JP5498131B2 - 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 supplying hydrogen to a fuel cell.

  Conventionally, as a hydrogen generating agent for generating hydrogen gas by supplying water, a main component is a metal such as iron or aluminum, or a main component is a metal hydride compound such as magnesium hydride or calcium hydride. Those are known (for example, see Patent Document 1).

  Patent Document 2 discloses a hydrogen generator in which a metal hydride is embedded in a solid water-soluble compound such as a water-soluble resin for the purpose of appropriately controlling the reaction rate between the metal hydride and moisture. Has been.

  On the other hand, Patent Document 3 discloses a hydrogen generation apparatus in which a hydrogen generating agent is accommodated in each accommodating space at a filling rate at which the reaction liquid is difficult to enter due to expansion of the hydrogen generating agent when the reaction is almost completed. Has been. Also, in this hydrogen generator, when the reaction nears completion in the storage space, it becomes difficult for the reaction liquid to enter due to the expansion of the hydrogen generating agent, and the reaction liquid is supplied to the adjacent storage space via the supply path. Is described.

Japanese Patent Laid-Open No. 2003-314792 International Publication WO2007 / 055146 JP 2007-63029 A

  As described in Patent Document 3, as a general property of the hydrogen generating agent, there is a property that it easily expands by reaction with water or the like. According to the study by the present inventors, the state is constrained to a container that does not allow deformation. It was found that when the hydrogen generating agent was accommodated, the progress of the reaction was likely to end during the reaction. Conversely, if the reaction is allowed to proceed with free expansion, the reaction rate is likely to be affected by changes in the environmental temperature, and the reaction rate is likely to become unstable due to the non-uniform expansion state. It turned out to be scarce. It has been found that such a phenomenon becomes particularly prominent due to the contact state between the water absorbing body and the hydrogen generating agent when water or the like is supplied through the water absorbing body.

  Accordingly, an object of the present invention is to provide a hydrogen generator having high stability and reproducibility of the hydrogen generation reaction.

  The inventors of the present invention have intensively studied to achieve the above object, and found that the stability and reproducibility of the hydrogen generation reaction are enhanced by allowing expansion while restraining the periphery of the hydrogen generator. The present invention has been completed.

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 expands by reaction with the reaction solution;
The hydrogen generating agent is accommodated, and a generating agent accommodating portion that can expand as the hydrogen generating agent expands,
A reaction liquid storage container provided outside the generating agent storage part and capable of storing the reaction liquid in a space between the generating agent storage part;
A reaction liquid supply section capable of supplying the reaction liquid 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 generating agent storage part is arranged in a state where expansion is not hindered by an inner wall of the reaction liquid storage container.

  According to the hydrogen generator according to the present invention, the generating agent storage part that stores the hydrogen generating agent is expandable with the expansion of the hydrogen generating agent, and thus allows expansion while constraining the periphery of the hydrogen generating agent. It has a configuration. Thereby, when the hydrogen generating agent reacts with a reaction liquid such as water and expands, non-uniform expansion hardly occurs, so that the reaction rate is easily stabilized and the reproducibility of the reaction is also improved. Further, since the generating agent storage part is arranged in a state where the expansion is not hindered by the inner wall of the reaction liquid storage container, the hydrogen generating agent stored in the generation agent storage part is not restrained from the inner wall of the reaction liquid storage container. I do not receive it. As a result, it is possible to provide a hydrogen generator having high stability and reproducibility of the hydrogen generation reaction. Furthermore, since the reaction liquid is stored in the space between the generating agent storage part and the reaction liquid storage container, and the hydrogen generating agent is surrounded by the reaction liquid through the generating agent storage part, the hydrogen generating agent The environmental temperature is easily kept constant, and the stability of the hydrogen generation reaction is high.

  In the present invention, at least one end of the generating agent container is fixed to a part of the inner wall of the reaction liquid container, and the generating agent container is also in the expanded state when the reaction of the hydrogen generating agent is completed. It is preferable that it is arrange | positioned so that it may have a clearance gap with the other inner wall part of a container.

  According to this configuration, the generating agent storage section has a gap with the inner wall portion of the reaction liquid storage container even in the expanded state when the reaction of the stored hydrogen generating agent is completed. From the start to the completion of the reaction, it is not restrained from the inner wall of the reaction solution container.

  In the present invention, when the hydrogen generator is installed so that one end of the fixed generating agent storage portion is at the top, and when the reaction liquid is put up to 90% of the depth of the internal space of the reaction liquid storage container, A generator containing portion is provided such that the liquid level of the reaction liquid at the completion of the reaction is 60% or more of that at the start of the reaction, and the reaction liquid supply section is a water-absorbing supply member. One end side of the member is in contact with the hydrogen generating agent, the other end side is provided outside the generating agent storage portion, and the other end side crosses a position of 50% of the depth of the internal space of the reaction liquid storage container. It is preferable to arrange.

  According to this configuration, the liquid level of the reaction liquid gradually decreases from 90% of the depth of the internal space of the reaction liquid storage container as the reaction proceeds. It becomes 56% or more of the depth of the internal space. On the other hand, the other end side of the supply member is disposed across a position of 50% of the depth of the internal space of the reaction solution storage container. Therefore, a part of the supply member always comes into contact with the reaction solution from the start of the reaction to the completion of the reaction, and the reaction solution is reliably supplied to the hydrogen generating agent via the supply member, so that the hydrogen generation reaction is stably performed. Progresses. Further, according to this configuration, even when the hydrogen generator is installed upside down, that is, when the hydrogen generator is installed so that one end of the fixed generating agent storage portion is at the lowest position, the supply member A part of the water always comes into contact with the reaction solution from the start of the reaction to the completion of the reaction, and the hydrogen generation reaction proceeds stably.

  In this invention, it is preferable that the said generating agent accommodating part has a heat-shrinkable coating | covering material which coat | covers at least the circumference | surroundings of the said hydrogen generating agent.

  When a heat-shrinkable coating material is used, when the environmental temperature is high, the reaction rate increases, and when the temperature of the hydrogen generating agent rises, the shrinkage force of the coating material increases and suppresses intrusion of the reaction liquid. As a result, the reaction rate is reduced, so that it is possible to realize a hydrogen generation reaction that is less susceptible to changes in the environmental temperature. Furthermore, when a heat-shrinkable coating material is used, the hydrogen generating agent can be restrained moderately and uniformly by simply heat-shrinking the coating material when coating the periphery of the hydrogen generating agent. This is also advantageous from the viewpoint of the manufacturing process. Furthermore, the heat-shrinkable coating material has a function for ensuring safety that causes a large heat shrinkage to stop the hydrogen generation reaction when heat is generated by a rapid reaction due to some trouble.

  In this invention, it is preferable that the said reaction liquid storage container has a ventilation part connected with the exterior via a hydrophobic porous member.

  The vent of the reaction liquid storage container communicates with the outside through a hydrophobic porous member, so that the reaction liquid does not leak to the outside, but the gas can be discharged to the outside, and the reaction liquid storage container is external to the reaction liquid storage container. When the reaction liquid is injected from the inside, it is possible to prevent the internal gas from becoming resistance and making it difficult to inject the reaction liquid.

  In the present invention, it is preferable that a plurality of the generating agent storage portions are provided at intervals in the reaction liquid storage container.

  By providing a plurality of generating agent accommodating portions at intervals, even if the hydrogen generating agent expands as the hydrogen generating agent expands, the generating agent accommodating portions do not come into contact with each other, and hydrogen can be stably generated. .

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 sectional view of a hydrogen generator is shown, (a) is the state at the time of hydrogen generation reaction start, and (b) is the state at the time of completion of hydrogen generation reaction. It is sectional drawing of the hydrogen generator installed in various attitude | positions.

  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 is provided outside the generating agent storage unit 1 that stores the hydrogen generating agent and the generating agent storage unit 1, and stores the reaction liquid in the space between the generating agent storage unit 1. Reaction between the possible reaction liquid storage container 2, the water absorber 3 (corresponding to a supply member) capable of supplying the reaction liquid in the reaction liquid storage container 2 to the generating agent storage section 1, and hydrogen generated in the generating agent storage section 1 A hydrogen supply pipe 4 (corresponding to a hydrogen supply path) for supplying the liquid container 2 to the outside is provided. However, the hydrogen supply path is not limited to a pipe shape, and may be a simple hole provided in the housing of the reaction solution storage container 2.

  In the present embodiment, an example is shown in which five generating agent storage portions 1 having the same configuration are provided. The five generating agent storage portions 1 are provided at intervals, and one end of each of the generating agent storage portions 1 is fixed to the upper inner wall of the reaction liquid storage container 2.

  The generating agent storage unit 1 includes a hydrogen generating agent 11 and 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.

  All the side surfaces and the lower surface of the hydrogen generating agent 11 are covered with the covering material 12a. However, only one side surface of the hydrogen generating agent 11 is covered with the covering material 12a through the water absorbing body 31 having water absorption. On the upper part of the hydrogen generating agent 11, a lid body 13 having a hydrogen discharge hole 13a is disposed. Hydrogen generated by the reaction of the hydrogen generating agent 11 and the reaction liquid is discharged from the hydrogen discharge hole 13a. The lid 13 is fixed to the upper end portion of the covering material 12a by thermally contracting the covering material 12a with the insertion portion 13b loosely inserted into the covering material 12a. A water supply hole 14 for supplying a reaction liquid to the hydrogen generating agent 11 is provided on one side wall of the covering material 12a. The reaction solution supplied from the water supply hole 14 is absorbed and diffused by the water absorbing body 31 and supplied to the entire side surface of the hydrogen generating agent 11. Further, the lid body 13 includes a collar portion 13c extending from the insertion portion 13b.

  A water absorbing body 3 is provided around the covering material 12 a that covers the hydrogen generating agent 11. The water absorbing body 3 has water absorption, and has a function of absorbing the reaction liquid in the reaction liquid storage container 2 and supplying it to the hydrogen generating agent 11 in the generating agent storage unit 1. One end side 3 a of the water absorbing body 3 is in contact with the side wall of the covering material 12 a provided with the water supply hole 14, and the reaction liquid is supplied into the covering material 12 a through the water supply hole 14. The water absorbing body 3 is fixed around the hydrogen generating agent 11 by the covering material 12b. Specifically, the hydrogen generating agent 11 covered with the covering material 12a and the one end side 3a of the water absorbing body 3 are loosely inserted into the cylindrical covering material 12b, and the covering material 12b is thermally contracted, thereby generating the hydrogen generating agent. The water absorbing body 3 is fixed around 11. The other end side 3b of the water absorbing body 3 protrudes from the end portion of the covering material 12b and is in a state capable of absorbing water in contact with the reaction solution. In the drawing, the thickness of the covering material 12a is emphasized, and the inner water absorbing body 31 and the outer water absorbing body 3 appear to be separated from each other, but the thickness of the covering material 12a is actually thin, Due to the thermal contraction of the covering material 12 b, the inner water absorbing body 31 and the outer water absorbing body 3 are in contact via the water supply hole 14.

  The shape of the hydrogen generating agent 11 covered with the covering material 12a and the covering material 12b may be any of a quadrangular prism, a cylinder, a plate shape, a rod shape, 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 2 includes a container body 21 and a container lid part 22. The container main body 21 can accommodate the reaction liquid therein. Five frame portions 21 a are arranged in a row at the top of the container body 21. The inner periphery of the frame portion 21a is slightly smaller than the outer periphery of the collar portion 13c formed on the lid 13 of the generating agent storage unit 1, and the collar portion 13c can be locked to the frame portion 21a. Thereby, the end of the generating agent accommodating part 1 can be fixed to the upper part of the container main body 21. A vent hole 21 b (corresponding to a vent portion) is formed in the side wall of the container body 21. The vent hole 21 b is closed by a hydrophobic sheet 23 (corresponding to a porous member) attached to the outside of the container body 21. A water injection hole 21c for supplying the reaction liquid to the reaction liquid storage container 2 may be provided on the side wall opposite to the side wall in which the vent hole 21b is formed.

  The container lid 22 is fixed to the upper end of the container main body 21 in a state where the generating agent storage unit 1 is fixed to the upper part of the container main body 21. A space 15 is provided between the upper surface of the lid 13 of the generating agent storage unit 1 and the container lid 22 as shown in FIG. Hydrogen generated by the hydrogen generating agent 11 is discharged into the space 15 from the hydrogen discharge hole 13 a of the lid 13. The hydrogen discharged into the space 15 is supplied to the outside of the reaction solution storage container 2 through the hydrogen supply pipe 4 provided in the container lid portion 22.

  In order to remove ammonia, which is an impurity, from the hydrogen generated from the hydrogen generator 11, an ammonia remover (not shown) may be provided in the space 15. Specifically, a sheet-like ammonia removing agent can be disposed in the space 15. Such an ammonia removing agent is commercially available in the form of a sheet, but it is also possible to use one in which a granular adsorbent or the like is contained in a breathable bag.

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

  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%.

  Below, the relationship between the reaction liquid accommodated in the reaction liquid storage container 2 and the water absorption body 3 is demonstrated in detail. 3A and 3B are cross-sectional views of the hydrogen generator, where FIG. 3A shows a state when the hydrogen generation reaction is started, and FIG. When the hydrogen generating agent 11 reacts with the reaction solution, it expands as shown in FIG. At the same time, the generating agent container 1 also expands as a whole.

  As shown in the figure, one end of the generating agent storage unit 1 is fixed to a part of the inner wall of the reaction liquid storage container 2. 3A and 3B show an example of a state in which the upper end of the generating agent storage unit 1 is fixed to the ceiling portion of the reaction liquid storage container 2 and the generating agent storage unit 1 is suspended from above.

  The reaction solution is stored in an internal space S formed between the generating agent storage unit 1 and the reaction solution storage container 2. Moreover, as shown in FIG. 3, the other end side 3b of the water absorbing body 3 is disposed so as to protrude from the lower end portion of the covering material 12b and wind up the generating agent accommodating portion 1, and is 50% of the depth H of the internal space S. Extends upward across the position of.

  At the start of the hydrogen generation reaction, as can be seen from FIGS. 1 and 2, the five generating agent accommodating portions 1 are provided at intervals. Moreover, the generating agent accommodating part 1 has a gap | interval between the inner walls of all the side walls of the container main body 21, and prevents it from contacting all the side walls. Further, at the start of the reaction, as shown in FIG. 3A, the reaction liquid is put to a liquid level height h1 of about 90% of the depth H of the internal space S.

  When the hydrogen generating agent 11 reacts with the reaction liquid, the generating agent storage unit 1 expands as described above, and the volume of the internal space S decreases accordingly. Thereby, the liquid level of the reaction liquid in the internal space S tends to increase. 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. Thereby, the liquid level of the reaction liquid in the internal space S tends to decrease. As described above, the increase in the liquid level of the reaction liquid due to the expansion of the generating agent container 1 and the decrease in the liquid level due to the consumption of the reaction liquid occur simultaneously in the internal space S. The volume of the internal space S can be reduced, and as a result, the size of the entire hydrogen generator can be reduced.

  FIG. 3B shows a state when the hydrogen generation reaction is completed, and the liquid level height h2 at the completion of the reaction is 60% or more of the liquid level height h1 at the start of the reaction. . In the present embodiment, as the hydrogen generation reaction proceeds, the generating agent storage unit 1 expands and the volume of the internal space S decreases, but a part of the reaction solution is consumed for the reaction. The surface height gradually decreases. The liquid level heights h1 and h2 at the start and completion of the hydrogen generation reaction are determined by the relationship between the type and amount of the hydrogen generating agent 11, the volume of the reaction liquid container 2, the volume of the reaction liquid, and the like. It can be set as appropriate. In the present embodiment, the level of the reaction liquid is set to gradually decrease during the hydrogen generation reaction, but the liquid level may be substantially constant.

  Further, according to the relationship between the liquid level of the reaction liquid and the water absorbing body 3 as described above, stable hydrogen generation is possible even when the hydrogen generator is not installed in the direction shown in FIG. 4A and 4B are cross-sectional views of the hydrogen generator installed in various positions. FIG. 4A shows a state where the hydrogen generator shown in FIG. 3 is rotated by 90 degrees, and FIG. 4B shows a state where the hydrogen generator shown in FIG. It is the state made to do. FIG. 4 shows the state when the hydrogen generation reaction is completed with the least amount of the reaction solution. As shown in the figure, in any posture, a part of the water absorbing body 3 is in contact with the reaction liquid, and the reaction liquid can be supplied to the hydrogen generating agent 11 through the water absorbing body 3.

  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.

  In the present embodiment, five generating agent storage portions 1 are provided. However, the present invention is not limited to this, and only one or six or more may be provided. Moreover, when providing the several generating agent accommodating part 1, you may connect the other end side 3b of each water absorbing body 3. FIG.

DESCRIPTION OF SYMBOLS 1 Generating agent accommodating part 2 Reaction liquid accommodating container 3 Water absorbing body 3a One end side 3b Other end side 4 Hydrogen supply pipe 11 Hydrogen generating agent 12 Coating | covering material 13 Lid 13a Hydrogen discharge hole 21 Container main body 21b Vent hole 22 Container lid part 23 Hydrophobic Sex sheet

Claims (6)

In a hydrogen generator that generates hydrogen by reacting a solid hydrogen generator and a reaction solution,
A hydrogen generating agent that expands by reaction with the reaction solution and contains a particulate hydrogen generating substance in the resin matrix ;
A hydrogen generating agent containing and constraining the periphery of the hydrogen generating agent, and a generating agent containing portion having a covering material that can expand as the hydrogen generating agent expands,
A reaction liquid storage container provided outside the generating agent storage part and capable of storing the reaction liquid in a space between the generating agent storage part;
A reaction liquid supply section capable of supplying the reaction liquid 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 generating apparatus according to claim 1, wherein the generating agent storage unit is disposed in a state in which expansion is not hindered by an inner wall of the reaction liquid storage container.   At least one end of the generating agent storage portion is fixed to a part of the inner wall of the reaction solution storage container, and the generation agent storage portion is not limited to the reaction solution storage container even in the expanded state when the reaction of the hydrogen generating agent is completed. The hydrogen generator according to claim 1, wherein the hydrogen generator is disposed so as to have a gap between the inner wall portion and the inner wall portion. When the hydrogen generator is installed so that one end of the fixed generating agent storage part is at the top, and the reaction liquid is put up to 90% of the depth of the internal space of the reaction liquid storage container, A generator containing part is provided such that the liquid level of the reaction liquid is 60% or more of the reaction start time,
The reaction liquid supply unit is a water-absorbing supply member, one end side of the supply member is in contact with the hydrogen generating agent, the other end side is provided outside the generating agent storage unit, and the other end side is a reaction liquid. The hydrogen generator according to claim 1, wherein the hydrogen generator is disposed across a position of 50% of the depth of the internal space of the container.   The hydrogen generator according to any one of claims 1 to 3, wherein the generating agent storage section includes a heat-shrinkable covering material that covers at least the periphery of the hydrogen generating agent.   The hydrogen generator according to any one of claims 1 to 4, wherein the reaction liquid storage container has a ventilation portion communicating with the outside through a hydrophobic porous member. The hydrogen generator according to any one of claims 1 to 5, wherein a plurality of the generating agent storage portions are provided at intervals in the reaction liquid storage container.

Images