JP5420270B2 - Hydrogen generating material and hydrogen generating method - Google Patents

Description

  The present invention relates to a practical technique for energy production in which hydrogen gas is produced by decomposing water molecules. The hydrogen gas produced by the hydrogen generating material and the hydrogen generating method of the present invention becomes a fuel gas for a small fuel cell that enables charging of a rapidly developing portable information communication device, as well as a hydrogen reduction chemical reaction, It can be used for various purposes such as control of biological reactions and hydrogen water for industrial cleaning.

  Hydrogen tanks using hydrogen storage alloys and small fuel cells using hydrogen gas as fuel are being put into practical use. How to manufacture hydrogen gas used in such a small fuel cell at low cost, simply and safely has become an important technical issue. Conventionally, there is a method of producing hydrogen by decomposing organic molecules such as methanol and natural gas as a method meeting this purpose, but it cannot solve technical problems related to the reactor, temperature, pressure, etc. At present, it has not been put to practical use.

  The present inventor has developed a method for producing hydrogen gas by using metal aluminum, other metals, and semiconductor materials, decomposing water molecules using its intrinsic energy, and has filed several patent applications for the results. (See Patent Documents 1 to 4).

JP 2003-304105 A JP 2004-123517 A JP 2006-045004 A JP 2006-063405 A

  At present, various types of fuel cells have been developed and put to practical use. In particular, mobile fuel cells (PEFC) for charging portable information and communication devices are about to be put into practical use for the first time. For this purpose, development of a small hydrogen generator is indispensable as a hydrogen supply source. It is. The present invention (1) without deteriorating the quality of the aluminum fine particles as a hydrogen generation source (for example, the aluminum fine particles are oxidized to deteriorate the quality when reacted with oxygen, but do not cause such deterioration). For the purpose of providing a technique capable of stably supplying a required amount of hydrogen by providing a technique that can be stored, and (2) controlling the amount of water supplied to the aluminum fine particles. Yes.

  The present inventor has developed a membrane that allows only water to pass and does not allow oxygen, nitrogen, and carbon dioxide molecules to permeate. By packaging aluminum fine particles with this membrane, the above objects (1) and (2) can be achieved. Developed technology to make it possible.

  It is not easy to develop a membrane that allows a required amount of water to pass through and has a gas barrier property. The present inventor has increased the water permeation amount by controlling a porous membrane in which an organic polymer such as polyethylene (PE), ethylene-vinyl alcohol copolymer (EVOH), and biodegradable resin are communicated. And developed a technology to release the generated hydrogen gas to the outside. The pores of the continuous porous membrane (hereinafter referred to as “communication porous membrane”) are preferably formed by irregularly shaped granular spaces. Here, the communicating porous membrane is defined as a membrane having continuous pores in which pores (granular spaces) continuously penetrate both surfaces of the membrane and the pores are connected to each other. The communicating porous membrane can be manufactured, for example, by a technique developed by the present applicant (see Japanese Patent Application Laid-Open No. 2007-314713). In addition, you may use a nonwoven fabric as a water-permeable film.

  There are two types of gas barrier membranes: a method of forming the gas barrier membrane separately from the water permeable membrane (for example, a double bag type or a bottled method) and a method of forming on the water permeable membrane. Among these, in the method of forming separately from the water permeable membrane, known gas barrier films such as glass, metal foil, aluminum vapor deposition film, silica vapor deposition film, ethylene vinyl alcohol resin film, PVDC resin film, PVA coat film and PVDC coat film Packs and seals the aluminum fine particles in the water permeable membrane in a bag or bottle shape using

A method for forming a gas barrier film that does not transmit oxygen molecules as a composite film inside, on the surface, or outside of the porous film is as follows. That is, when a gas barrier film is to be formed inside or on the surface (including both one side and both sides) of the porous film, the gas barrier material is water-soluble, water-disintegrating, water-peeling and water-permeable. It is preferable to use a material having at least one property.
By using a water-soluble, water-disintegrating, and water-peeling gas barrier material, water can enter the porous membrane. In this case, the invading water starts to react with the aluminum fine particles and generates hydrogen gas. The generated hydrogen gas can be released to the outside through the water dissolution, water collapse, and water separation of the porous membrane. become.
In addition, when a water-permeable gas barrier material is used, water that has entered the inside starts to react with the aluminum fine particles to generate hydrogen gas, the internal pressure increases, and the gas barrier film is broken or drowned. This makes it possible to release the hydrogen gas generated outside.

  As a material for forming a gas barrier film having water permeability and the like, a known material suitable for a required storage period and a hydrogen generating material can be used as long as a film can be formed on the water permeable film. However, it is preferable to use an inorganic compound such as water-swellable synthetic mica or montmorillonite, an organic compound such as polyvinyl alcohol, ethylene vinyl alcohol, or saccharide, or a composite material of an inorganic compound and an organic compound. By packaging with a water permeable membrane formed with such a gas barrier film (hereinafter referred to as “gas barrier film”), the hydrogen generating material can be stored in the atmosphere for a long period of time. It is easy to use because it only needs to be put into the water as it is during use.

The method for forming the gas barrier coating on the water permeable membrane is not limited to a specific method, and a known method such as a coating method or an impregnation method can be used.
As the coating method, a known coating method such as gravure coating, reverse coating, air knife coating, metering bar coating and the like can be applied, and a coating film of a plurality of gas barrier layers can be formed by appropriately combining them. . The formation of the coating film may be carried out at any stage, for example, a method of in-line coating such as a method of forming a coating film subsequently after the formation of the porous film, or winding up after forming the porous film, Any of a method of off-line coating in a separate line and a method of dipping in a bag-making state may be employed. An off-line coating is preferred from the viewpoint of easy control of drying conditions. The base film is subjected to a known adhesion promoting treatment (for example, corona discharge treatment in air, nitrogen gas, nitrogen / carbon dioxide mixed gas, or other atmosphere, decompression before application of the gas barrier resin composition. Underneath plasma treatment, flame treatment, ultraviolet treatment, etc.) may be performed. Of course, you may perform an anchor process using well-known anchor processing agents, such as a urethane resin, an epoxy resin, an acrylic resin, and a polyethyleneimine.
Further, a gas barrier film can be formed inside the water permeable membrane by an impregnation method such as vacuum injection. In this case, the gas barrier coating can be formed deep inside the water permeable membrane.
The drying method of the coating film composed of the gas barrier layer is not limited to a specific method, and a hot roll contact method, a heating medium (air, oil, etc.) contact method, an infrared heating method, a microwave heating method, or the like is used. be able to.

  When packaging the outside with a gas barrier film, even if this package is opened in the air, it is necessary to wrap it in a gas atmosphere that does not impair the quality of aluminum fine particles such as nitrogen gas. The interior is structured so that the granular spaces filled with these gases communicate with each other, so the atmosphere does not immediately enter the interior, and you can get a time delay before water is added. Is preferred. When the container for containing the aluminum fine particles is formed of a non-woven fabric, the aluminum fine particles leak and have a sealing property that is inferior to that of the porous film, and the air enters quickly. In addition, it is not easy to form a gas barrier coating uniformly.

The hydrogen generating material according to claim 1 of the present invention is composed of a multilayer film in which fine particles of aluminum or an aluminum alloy are laminated with a continuous porous film and a water-soluble, water-disintegrating, or water-peeling film. Further, it is packaged by a gas barrier water permeable membrane.

The hydrogen generating material according to claim 2 of the present application is characterized in that, in the hydrogen generating material of claim 1 , a moisture absorbing material or a water absorbing material is contained inside the gas barrier water permeable membrane .

The hydrogen generating material according to claim 3 of the present invention is the hydrogen generating material according to claim 1 or 2 , wherein the communicating porous membrane communicates the internal granular spaces with each other and the granular spaces are open on the surface. It is formed of a substrate material.

The hydrogen generation method according to claim 4 of the present application is characterized in that hydrogen is generated by bringing the hydrogen generation material according to any one of claims 1 to 3 into contact with water. is there.

  The present invention enables storage for a long period of time without impairing the quality of the aluminum fine particles as a hydrogen generation source, and controls the supply amount of water to the aluminum fine particles to stably supply the required amount of hydrogen. It becomes possible to do. By the technique of the present invention, hydrogen gas can be easily produced anytime and anywhere. Since the technology of the present invention does not conflict with the regulations of the high pressure method, it can meet the needs for supplying low pressure and a small amount of hydrogen gas. The technology of the present invention can provide a mobile hydrogen generator that is small, lightweight, and inexpensive, and enables early commercialization of mobile fuel cells. In addition, hydrogen gas can be supplied to a small hydrogen storage tank using a hydrogen storage alloy. As a result, portable fuel cells are put into practical use, and the performance of portable information communication devices such as mobile phones and digital cameras is further enhanced, contributing to the advancement of the information society.

  The hydrogen generating material according to a preferred embodiment of the present invention will be described in detail. The hydrogen generating material according to the first embodiment of the present invention is obtained by further packaging aluminum fine particles packaged with a water permeable membrane with a gas barrier plastic film. As the gas barrier plastic film, a known material having low oxygen permeability may be used. However, EVOH resin, PVDC resin, or a composite film in which a barrier material such as aluminum vapor deposition, silica vapor deposition, or aluminum foil is laminated with a heat sealable film. Is preferably used. By packaging with a gas barrier plastic film, the hydrogen generating material can be stored for a long time in the atmosphere.

  The hydrogen generating material according to the second embodiment of the present invention is a water permeable film in which a gas barrier film having water permeability is formed, and aluminum fine particles are packaged. As a gas barrier film, in addition to those having water permeability, those having any of water solubility, water disintegration, or water peelability may be used. As a material for forming a gas-barrier film having water permeability and the like, any known material suitable for the required storage period and hydrogen generation time may be used as long as the film can be formed on the water-permeable film. However, it is preferable to use an inorganic compound such as water-swelling synthetic mica or montmorillonite, an organic compound such as polyvinyl alcohol, ethylene vinyl alcohol, or saccharide, or a composite material of an inorganic compound and an organic compound. Packaging with the above-described water-permeable membrane with a gas barrier coating makes it possible to store the hydrogen-generating material in the atmosphere for a long period of time, and it is easy to use because it only needs to be put into water as it is in use. .

  The hydrogen generating material according to the third embodiment of the present invention is one in which a moisture absorbing material or a water absorbing material is contained inside and aluminum fine particles are packaged with a water permeable membrane. The hygroscopic or water-absorbing material is appropriately selected according to the hydrogen generation rate, but is a polysaccharide such as carboxymethylcellulose, sucrose or soluble starch, a water-absorbing polymer such as polyacrylate, sodium hydroxide or hydroxylated. It is preferable to use an inorganic hygroscopic material such as calcium. The method for containing the moisture-absorbing material or the water-absorbing material is not particularly limited as long as it does not impair the reaction of the aluminum fine particles, and is appropriately selected according to the required reaction start time and reaction rate. In addition to being contained inside the water permeable membrane, it may be contained on the water permeable membrane as a coating or particles, or may be mixed with aluminum fine particles.

  The hydrogen generating material according to the fourth embodiment of the present invention is a container in which aluminum fine particles are filled in a container formed of a continuous porous film. The material for forming the continuous porous membrane is not particularly limited as long as it contains a thermoplastic resin, and is a polyolefin resin such as polyethylene or polypropylene, nylon resin, polyester resin, ethylene vinyl alcohol copolymer or polylactic acid, It is preferable to use a biodegradable thermoplastic resin such as polybutylene succinate. In order to shorten the time required for water permeation, it is more preferable to use a highly hydrophilic resin such as ethylene vinyl alcohol as the material for forming the continuous porous membrane.

  Further, even when a poorly hydrophilic material such as polyethylene or polypropylene resin is used, the same effect as that of a highly hydrophilic resin can be obtained by subjecting a part or the whole of the material to a hydrophilic treatment. As a hydrophilic treatment method, a known method such as application of a hydrophilic substance such as polyethylene glycol or a surfactant or plasma treatment can be used. Furthermore, the time required for water permeation may be shortened by adding a substance that lowers the surface tension of water such as a hydrophilic solvent such as ethanol or a surfactant to the water to be contacted. The addition method is not particularly limited as long as hydrogen generation is not impaired. It may be mixed with water in advance, or may be added simultaneously with the hydrogen generating material, may be included in a dry state, or may be adhered.

  By including a thermoplastic resin as a material for forming the continuous porous membrane, it becomes easy to form the container into various desired shapes such as a bag shape, a tetrapack shape, a box shape, a cylindrical shape, and a capsule shape.

  In addition, it is preferable that the continuous porous membrane is excellent in air permeability. As a result, the generated hydrogen gas can be released out of the film with less resistance. Moreover, it is preferable that the communicating path of a communicating porous membrane is what connected granular space. Thereby, even after the gas barrier plastic film of the exterior is opened, the atmosphere does not immediately enter the inside, and it is possible to give a time delay until the water is added.

  It is preferable to seal the aluminum fine particles inserted or filled in the water-permeable membrane in an environment that does not come into contact with oxygen and water as much as possible, to which a gas barrier property is imparted. This makes it possible to produce a hydrogen generating material having an excellent hydrogen generating ability.

  As the hydrogen generating material of the present invention, active aluminum fine particles developed by the present inventor are preferably used, but aluminum or aluminum alloy fine particles other than the active aluminum fine particles may be used. Here, the active aluminum fine particle is a material developed by the present inventor, which is an aluminum fine particle in which aluminum hydride is accumulated, and has a remarkable hydrogen generation capability (for details, see For example, it is described in Patent Documents 3 and 4).

  A hydrogen production device for producing hydrogen using the hydrogen generating material of the present invention was prototyped. This hydrogen generator is made of stainless steel and has a palm size, and its internal volume is 200 ml to 300 ml. This hydrogen generator is provided with an insertion port for water and a hydrogen generating material pack, a discharge port for generated hydrogen gas, and a pressure safety valve. A hydrogen generating material pack (see FIG. 2) of active aluminum fine particles comprising an outer bag a and an inner bag b is prepared, about 100 ml of tap water is put into a hydrogen generator, and then the outer bag a is removed ( That is, the inner bag b) is put into the hydrogen generator from the insertion port. Then, the water that permeated the water permeable membrane contacted the active aluminum fine particles, and generation of hydrogen was confirmed after several minutes. Note that water may be supplied after the hydrogen generating material pack is put into the hydrogen generator.

  With reference to FIG. 1, Example 1-Example 12 performed in order to verify the effect of the hydrogen generating material of this invention are demonstrated. In FIG. 1, the configuration of the pack means a packaging form of aluminum fine particles, and the configuration of the packing means the amount of aluminum fine particles filled in the pack, the presence / absence of a moisture absorbent / water absorbent, and the like. In the evaluation column of FIG. 1, generation of hydrogen started within 30 minutes, the generation rate was stable, and over 1 liter / 1 g (aluminum fine particles (hereinafter also referred to as “Al”)) within 24 hours. ◯ means that hydrogen generation starts within 30 minutes, but the change in the generation rate is large and unstable, and 1 liter / 1 g (Al) or more within 24 hours. It means that there is a hydrogen generation amount, and the hydrogen generation amount is too much and the surplus is wasted. Δ indicates that it takes 30 minutes or more to start generation of hydrogen, and 1 liter / g within 24 hours It means that there is a hydrogen generation amount equal to or greater than (Al), and x means that the total hydrogen generation amount is less than 1 liter / 1 g (Al).

FIG. 3 is a schematic diagram showing a cross-sectional structure of the hydrogen generating material of Example 1. In Example 1, a continuous porous membrane having a granular space formed of ethylene vinyl alcohol copolymer resin (EVOH) having a porosity of 70% by volume is used as the water permeable membrane, and a 4 cm × 5 cm three-side sealed bag b (The air permeability of the water-permeable membrane (Gurley type) was 1.8 sec / 100 m lair). Also, as the gas barrier film, a composite biaxially stretched polypropylene film made of ethylene vinyl alcohol copolymer resin (ECO-BQ2 # 20, manufactured by Futamura Chemical Co., Ltd.) and an unstretched polypropylene film (FHK2 # 30, manufactured by Futamura Chemical Co., Ltd.) Using a composite film obtained by dry laminating, a three-side sealed bag a of 8 cm × 10 cm was prepared. And the pack was constituted as a double bag type in which the bag b was put in the bag a (the oxygen permeability of the pack constituent material was 4 cc / m ² · atm · day).
The porosity is based on the density ρ _r (g / cm ³ ) of the resin used for forming the continuous porous film and the density ρ _s (g / cm ³ ) of the continuous porous film.
Porosity (%) = {1- (ρ _s / ρ _r )} × 100
And calculate.

  The bag b was filled with 3 g of active aluminum fine particles in a glove box maintained at an oxygen concentration of 2% by volume or less by nitrogen gas purge, and the opening was heat sealed. Next, the bag b was put in the bag a, and the opening of the bag a was heat-sealed to prepare a hydrogen generating material which is active aluminum fine particles packaged with a water permeable membrane and a gas barrier membrane.

  This hydrogen generating material (pack) is tested as follows. After this hydrogen generating material (pack) was stored indoors in the atmosphere for 7 days, the bag a was opened and the bag b was taken out. After the bag b taken out is left in the room air for 1 hour, it is submerged in water (water temperature 20 ° C.) in a beaker filled with tap water, and inverted by a graduated cylinder filled with water. When hydrogen gas containing water vapor was collected (see FIG. 6), 1.2 liters / 3 g (Al) 1 hour after the bag b was put into water, 3.3 liters / 3 g (Al) after 24 hours. Of hydrogen gas could be obtained.

  Example 2 is the same as Example 1 except for the test method. That is, in Example 2, the hydrogen generating material (pack) was stored indoors in the atmosphere for 120 days, and then the bag a was opened and the bag b was taken out. After the bag b taken out is left in the room air for 1 hour, it is submerged in water (water temperature 20 ° C.) in a beaker filled with tap water, and inverted by a graduated cylinder filled with water. When hydrogen gas containing water vapor was collected, 1.1 liters / 3 g (Al) of hydrogen gas was obtained 1 hour after charging bag b into water, and 3.2 liters / 3 g (Al) of hydrogen gas was obtained 24 hours later. I was able to.

Example 3 is the same as Example 2 except that the bag a is formed of a low gas barrier material (the oxygen permeability of the outer bag is 2000 cc / m ² · atm · day). In Example 3, the hydrogen gas generation amount after 1 hour was 0.1 liter / 1 g (Al), and the hydrogen gas generation amount after 24 hours was 0.5 liter / 1 g (Al).

In Example 4, a continuous porous membrane having a granular space (air permeability: 1.2 seconds) formed of polybutylene succinate resin (PBS), which is a biodegradable resin having a porosity of 70% by volume, as a water permeable membrane. 2 cm × 8 cm three-side sealed bag b, filled with active aluminum fine particles (1 g) (water permeability of the water-permeable membrane (Gurley type) is 1.2 sec / 100 m lair). Moreover, the composite film similar to Example 1- Example 3 was used as a gas-barrier film | membrane, and it was set as the 3-way seal bag a of 8 cm x 10 cm. And the pack was constituted as a double bag type in which the bag b was put in the bag a (the oxygen permeability of the pack constituent material was 4 cc / m ² · atm · day).

  This hydrogen generating material (pack) was tested in the same manner as in Example 1. As a result, 0.2 l / 1 g (Al) was added 1 hour after bag b was put into water, and 1.1 l / 24 after 24 hours. 1 g (Al) of hydrogen gas could be obtained.

  FIG. 4 is a schematic diagram showing a film cross-sectional configuration of the hydrogen generating material of Example 5. In Example 5, water was sprayed on the inner surface of the bag b prepared in the same manner as in Example 4 except for the vicinity of the opening, and carboxymethylcellulose (CMC) powder (manufactured by Daicel Chemical Industries, Ltd.) as a water-absorbing material. , Daicel 1170) was deposited. And after making it fully dry, it carried out similarly to Example 4, the active aluminum microparticles | fine-particles (1g) were filled into the bag b, and the hydrogen generating material was created.

  When hydrogen gas was collected in the same manner as in Example 1 and Example 4, 1.0 liter / 1 g (Al) 1 hour after the bag b was put into water, 1.1 liter / 24 after 24 hours. 1 g (Al) of hydrogen gas could be obtained. FIG. 7 is a graph showing the generation state of hydrogen gas (including saturated water vapor) in Example 5.

  FIG. 5 is a schematic diagram showing a film cross-sectional configuration of the hydrogen generating material of Example 6. In Example 6, an aqueous dispersion of water-swellable synthetic mica was used as the gas barrier film-forming material instead of the above-described outer packaging gas barrier film. A three-sided seal bag prepared in the same manner as in Example 4 was dipped in an aqueous dispersion with its opening facing up, and then sufficiently dried to dry the gas-permeable coating of water-swelling synthetic mica on the outer surface of the water-permeable membrane. In the same manner as in Example 4 except that was formed, a three-side sealed bag was filled with active aluminum fine particles (1 g) to prepare a hydrogen generating material.

  When hydrogen gas was collected in the same manner as in Example 1 and Example 4, 0.1 liter / g (Al) was added 1 hour after the bag b was put into water, and 1.1 liter / liter after 24 hours. 1 g (Al) of hydrogen gas could be obtained.

  As a comparative example with respect to Examples 1 to 6 described above, a hydrogen generating material was obtained in the same manner as in Example 1 except that no gas barrier film-forming material such as gas barrier packaging by bag a or water-swellable synthetic mica was used. It was created. After this hydrogen generating material was stored indoors in the atmosphere for 7 days, the hydrogen generating material (bag) was put into water, but no hydrogen gas was generated.

In Example 8, a continuous porous membrane having a granular space made of polypropylene resin (PP) having a porosity of 60% by volume was used as the water permeable membrane, and 90% of the entire continuous porous membrane was hydrophilized. (After applying the surfactant, it was dried) to give a 2 cm × 8 cm three-side sealed bag b (the air permeability of the water-permeable membrane (Gurley type) was 1.9 sec / 100 m lair). A pack was constructed as a double bag type in which a bag b was placed in an 8 cm × 10 cm three-side sealed bag a formed of a gas barrier film (the oxygen permeability of the pack constituent material was 4 cc / m ^{2 for the} outer bag).・ Atm ・ day). The bag b was filled with activated aluminum fine particles (1 g) and calcium hydroxide / polyacrylate as a moisture absorbent / water absorbent.

  After this hydrogen generating material (pack) was stored indoors in the atmosphere for 7 days, the bag a was opened and the bag b was taken out. After the bag b taken out is left in the room air for 1 hour, it is submerged in water (water temperature 20 ° C.) in a beaker filled with tap water, and inverted by a graduated cylinder filled with water. When hydrogen gas containing water vapor is collected, 1.0 liter / 1 g (Al) hydrogen gas is obtained 1 hour after the bag b is put into water, and 1.1 liter / 1 g (Al) hydrogen gas is obtained 24 hours later. I was able to.

  Example 9 is the same as Example 8 except for the test method. That is, in Example 9, after the hydrogen generating material (pack) was stored indoors in the atmosphere for 7 days, the bag a was opened and the bag b was taken out. The taken bag b was left in the room air for 1 hour, then submerged in water (water temperature 20 ° C.) in a beaker containing tap water to which a surfactant was added, and the inside was inverted and filled with water. When hydrogen gas containing saturated water vapor generated was collected by the cylinder, 1.0 liter / 1 g (Al) was added 1 hour after the bag b was put into water, and 1.1 liter / 1 g (Al) after 24 hours. ) Hydrogen gas was obtained.

In Example 10, a non-woven fabric formed by combining cellulose fibers and polypropylene fibers was used as the water permeable membrane to form a three-side sealed bag b (water permeability of the water permeable membrane (Gurley type) was 0.1 sec / 100 m lair) . A pack was constructed as a double bag type in which a bag b was placed in a gas barrier film bag a (the oxygen permeability of the pack component was 4 cc / m ² · atm · day). The bag b was filled with activated aluminum fine particles (1 g) and calcium hydroxide / polyacrylate as a moisture absorbent / water absorbent.

  In Example 10, the hydrogen generating material (pack) was stored indoors in the atmosphere for 7 days, then the bag a was opened and the bag b was taken out. After the bag b taken out is left in the room air for 1 hour, it is submerged in water (water temperature 20 ° C.) in a beaker filled with tap water, and inverted by a graduated cylinder filled with water. When hydrogen gas containing water vapor was collected, only 0.3 liter / 1 g (Al) of hydrogen gas was obtained 1 hour after charging bag b into water, and 0.6 liter / 1 g (Al) of hydrogen gas was obtained 24 hours later. I couldn't.

In Example 11, a continuous porous membrane having a granular space made of polypropylene resin (PP) having a porosity of 60% by volume was used as the water permeable membrane to obtain a three-side sealed bag b (the air permeability of the water permeable membrane ( Gurley type) is 1.9sec / 100m lair). Then, the molten sucrose was poured and filled into the granular space to form a pack (the oxygen permeability of the pack component was 264 cc / m ² · atm · day). The bag b was filled with activated aluminum fine particles (1 g) and calcium hydroxide / polyacrylate as a moisture absorbent / water absorbent.

  In Example 11, after the hydrogen generating material (pack) was stored indoors in the atmosphere for 7 days and then submerged in tap water (water temperature 20 ° C.) as it was, 1 hour after the bag b was put into water. The amount of hydrogen gas generated was 0/1 g (Al), and the amount generated after 24 hours was 1.0 liter / 1 g (Al).

In Example 12, a non-permeable membrane formed of ethylene vinyl alcohol copolymer resin (EVOH) was used as the water permeable membrane, and a 4 cm × 5 cm three-sided seal bag b was formed (air permeability of water permeable membrane (Gurley type)). Is over 10000sec / 100mlair). In addition, as a double bag type in which a bag b is put in a three-side sealed bag a (8 cm × 10 cm) formed of a gas barrier film, a pack is configured (the oxygen permeability of the pack constituent material is the inner bag / outer bag, 4cc / m ² · atm · day). The bag b was filled with activated aluminum fine particles (1 g) and calcium hydroxide / polyacrylate as a moisture absorbent / water absorbent.

  In Example 12, the hydrogen generating material (pack) was stored indoors in the atmosphere for 7 days, and then the bag a was opened and the bag b was taken out. The bag b taken out was left in the atmosphere for 1 hour and then submerged in water (water temperature 20 ° C.) in a beaker containing tap water. After 24 hours, the bag b expanded, but hydrogen gas was generated. I did not.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the invention described in the claims, and these are also included in the scope of the present invention. Needless to say, it is something.

The present invention can be used for various applications as described below, and is considered to be widely used as a hydrogen supply apparatus that is safe at a constant pressure in the future.
(1) Hydrogen fuel source for mobile fuel cells (2) Hydrogen source for small hydrogen engines (3) Simple, low-pressure hydrogen supply device for laboratories (4) Oxygen-free water, hydrogen water, and industrial wash water (5) Hydrogen source for portable fuel cells for emergencies and disasters

It is the table | surface which showed each main point in Example 1- Example 12. It is the figure which showed the state at the time of storage of the hydrogen generating material demonstrated in Example 1. FIG. FIG. 3 is a schematic diagram showing a cross-sectional structure of a hydrogen generating material of Example 1. 6 is a schematic diagram showing a cross-sectional structure of a hydrogen generating material of Example 5. FIG. 6 is a schematic diagram showing a cross-sectional structure of a hydrogen generating material of Example 6. FIG. It is the figure which showed roughly the method of collecting hydrogen gas demonstrated in Example 1. FIG. 6 is a graph showing a generation state of hydrogen gas (including saturated water vapor) in Example 5.

Claims (4)

Aluminum or aluminum alloy fine particles are packaged by a gas barrier water permeable membrane composed of a multi-layer membrane in which a continuous porous membrane and a water-soluble, water-disintegrating, or water-peeling membrane are laminated. A hydrogen generating material characterized by that. The hydrogen generating material according to claim 1, wherein the gas barrier water permeable membrane contains a moisture absorbing material or a water absorbing material. 3. The hydrogen according to claim 1, wherein the communicating porous membrane is formed of a resin substrate material that allows internal granular spaces to communicate with each other and has a granular space open on a surface thereof. Generating material . A hydrogen generating method for generating hydrogen by bringing the hydrogen generating material according to any one of claims 1 to 3 into contact with water .

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