JP5400596B2 - Hydrogen generator - Google Patents

Description

  The present invention relates to a hydrogen generator that generates hydrogen by reacting a solid hydrogen generator and a reaction solution, and is particularly useful as a technique for generating hydrogen to be supplied to a fuel cell.

  As a hydrogen generator for generating hydrogen by reacting a solid hydrogen generator and a reaction solution, for example, it is disclosed in Patent Document 1 below. The hydrogen generator of Patent Document 1 includes a small liquid supply device that supplies a reaction liquid to a hydrogen generating agent. The small liquid supply device includes a liquid storage section that stores the supplied reaction liquid, and the liquid storage section. A movable partition that is arranged to partition, a discharge unit that discharges the reaction solution from the liquid storage unit, a discharge suppression unit that is provided in the discharge unit, and pressurizes the movable partition unit to pressurize the reaction solution An urging means and an urging force adjusting mechanism for adjusting the urging force of the urging means are provided.

JP 2007-111670 A

  The hydrogen generator of Patent Document 1 includes an urging means for urging the movable partition wall and an urging force adjusting mechanism for adjusting the urging force of the urging means, and the structure is complicated. . Further, the space where the urging means and the urging force adjusting mechanism are arranged becomes a dead space both when the reaction liquid is discharged from the liquid container and when the discharge is completed. It cannot be said that this is a preferable structure for conversion. In addition, since the reaction vessel containing the hydrogen generating agent and the liquid containing portion containing the reaction liquid are always in communication with each other at the discharge part, the hydrogen generating agent easily contacts and reacts with the reaction liquid, and is ineffective. There is a risk of generating hydrogen in preparation.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a hydrogen generator that has a simple structure and can be downsized. More preferably, the present invention provides a hydrogen generator capable of completely separating the reaction liquid and the hydrogen generator and starting the hydrogen generation reaction at an arbitrary timing.

In order to solve the above problems, a hydrogen generator according to the present invention provides:
In a hydrogen generator that generates hydrogen by reacting a solid hydrogen generator and a reaction solution,
A hydrogen generator that generates hydrogen by reaction with the reaction solution;
A generating agent containing portion for containing the hydrogen generating agent;
A bottomed cylindrical reaction liquid storage section for storing the reaction liquid before the start of the reaction;
A reaction liquid storage container that is provided outside the generating agent storage part, and is filled with a reaction liquid in the reaction liquid storage part in a space between the generating agent storage part and
A reaction liquid supply section capable of supplying the reaction liquid filled in the reaction liquid storage container to the generating agent storage section;
A hydrogen supply path for supplying hydrogen generated in the generating agent storage unit to the outside of the reaction liquid storage container,
By inserting the reaction liquid storage container from the opening end of the reaction liquid storage section, the reaction liquid is filled into the space via a reaction liquid passage formed on the bottom surface of the reaction liquid storage container.

  A hydrogen generator according to the present invention is a reaction liquid that is provided outside a generating agent storage section that stores a hydrogen generating agent and a space between the generating agent storage section and filled with a reaction liquid. A storage container. The hydrogen generator further includes a bottomed cylindrical reaction liquid storage section that stores the reaction liquid before the start of the reaction. When the reaction liquid storage container is inserted from the open end of the bottomed cylindrical reaction liquid storage section, the reaction liquid stored in the reaction liquid storage section is compressed by the reaction liquid storage container. A reaction liquid passage is formed on the bottom surface of the reaction liquid storage container, and the compressed reaction liquid is injected into the reaction liquid storage container through the reaction liquid passage, and the generating agent storage section and the reaction liquid storage container The space between them is filled with the reaction solution. The reaction liquid filled in the reaction liquid storage container is supplied to the generating agent storage part by the reaction liquid supply part, and reacts with the hydrogen generating agent to generate hydrogen. The generated hydrogen is supplied to the outside of the reaction solution storage container through the hydrogen supply path. Therefore, the hydrogen generator of the present invention can easily inject the reaction liquid into the reaction liquid storage container simply by inserting the reaction liquid storage container from the open end of the reaction liquid storage part, and does not include an urging means. Therefore, there is little dead space and the structure is simple. Further, since the reaction liquid storage container is inserted into the reaction liquid storage part while the reaction liquid in the reaction liquid storage part is being injected, the volume of the reaction liquid storage part is the volume of the reaction liquid injected into the reaction liquid storage container. Therefore, the entire hydrogen generator can be reduced in size.

  In the present invention, it is preferable that the reaction liquid passage is closed with a closing member.

  Since the reaction liquid passage is blocked by the blocking member, it is possible to prevent the reaction liquid in the reaction liquid reservoir from being inadvertently injected into the reaction liquid storage container. On the other hand, the reaction liquid can be injected into the reaction liquid storage container by removing the blocking member from the reaction liquid passage. Therefore, according to this configuration, the hydrogen generator capable of starting the hydrogen generating reaction at an arbitrary timing while being able to completely separate and arrange the reaction liquid and the hydrogen generating agent accommodated in the generating agent accommodating portion. Can be provided. Examples of the closing member include a lid-like body and a plug-like body that close the entrance / exit of the reaction liquid passage.

  In the present invention, the closing member is a film-like member, and the film is formed by a protrusion provided on the inner bottom surface of the reaction liquid reservoir by inserting the reaction liquid container from the open end of the reaction liquid reservoir. The shaped member is preferably broken.

  According to this configuration, the reaction liquid passage is blocked by the film-like member, so that the reaction liquid in the reaction liquid reservoir is not inadvertently injected into the reaction liquid storage container. On the other hand, a protrusion is provided on the inner bottom surface of the reaction liquid reservoir, and the film member is broken by the protrusion by inserting the reaction liquid container from the opening end of the reaction liquid reservoir. The reaction liquid stored in the reaction liquid storage section can be reliably injected into the reaction liquid storage container via the reaction liquid passage on the bottom surface of the container.

  In the present invention, the reaction liquid passage is a through-hole formed in the bottom surface of the reaction liquid storage container, and the protrusion can be inserted into the through-hole, and is along the outer peripheral surface along the height direction. It is preferable to have a concave groove.

  According to this configuration, since the protrusion has a groove along the height direction on the outer peripheral surface thereof, when the film-like member blocking the through hole is broken, the periphery of the protrusion and the film-like member are A gap is likely to occur between them, and the reaction liquid easily passes through this gap and is injected into the reaction liquid container.

  In this invention, it is preferable that the container lower part of a reaction liquid storage container can be latched to the said opening end of a reaction liquid storage part in the state with which the reaction liquid was stored by the reaction liquid storage part.

  According to this configuration, the lower part of the reaction liquid storage container is locked to the opening end of the reaction liquid storage part, and the reaction liquid is stored in the reaction liquid storage part, and the reaction liquid is injected into the reaction liquid storage container It does not react with the hydrogen generating agent in the generating agent storage unit. From this state, the reaction liquid container is inserted into the reaction liquid container by inserting the reaction liquid container from the open end of the reaction liquid reservoir, and the reaction between the hydrogen generating agent and the reaction liquid is started at an arbitrary timing. Can do.

  In the present invention, a seal member for sealing the reaction liquid between the outer wall of the reaction liquid storage container and the inner wall of the reaction liquid storage part is provided on the outer peripheral surface of the lower part of the container or the inner peripheral surface of the opening end. Is preferred.

  According to this configuration, since the reaction liquid can be sealed between the outer wall of the reaction liquid storage container and the inner wall of the reaction liquid storage part, the reaction liquid stored in the reaction liquid storage part can be It can be reliably injected into the reaction liquid container through the passage.

It is a disassembled perspective view which shows an example of the hydrogen generator of this invention. It is a figure which shows an example of a hydrogen generator, (a) is a front view, (b) is II sectional view taken on the line of (a). The state which inserts a reaction liquid storage container from the opening end of a reaction liquid storage part is shown, (a) is the insertion start time, (b) is in the middle of insertion, (c) is sectional drawing of the hydrogen generator at the time of insertion completion It is. It is the elements on larger scale which expanded the front-end | tip part of a projection part.

  A preferred embodiment of a hydrogen generator according to the present invention will be described with reference to the drawings. FIG. 1 is an exploded perspective view showing an example of the hydrogen generator of the present invention, FIG. 2 is a view showing an example of the hydrogen generator, (a) is a front view, and (b) is a diagram of (a). It is II sectional view taken on the line.

  The hydrogen generator of the present invention is a device for generating hydrogen by reacting a solid hydrogen generator and a reaction solution. As shown in the figure, the hydrogen generator includes a generating agent storage unit 1 that stores a hydrogen generating agent 11, a bottomed cylindrical reaction liquid storage unit 2 that stores the reaction liquid before the start of the reaction, and a generating agent. A reaction liquid storage container 3 provided outside the storage section 1 and filled with a reaction liquid in the reaction liquid storage section 2 in a space between the generating agent storage section 1 and a reaction liquid filled in the reaction liquid storage container 3 And a hydrogen supply hole 5 for supplying the hydrogen generated in the generating agent storage unit 1 to the outside of the reaction solution storage container 3. (Corresponding to a hydrogen supply path).

  The generating agent storage unit 1 includes a covering material 12 that restrains the periphery of the hydrogen generating agent 11 and allows deformation. The hydrogen generating agent 11 of the present invention has the property that the product produced by the reaction with the reaction liquid expands from the original volume. The covering material 12 can be deformed with the expansion of the hydrogen generating agent 11, and the generating agent containing portion 1 can expand as the hydrogen generating agent 11 expands as a whole. Moreover, the coating | covering material 12 has heat shrinkability.

  Since the generating agent storage portion 1 that stores the hydrogen generating agent 11 is expandable as the hydrogen generating agent 11 expands, it is configured to allow expansion while restraining the periphery of the hydrogen generating agent 11. Thereby, when the hydrogen generating agent 11 reacts with a reaction liquid such as water and expands, non-uniform expansion is unlikely to occur, so that the reaction rate is easily stabilized and the reproducibility of the reaction is improved.

  The periphery of the hydrogen generating agent 11 is covered with a cylindrical covering material 12. However, one side surface of the hydrogen generating agent 11 is covered with the covering material 12 through a water absorbing body 41 having water absorption. A lid member 13 is disposed above the hydrogen generating agent 11, and a bottom member 14 is disposed below the hydrogen generating agent 11. The lid member 13 may include a hydrogen discharge hole (not shown). However, since hydrogen can pass through even a minute gap, the hydrogen generated by the reaction of the hydrogen generating agent 11 and the reaction liquid is not provided with a hydrogen discharge hole, but around the lid member 13 and the bottom member 14. It is discharged from a gap between the covering material 12 and the like. The lid member 13 and the bottom member 14 are fixed to the upper end portion and the lower end portion of the covering material 12 by thermally shrinking the covering material 12 while being loosely inserted into the covering material 12. A slit 12 a for supplying a reaction liquid to the hydrogen generating agent 11 is provided on one side wall of the covering material 12. The reaction liquid supplied from the slit 12 a is absorbed and diffused by the water absorbing body 41 and supplied to the entire side surface of the hydrogen generating agent 11.

  A water absorbing body 42 is disposed around the generating agent storage unit 1. The water absorbing body 42 has water absorption, and has a function of absorbing the reaction liquid in the reaction liquid storage container 3 and supplying it to the hydrogen generating agent 11 in the generating agent storage part 1. One end side 42 a of the water absorbing body 42 extends into the covering material 12 through the slit 12 a and is in contact with the water absorbing body 41. In addition, the position which provides the slit 12a in the side wall of the coating | covering material 12 is not specifically limited. Moreover, the slit 12a is not provided in the covering material 12, but the one end side 42a of the water absorbing body 41 may be extended from the upper end or the lower end of the covering material 12 to the inside. The other end side 42 b of the water absorbent 42 extends around the generating agent storage unit 1 and is in a state capable of absorbing water in contact with the reaction liquid in the reaction liquid storage container 3. The water absorbing body 42 and the water absorbing body 41 may be constituted by one continuous water absorbing body 4.

  A water retaining body 43 is disposed on the side of the generating agent storage unit 1. As the water retaining body 43, a sponge or water-absorbing paper can be used as long as it can temporarily hold the reaction liquid. The water retaining body 43 holding the reaction liquid is in contact with the water absorbing body 42.

  The shape of the hydrogen generating agent 11 covered with the covering material 12 may be any of a quadrangular prism, a cylinder, a plate, a rod, a rectangular parallelepiped, a cube, and the like. In the example shown in the figure, a hydrogen generating agent 11 having a quadrangular prism shape is used.

  The reaction liquid storage container 3 has a square columnar appearance. The reaction liquid storage container 3 includes a container body 31 and a container bottom 32. The reaction liquid storage container 3 is provided outside the generating agent storage section 1 and can store the reaction liquid in a space 3 a between the generating agent storage section 1. A rectangular recess 31 a is formed on the upper surface of the container body 31. A hydrogen supply hole 5 is formed on the bottom surface of the recess 31 a, and the generated hydrogen is supplied from the hydrogen supply hole 5 to the outside of the reaction liquid storage container 3. An ammonia removing agent (not shown) is provided in the space of the recess 31a. The hydrogen generated from the hydrogen generator 11 contains ammonia as an impurity, and the ammonia can be removed by the ammonia remover. Such an ammonia removing agent is commercially available in the form of a sheet, but it is also possible to use one in which a granular adsorbent or the like is contained in a breathable bag. After disposing the ammonia removing agent in the space of the recess 31a, the upper portion of the recess 31a may be covered with a lid-like body (not shown). The lid-like body is provided with a hydrogen supply hole for supplying hydrogen to the outside.

  A groove 31 c is formed on the outer periphery of the container lower part 31 b of the container body 31. An annular packing 33 (corresponding to a seal member) is fitted into the groove 31c.

  The container bottom 32 has a rectangular plate shape, and a protrusion 32a is formed around the upper surface. Corresponding to the protrusions 32 a, a recess 31 d is formed at the lower end of the container body 31, and the container bottom 32 is fixed to the container body 31. A reaction liquid passage 32 b is formed in the container bottom 32. An aluminum foil 34 (corresponding to a film-like member) is stuck on the outer surface of the container bottom 32, and the reaction liquid passage 32 b is closed with the aluminum foil 34.

  The reaction liquid storage unit 2 has a bottomed cylindrical shape with an open upper end, and can store the reaction liquid before starting the reaction. The inner wall of the reaction liquid storage section 2 is slightly larger than the outer wall of the reaction liquid storage container 3, that is, the outer periphery of the container main body 31 and the container bottom 32, and the reaction liquid storage container 3 is inserted from the open end 2a of the reaction liquid storage section 2. Can do. The outer wall of the reaction liquid storage container 3 and the inner wall of the reaction liquid storage part 2 are sealed with a packing 33 fitted in the groove 31 c of the reaction liquid storage container 3. Further, the packing 33 is slidable with respect to the inner wall of the reaction liquid storage unit 2 in a state where the space between the outer wall of the reaction liquid storage container 3 and the inner wall of the reaction liquid storage unit 2 is sealed.

  FIG. 3 shows a state in which the reaction solution storage container 3 is inserted from the open end 2a of the reaction solution storage unit 2, wherein (a) is at the start of insertion, (b) is in the middle of insertion, and (c) is at the completion of insertion. Is shown.

  The packing 33 has a function of sealing the space between the outer wall of the reaction solution storage container 3 and the inner wall of the reaction solution storage unit 2, and stores the reaction solution in the reaction solution storage unit 2 as shown in FIG. In this state, it also has a function of locking the container lower portion 31b of the reaction solution storage container 3 to the opening end 2a of the reaction solution storage unit 2.

  A projection 21 is provided on the inner bottom surface 2 b of the reaction liquid storage unit 2. The protrusion 21 is provided at a position facing the reaction liquid passage 32 b of the reaction liquid storage container 3 in a state where the reaction liquid storage container 3 is inserted from the opening end 2 a of the reaction liquid storage section 2. Thereby, by inserting the reaction liquid storage container 3 from the opening end 2 a of the reaction liquid storage part 2, the aluminum foil 34 closing the reaction liquid passage 32 b by the protrusion 21 can be broken through. The reaction liquid passage 32b is provided in the vicinity of the inner wall of the reaction liquid storage container 3, and the protrusion 21 provided facing the reaction liquid passage 32b passes through the reaction liquid passage 32b and then the generating agent storage portion. 1 and the water retaining body 43 are not interfered.

  The protruding portion 21 has a tapered shape as a whole, and easily breaks through the aluminum foil 34. The height of the protrusion 21 is lower than the side wall of the reaction liquid reservoir 2. FIG. 4 shows a partially enlarged view in which the tip of the protrusion 21 is enlarged. As shown in the figure, the protruding portion 21 has a substantially square cross-sectional shape, but a concave groove 21 a is continuously formed on one side surface of the protruding portion 21. Since the protrusion 21 has the concave groove 21a, when the protrusion 21 breaks through the aluminum foil 34, a gap is easily generated between the periphery of the protrusion 21 and the aluminum foil 34, and the reaction liquid passes through this gap. Cheap. The cross-sectional shape of the protrusion 21 is not limited to a substantially square shape, and may be a circle or an ellipse.

  As shown in FIG. 3A, the reaction liquid reservoir 2 is almost entirely filled with the reaction liquid, but a part of the air layer 22 exists above. When all of the reaction liquid reservoir 2 is filled with the reaction liquid, it is difficult to insert the reaction liquid container 3 into the reaction liquid reservoir 2 because the liquid is difficult to compress. On the other hand, if there is too much air, the air may expand due to a temperature rise, and the reaction liquid storage unit 2 may expand.

  The height of the protrusion 21 is set so that the tip of the protrusion 21 does not contact the lower surface of the aluminum foil 34 in the state of FIG. The distance from the tip of the protrusion 21 to the lower surface of the aluminum foil 34 is preferably about half the thickness of the air layer 22 described above. The distance from the tip of the protrusion 21 to the lower surface of the aluminum foil 34 is preferably about 0.1 to 0.2 mm.

  When the reaction liquid storage container 3 is inserted into the reaction liquid reservoir 2 against the resistance of the reaction liquid and air from the state of FIG. 3A, the tip of the protrusion 21 reaches the aluminum foil 34, and the reaction The aluminum foil 34 blocking the liquid passage 32b is broken through. Further, when the reaction liquid storage container 3 is inserted into the reaction liquid storage section 2, the pressurized reaction liquid passes through the reaction liquid passage 32b and the space of the reaction liquid storage container 3 as shown in FIG. It is injected into 3a.

  By inserting the reaction liquid storage container 3 into the reaction liquid storage section 2 until the container bottom 32 (or aluminum foil 34) of the reaction liquid storage container 3 reaches the inner bottom surface 2b of the reaction liquid storage section 2, FIG. As in c), all the reaction solutions in the reaction solution storage unit 2 are injected into the space 3 a of the reaction solution storage container 3. Thus, since all the reaction liquid of the reaction liquid storage part 2 is inject | poured into the reaction liquid storage container 3, the volume of the reaction liquid storage part 2 becomes small and the whole hydrogen generator also becomes small. A part or all of the reaction liquid filled in the space 3 a is held in the water retaining body 43.

  When the reaction liquid is injected into the space 3 a of the reaction liquid storage container 3, most of the air originally present in the space 3 a is discharged from the hydrogen supply hole 5. There is very little air present.

  The reaction solution filled in the space 3 a of the reaction solution storage container 3 is supplied to the generating agent storage unit 1 by the water absorber 42 and the water absorber 41. The hydrogen generated by the reaction between the hydrogen generating agent 11 in the generating agent storage unit 1 and the reaction liquid is once discharged into the space 3 a of the reaction liquid storage container 3. At this time, since the air in the space 3 a is small as described above, the space 3 a is immediately filled with the generated hydrogen, and hydrogen is immediately supplied to the outside from the hydrogen supply hole 5 of the reaction solution storage container 3.

  The hydrogen generating agent 11 expands when it reacts with the reaction solution, and the generating agent containing portion 1 also expands as a whole. On the other hand, when the hydrogen generating agent 11 and the reaction solution react, the reaction solution is consumed and the volume of the reaction solution decreases. That is, since the expansion of the generating agent storage unit 1 and the decrease of the reaction solution occur simultaneously inside the reaction solution storage container 3, the combined volume of the generating agent storage unit 1 and the reaction solution ends from the start of the hydrogen generation reaction. It doesn't change much until time. As a result, the size of the reaction liquid storage container 3 can be reduced, and the entire hydrogen generator can be reduced in size.

  Moreover, since the generating agent storage part 1 is surrounded by the reaction liquid, the temperature increase of the hydrogen generating agent 11 when reacting with the reaction liquid can be suppressed, and the hydrogen generating reaction is stably performed. .

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

  As the hydrogen generating agent used in the present invention, it is possible to use a hydrogen generating material such as a particle alone (without embedding the resin), but a granular hydrogen generating material in the resin base material. The thing containing is preferable. In that case, as the resin to be used, those other than the water-soluble resin are preferable from the viewpoint of exerting the restraining force by the coating material.

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

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

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

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

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

  When using hydrogen generating materials such as particulates without embedding the resin, from the viewpoint of applying the restraining force of the coating material with an appropriate force, the hydrogen generating materials are bound with resin as a binder, or particulate hydrogen generating materials. Is preferably tableted by press molding.

  As the resin, a resin other than the water-soluble resin is preferably used, and examples thereof include a thermosetting resin, a thermoplastic resin, and a heat resistant resin, and a thermosetting resin is preferable. By using a thermosetting resin, the resin base material generally tends to be brittle, the resin base material collapses more easily during the reaction, and the reaction easily proceeds naturally. Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylic resin, fluororesin, polyester, and polyamide. Examples of the heat resistant resin include aromatic polyimide, polyamide, and polyester.

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

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

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

  The hydrogen generating agent may have a porous structure, but a substantially solid structure is preferable. That is, in the hydrogen generating agent of the present invention, porosity (%) = pore volume / total volume × 100 is preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less. Usually, in such a structure with few vacancies, the reaction does not easily proceed inside, but in the present invention, the reaction can proceed even at such a low porosity by using calcium hydride at a high concentration. And volume efficiency can be increased.

  In addition, hydrogen generating substances such as calcium hydride may generate hydrogen during mixing or reaction with the resin, resulting in vacancies. However, by performing reaction hardening or cooling solidification under pressure, In particular, a solid structure can be obtained.

  The hydrogen generating agent to be used may be any shape such as a sheet shape, a granular shape (pulverized product), and a lump shape (molded product), but from the viewpoint of controlling the reaction rate, a sheet shape, a plate shape, a column shape and the like are preferable. When pulverizing, the particle size is preferably 1 to 10 mm, more preferably 2 to 5 mm.

  The hydrogen generator in the present invention is preferably produced by a production method including a step of curing a mixture containing 60% by weight or more of granular calcium hydride in an uncured thermosetting resin. The mixture can contain components such as other components and curing agents described above.

  In the present invention, it is particularly preferable that the step of curing the mixture is performed under pressure. As a pressurizing condition in the case of performing pressurization, 1-100 MPa is preferable, 2-50 MPa is more preferable, and 5-30 MPa from the viewpoint of lowering the porosity of the hydrogen generating agent in consideration of manufacturing equipment and manufacturing cost. Is more preferable. A press mold or the like can be used for pressurization.

  For example, when a thermoplastic resin is used as a resin other than the thermosetting resin, 60% by weight or more of granular calcium hydride is mixed at a temperature equal to or higher than the softening point of the resin, and this is cooled and solidified. Generators can be produced. In the case of a heat resistant resin, a method of mixing and curing calcium hydride in a softened precursor, and the like, as in the case of a thermoplastic resin, may be mentioned.

  The covering material used in the present invention restrains the periphery of the hydrogen generating agent and allows elastic deformation and / or plastic deformation, but is preferably a covering material that allows elastic deformation. The covering material is preferably covered only by one layer, but it is also possible to form two or more layers.

  Examples of coating materials that allow elastic deformation include resin elastic tube, resin base adhesive tape, rubber tube, rubber base adhesive tape, and metal elastic body C-shaped sleeve. Examples of the covering material include a plastically deformable resin tube and a resin base adhesive tape.

  In the present invention, it is particularly preferable to use a heat-shrinkable coating material, and it is more preferable to use a heat-shrinkable tube. The heat-shrinkable tube generally has a property that enables elastic deformation or plastic deformation before the shrinkage is completed.

  As a material of the heat shrinkable tube, a general heat shrinkable tube such as vinyl chloride, polyvinylidene fluoride, ethylene propylene rubber, or neoprene can be used, but a heat resistant heat shrinkable tube is preferably used. The heat-resistant heat-shrinkable tube includes tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-ethylene copolymer (ETFE), poly Examples thereof include tetrafluoroethylene (PTFE) and silicone rubber.

  The thickness of the coating material is, for example, 1 μm to 5 mm. In particular, when a heat-shrinkable coating material is used, the thickness is preferably 10 to 3000 μm, more preferably 100 to 2000 μm, from the viewpoint of obtaining an appropriate binding force. .

  In the present invention, when the water absorbing body is provided, a part of the hydrogen generating agent is brought into contact with the hydrogen generating agent. Any water absorbent material can be used as long as it can be impregnated with water, but filter paper, water absorbent felt, water absorbent resin, absorbent cotton, water absorbent nonwoven fabric, water absorbent paper and the like are preferable.

  The thickness of the water absorbing body is preferably 0.05 to 3 mm, more preferably 0.1 to 1 mm, from the viewpoint of appropriately supplying a reaction liquid such as water to the hydrogen generating agent.

  The inner diameter of the covering material is preferably 100 to 500%, more preferably 110 to 300% of the outer diameter of the hydrogen generating agent from the viewpoint of obtaining a uniform restrained state.

  Although the temperature at which the coating material is thermally shrunk depends on the shrinkage characteristics of the coating material, it is preferably 70 to 150 ° C., more preferably 80 to 120 ° C. in consideration of the temperature of the hydrogen generator during the reaction. In this temperature range, it is preferable to use a heat-shrinkable coating material having a shrinkage rate of 20 to 95%, and more preferably 50 to 80%.

  The hydrogen generator of the present invention generates hydrogen by supplying a reaction solution to a hydrogen generating agent. Examples of the reaction solution include water, an aqueous acid solution, and an alkaline aqueous solution. The temperature of the reaction solution to be supplied may be room temperature, but may be heated to 30 to 80 ° C.

  In the present invention, a method of generating hydrogen by supplying a reaction liquid to the hydrogen generating agent through a water absorbent partly in contact with the hydrogen generating agent is preferable for keeping the reaction rate constant.

  Although the supply amount of the reaction liquid can be adjusted according to the amount of hydrogen gas to be generated, the reaction rate is controlled even in the case of excessive supply in the present invention. Hydrogen generation is possible.

<Another embodiment>
In the above embodiment, the reaction liquid passage 32 b is closed with a film-like member, and the reaction liquid storage container 2 is inserted into the reaction liquid storage container 2 from the open end 2 a of the reaction liquid storage part 2. The example which comprises so that a film-like member may be fractured | ruptured by the projection part 21 provided in the bottom face 2b was shown. However, the reaction liquid passage 32b may be closed with a film-like member that can be broken by the pressure of the pressurized reaction liquid. That is, since the reaction liquid in the reaction liquid storage section 2 is pressurized by inserting the reaction liquid storage container 3 from the open end 2a of the reaction liquid storage section 2, the strength that can be broken by the pressure of the reaction liquid. The reaction liquid passage 32b can be closed with a film-like member having At this time, the film-like member may be half-cut and easily broken by the pressure of the reaction solution.

DESCRIPTION OF SYMBOLS 1 Generating agent accommodating part 2 Reaction liquid storage part 2a Open end 2b Inner bottom face 3 Reaction liquid accommodating container 3a Space 4 Water absorbing body 5 Hydrogen supply hole 11 Hydrogen generating agent 12 Coating | covering material 21 Protrusion part 21a Groove 31 Container main body 31b Container lower part 32 Container bottom part 32b Reaction liquid passage 33 Packing 34 Aluminum foil 41 Water absorbing body 42 Water absorbing body

Claims (6)

In a hydrogen generator that generates hydrogen by reacting a solid hydrogen generator and a reaction solution,
A hydrogen generator that generates hydrogen by reaction with the reaction solution;
A generating agent containing portion for containing the hydrogen generating agent;
A bottomed cylindrical reaction liquid storage section for storing the reaction liquid before the start of the reaction;
A reaction liquid storage container that is provided outside the generating agent storage part, and is filled with a reaction liquid in the reaction liquid storage part in a space between the generating agent storage part and
A reaction liquid supply section capable of supplying the reaction liquid filled in the reaction liquid storage container to the generating agent storage section;
A hydrogen supply path for supplying hydrogen generated in the generating agent storage unit to the outside of the reaction liquid storage container,
The hydrogen is characterized in that the reaction liquid is filled into the space through the reaction liquid passage formed in the bottom surface of the reaction liquid storage container by inserting the reaction liquid storage container from the open end of the reaction liquid storage section. Generator.   The hydrogen generation apparatus according to claim 1, wherein the reaction liquid passage is closed with a closing member. The closing member is a film-like member,
The hydrogen generating apparatus according to claim 2, wherein the film-like member is broken by a protrusion provided on the inner bottom surface of the reaction liquid reservoir by inserting the reaction liquid container from the open end of the reaction liquid reservoir. The reaction liquid passage is a through hole formed in the bottom surface of the reaction liquid storage container,
The hydrogen generating apparatus according to claim 3, wherein the protrusion is insertable into the through-hole and has a groove along the height direction on an outer peripheral surface thereof.   The hydrogen generator according to any one of claims 1 to 4, wherein the lower part of the reaction liquid storage container can be locked to the opening end of the reaction liquid storage part in a state where the reaction liquid is stored in the reaction liquid storage part. .   The seal member which seals a reaction liquid between the outer wall of a reaction liquid storage container and the inner wall of a reaction liquid storage part is provided in the outer peripheral surface of the said container lower part, or the inner peripheral surface of the said opening end. Hydrogen generator.

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