, illustration is omitted here.

  The hydrogen generator according to the third embodiment shown in FIG. 7 to FIG. 9 is suitable as a device corresponding to a large output for a long time, and instead of making the water absorbing material 8 movable, the water permeable material 6 and the hydrogen The impermeable membrane 9 interposed between the layers of the chemical compound 7 is made movable and can be pulled out in accordance with the fluctuation of the internal pressure of the hydrogen generator 3, and the overall shape of the apparatus is rectangular (for example, rectangular). ) It is a structural feature that it is formed on the board.

  Referring to FIG. 7, a hydrogen generating unit 3 provided in a container body formed in a rectangular board, for example, a rectangular board, is closed by a water permeable material 6 made of a rectangular water permeable film, and a sealed water side chamber (lower side chamber provided with a diaphragm). ) And a sealed hydrogen side chamber (upper side chamber) provided with a hydrogen outlet. In the hydrogen side chamber, a layer of a rectangular hydride 7 is disposed in contact with the moisture permeable material 6 and immediately above it. Further, a cushioning material 14 having the same rectangular disk shape is disposed so as to be directly above. On the other hand, in the water side chamber, a water absorbing material 8 impregnated with water W having a rectangular disk shape that is the same shape as the hydride 7 layer sandwiches the moisture permeable material 6 and is congruent to the hydride 7 layer. It is arranged.

  Further, in the hydrogen side chamber, an impermeable film 9 made of an impermeable sheet thin film is drawn and moved in one direction parallel to the long side of the rectangle between the hydride 7 layer and the moisture permeable material 6. Intervened possible. A winding roll 13 is provided close to the laminated structure (see FIG. 9) formed in a rectangular shape, and this winding roll 13 is brought close to the end portion on the diaphragm side and rotated. The shaft is provided parallel to the end side, and the edge of the water-impermeable film 9 is wound around the winding roll 13. By connecting the rotating shaft of the winding roll 13 and the spring force-rotational force conversion mechanism (the aforementioned spring spring) as the winding means 12 disposed in the water side chamber in relation to the diaphragm, The water-impermeable film 9 can be wound up and pulled out by a winding roll 13 in conjunction with the operation of the diaphragm 5.

  Next, an operation mode of the hydrogen generator according to the third embodiment will be described. The state immediately before the hydrogen generation operation in which the layer of unreacted hydride 7 and the water absorbing material 8 impregnated with the amount of moisture (W) corresponding to the required amount of hydrogen generation are stored (FIG. ))), The hydrogen generation is stopped because the water-impermeable membrane 9 is interposed in a state of covering the entire reaction part. When the diaphragm 5 moves in a concave or convex manner in response to fluctuations in the internal pressure of the hydrogen generator 3 that changes with the amount of hydrogen used in the fuel cell connected to the hydrogen outlet through a connecting pipe (not shown). The winding means 12 interlocked with the diaphragm 5 is driven when the internal pressure decreases, and winding of the water-impermeable film 9 by the winding roll 13 starts.

With the start of winding, the water that comes out of the water absorbing material 8 and permeates the moisture permeable material 6 through the impermeable membrane-free portion corresponding to the direct contact portion between the layer of the hydride 7 and the moisture permeable material 6. Molecules react with the hydride 7 to initiate hydrogen generation. With the reaction due to the change in the amount of hydrogen used in the fuel cell, the internal pressure of the water-impermeable membrane 9 is increased on the basis of the operation of the winding means 12 linked to the diaphragm 5 that is displaced according to the pressure change in the hydrogen generator 3. Sometimes it is not wound, but when the internal pressure is reduced, it is wound and the non-intervening part is displaced under increasing area conditions (see FIG. 7 (b)). The amount of water molecules that pass through the moisture permeable material 6 is controlled.

  Since the hydrogen generator according to the present embodiment can be realized as a rectangular cartridge, the hydride can be filled to every corner, so that the arrangement of the hydride can be performed efficiently without waste, without taking up space, and the output. It is possible to provide a hydrogen generator that can be output stably, and it is a flat-plate type medium output hydrogen cartridge for medium-sized equipment such as notebook personal computers. Incidentally, in the layer of hydride 7 and at least the layer of hydride 7 of the buffer material 14, as shown in FIG. It is a preferable means to provide an interval. That is, when the hydride 7 is section-molded into a polygonal shape such as a strip, a triangle, a square, or a honeycomb by the partition wall 31, the moisture (W) spreads in the hydride layer in the lateral direction. This has the advantage that hydrogen generation can be stably controlled quantitatively.

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Moreover, in the hydrogen generator according to the present embodiment, as shown in FIG. 8, the water content is divided into small areas by providing partition walls 32 arranged in a grid shape with an appropriate pitch with respect to the water absorbing material 8. Is a preferred embodiment, and has the effect of allowing more stable freezing when the size is increased.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a conceptual diagram of a front view of a hydrogen generator according to a first embodiment of the present invention, where (A) indicates when the internal pressure is increased and (B) indicates when the internal pressure is decreased. It is a time-course diagram of the hydrogen generation operation condition in Example 1 of the hydrogen generator which concerns on this invention. It is a top view of the hydrogen generator which concerns on the 2nd Embodiment of this invention. (A) is sectional drawing of the arrow direction which follows the AA line in FIG. 3, (b) is sectional drawing of the arrow direction which similarly follows the BB line. It is sectional drawing of the arrow direction which follows the CC line in FIG. It is a time-course diagram of the hydrogen generation operating condition in Example 2 of the hydrogen generator concerning the present invention. FIG. 5 is a conceptual diagram showing a slope of the structure of the main part of a hydrogen generator according to a third embodiment of the present invention, where (a) shows the time immediately before the hydrogen generation operation and (b) shows the intermediate time of the hydrogen generation operation. It is a perspective view which shows the modification of the water absorbing material 8 in the hydrogen generator shown in FIG. It is explanatory drawing which shows separately the lamination | stacking aspect of the component member in the hydrogen generator shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Main body container 2 ... Pressure regulation part 3 ... Hydrogen generating part 4 ... Hydrogen introduction port 5 ... Diaphragm 6 ... Water permeation material 7 ... Hydride 8 ... Water absorption material 9 ... Opaque aqueous film 10 ... Notch 11 ... Rotation drive means 12 ... take-up means 13 ... take-up roll 14 ... buffer material 31 ... partition wall W ... moisture

Claims (8)

In the hydrogen generation method of generating hydrogen by hydrolyzing the hydride (7) in a sealable main body container (1), a water absorbing material impregnated with the hydride (7) layer and moisture (W) ( 8) is isolated by a moisture permeable material (6) formed of a moisture permeable membrane having a large number of fine pores through which a minute amount of moisture and water vapor can permeate. 6) reacts water molecules permeating with the hydride (7) to generate hydrogen, and the moisture permeable material (6) according to the internal pressure change of the main body container (1) during the reaction. And the water absorbing material (8) are separated when the internal pressure is increased, and are contacted when the internal pressure is decreased, thereby controlling the amount of water molecules that permeate the moisture permeable material (6), thereby controlling the hydride (7) and the water molecules. Characterized by controlling the reaction with Hydrogen generation method. In the hydrogen generation method of generating hydrogen by hydrolyzing the hydride (7) in a sealable main body container (1), a water absorbing material impregnated with the hydride (7) layer and moisture (W) ( 8) is isolated by a moisture permeable material (6) formed of a moisture permeable membrane having a large number of fine pores through which a minute amount of moisture and water vapor can permeate, and the moisture permeable material (6) and the water absorbing material (8). The water-impermeable membrane (9) is interposed between the water-impermeable membrane (9) so as to be movable in a plane, and the water-impermeable membrane (9) is not moved by moving the water-impermeable membrane (9). By allowing the moisture permeable material (6) and the water absorbing material (8) to be formed while being displaced in either one of the constant area state and the increasing area state, by contacting the water absorbing material (8) partly directly. , Get out of the water absorbing material (8) and pass through the moisture permeable material (6) through the contact point The water hydride (7) reacts with the hydride (7) to generate hydrogen, and the impermeable membrane (9) moves when the internal pressure rises in response to changes in the internal pressure of the main body container (1). The amount of water molecules that permeate the moisture permeable material (6) is controlled by operating when the internal pressure is reduced without operating, thereby controlling the reaction between the hydride (7) and water molecules. A hydrogen generation method characterized by comprising: In the hydrogen generator for hydrolyzing the hydride (7) to generate hydrogen,
A sealable body container (1) having a hydrogen outlet (4);
A diaphragm (5), which is provided in the main body container (1) and divides the inside of the vessel into a pressure regulating part (2) and a sealable hydrogen generating part (3) provided with the hydrogen outlet (4). When,
A water-side chamber and a hydrogen outlet (4) which are formed from a water-permeable membrane having a large number of fine pores through which a very small amount of moisture and water vapor can permeate and which are interposed in the hydrogen generating part (3) and provided with a diaphragm (5) in the part. A water permeable material (6) partitioned into a hydrogen side chamber provided with
A layer of hydride (7) disposed in the hydrogen side chamber in contact with the moisture permeable material (6);
A water-absorbing material (8) that is connected to the diaphragm (5) and movably disposed in the water-side chamber so as to be able to contact and separate from the water-permeable material (6) and impregnated with moisture (W). ,
The water molecules that exit from the water absorbing material (8) and permeate the moisture permeable material (6) react with the hydride (7) to generate hydrogen, and the hydrogen generating part ( based 3) in response to pressure changes in the relative moisture transmission member (6) for the operation of the diaphragm (5) to be displaced moving the contact and separation direction, leaving the water-absorbing material (8) when internal pressure rises to the water transmitting material (6) The amount of water molecules that permeate the moisture permeable material (6) is controlled by contacting when the internal pressure is reduced, and the hydrogen generation amount is thereby controlled. . In the hydrogen generator for hydrolyzing the hydride (7) to generate hydrogen,
A sealable body container (1) having a hydrogen outlet (4);
A diaphragm (5), which is provided in the main body container (1) and divides the inside of the vessel into a pressure regulating part (2) and a sealable hydrogen generating part (3) provided with the hydrogen outlet (4). When,
A water-side chamber and a hydrogen outlet (4) which are formed from a water-permeable membrane having a large number of fine pores through which a minute amount of moisture and water vapor can permeate and which are interposed in the hydrogen generator (3) and have a diaphragm (5) in the portion. A water permeable material (6) partitioned into a hydrogen side chamber provided with
A layer of disc-shaped hydride (7) disposed in the hydrogen side chamber in contact with the moisture permeable material (6);
The hydride (7) layer is formed in a disc shape having the same diameter, the moisture permeable material (6) is sandwiched between the hydride (7) layer and coaxially with the hydride (7) layer so as to be rotatable about the central axis. A water-absorbing material (8) disposed in the water-side chamber and impregnated with moisture (W);
The water-absorbing material (8) is formed of an impermeable thin film attached to the surface of the water-absorbing material (6) facing the water-permeable material (6), and is provided with a fan-shaped notch (10) extending from the center to the circumference. A notched circularly impermeable membrane (9);
Rotation drive means (11) provided in connection with the water absorbing material (8) and rotating the water absorbing material (8) about its central axis in conjunction with the diaphragm (5);
Water molecules and hydrogen that come out of the water-absorbing material (8) and permeate the water-permeable material (6) through the notch (10) corresponding to the direct contact portion between the water-absorbing material and the water-permeable material (6) Rotation drive means (11) interlocking with the diaphragm (5) that moves in response to a change in the internal pressure of the main body container (1) during the reaction. When the internal pressure rises, the rotation drive means (11) is inactivated and the notch (10) is not displaced. When the internal pressure is reduced, the rotation drive means (11) is activated to determine the notch (10). Displacement under the area state controls the amount of water molecules that permeate the moisture permeable material (6), thereby controlling the reaction between the hydride (7) and water molecules. Characteristic hydrogen generator. In the hydrogen generator for hydrolyzing the hydride (7) to generate hydrogen,
A sealable body container (1) having a hydrogen outlet (4);
A diaphragm (5), which is provided in the main body container (1) and divides the inside of the vessel into a pressure regulating part (2) and a sealable hydrogen generating part (3) provided with the hydrogen outlet (4). When,
A water-side chamber and a hydrogen outlet (4) which are formed from a water-permeable membrane having a large number of fine pores through which a minute amount of moisture and water vapor can permeate and which are interposed in the hydrogen generator (3) and have a diaphragm (5) in the portion. A water permeable material (6) partitioned into a hydrogen side chamber provided with
A layer of a rectangular hydride (7) disposed in the hydrogen side chamber in contact with the moisture permeable material (6);
The hydride (7) layer has the same rectangular shape as that of the hydride layer (7), and the moisture permeable material (6) is sandwiched between the hydride layer (7) and disposed in the water side chamber. A water absorbing material (8) impregnated and retained (W);
An impermeable membrane (9) comprising an impermeable sheet thin film interposed between the hydride layer (7) and the moisture permeable material (6) so as to be movable in one direction parallel to one side of the square. )When,
Winding means (12) for winding up and pulling out the water-impermeable membrane (9) in conjunction with the diaphragm (5) by a winding roll (13) provided close to one side of the water-absorbing material (8); Including
The water-permeable material (6) permeates through the water-impermeable membrane non-intervening part corresponding to the direct contact part of the hydride (7) layer and the water-permeable material (6) from the water-absorbing material (8). The water molecule and the hydride (7) react with each other to generate hydrogen, and the reaction with the diaphragm (5) is changed according to the change in the internal pressure of the main body container (1) during the reaction. Based on the operation of the winding means (12), the impermeable membrane (9) is not wound when the internal pressure is increased, but is wound when the internal pressure is decreased, and the non-intervening portion is displaced under the increasing area state. The hydrogen generator is characterized in that the amount of water molecules that permeate the moisture permeable material (6) is controlled, thereby controlling the reaction between the hydride (7) and water molecules. The rotation drive means (11) is a spring force-rotation force conversion mechanism provided with a spring timer and a pendulum, and the diaphragm (5) stops its movement when the internal pressure rises and allows the movement when the internal pressure falls. The hydrogen generator of Claim 4 or 5 provided in relation to. In the hydrogen side chamber, a buffer material (14) is provided adjacent to the layer of the hydride (7), and the buffer material (14) has elasticity and has an infinite number of communicating voids, The hydrogen generator according to claim 4, 5 or 6, which absorbs the expansion of the hydride (7) and holds it while allowing passage of the generated hydrogen. The hydrogen generator according to any one of claims 4 to 7, wherein the hydride (7) is formed into a strip shape or a polygonal shape by partition walls (31).