JP2009249235A - Sheet type hydrogen generating agent, pleated type hydrogen generating agent, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet type hydrogen generating agent and a pleated type hydrogen generating agent having good handling property, capable of gradually effecting a reaction with a reaction liquid to obtain a more stable hydrogen generation rate, and having a sufficiently high reactivity, and to provide a method for manufacturing these generating agents. <P>SOLUTION: The sheet type hydrogen generating agent has a hydrogen generating layer 2 containing a hydrogen generating agent and a resin, formed on a water absorption sheet 1, wherein, preferably, a hydrophobic porous film 3 is provided on the surface of the hydrogen generating layer 2. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a sheet-like hydrogen generating agent containing a hydrogen generating agent that reacts with a reaction liquid such as moisture to generate hydrogen gas, a pleated hydrogen generating agent, and a manufacturing method thereof, and particularly supplies hydrogen to a fuel cell. It is useful as a technique for

  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). In particular, when using a highly reactive hydrogen generator such as calcium hydride, the reaction rate with water is steep, so if water is supplied as liquid (water), hydrogen gas will explode in the initial stage. There was a problem that it occurred.

  Therefore, in Patent Document 2, for the purpose of appropriately controlling the reaction rate between the metal hydride compound and moisture, a water-repellent porous body is interposed between the metal hydride compound and water, through which water vapor is generated. A method for generating hydrogen to be supplied to a metal hydride compound is disclosed. However, this method has a problem that the handling of the hydrogen generating agent becomes complicated and the structure of the hydrogen generating apparatus becomes complicated.

  On the other hand, Patent Document 3 discloses a compression molded body for hydrogen generation obtained by compression molding after mixing a metal hydride complex compound powder that reacts with an acid aqueous solution to generate hydrogen gas and a thermoplastic resin powder. Has been. In this compression molding for hydrogen generation, hydrogen gas is generated using a device that supplies and reacts with an aqueous acid solution while scraping the surface with a rotating plate.

  However, the above-mentioned compression molded body for hydrogen generation is compression-molded at a high density so as not to permeate the aqueous acid solution for the purpose of shortening the time until the hydrogen generation is stopped, so that the reaction does not proceed to the inside. It is. For this reason, there is a problem that the reaction does not proceed only in the vicinity of the surface only by contacting with the acid aqueous solution, and the reaction rate is remarkably lowered when the above apparatus is not used.

  Patent Document 4 discloses a hydrogen generator in which calcium hydride or the like is embedded in a water-soluble polymer. According to this hydrogen generating agent, it is possible to suppress a rapid reaction between calcium hydride or the like and water by embedding in a water-soluble polymer.

Japanese Patent Laid-Open No. 2003-314792 JP 2003-313001 A JP 2003-146604 A International Publication WO2007 / 055146

  However, the hydrogen generating agent described in Patent Document 4 has a granular or tablet shape, and generates hydrogen gas by a method of directly supplying water or the like, so that it is difficult to proceed gradually while controlling the reaction. Met. That is, in the case of a tablet-like hydrogen generator, water penetrates from the surface to the inside, but the distance when penetrating to the center is long, and the cross-sectional area at the penetration tip position becomes small with the penetration, so that process Therefore, it was difficult to control the water penetration rate and reaction amount. In addition, in the case of a granular hydrogen generator, since the distance when penetrating to the center is short, the permeation rate of water is almost the same for each particle. It was difficult to proceed and the reaction was difficult to proceed gradually.

  Accordingly, an object of the present invention is a sheet-like hydrogen generator, a pleated hydrogen generator, which has good handleability, gradually proceeds with the reaction with the reaction solution to make the hydrogen generation rate more constant, and has a sufficiently high reaction rate. And a method of manufacturing the same.

The above object can be achieved by the present invention as follows.
That is, the sheet-like hydrogen generator of the present invention is characterized in that a hydrogen generation layer containing a hydrogen generator and a resin is formed on the water-absorbent sheet. According to the sheet-like hydrogen generating agent of the present invention, since the hydrogen generating layer is formed on the water absorbent sheet, by gradually infiltrating the reaction liquid along the surface of the water absorbent sheet, the surface of the hydrogen generating layer is formed. The reaction liquid sequentially permeates along, and the reaction between the reaction liquid and the hydrogen generating agent can be gradually advanced. In addition, since the hydrogen generation layer contains a resin, rapid reaction with the reaction solution can be suppressed, the handleability is improved, and the thickness of the hydrogen generation layer is sufficiently small relative to the area, so that the entire thickness The reaction is likely to occur at the same time, and the reaction in each area is uniform as compared with the bulk type. As a result, it is possible to provide a sheet-like hydrogen generating agent that is easy to handle, gradually proceeds with the reaction with the reaction liquid, has a more constant hydrogen generation rate, and has a sufficiently high reaction rate.

  In the above, it is preferable that the hydrogen generation layer is formed in a plurality of sections on one water absorbent sheet. Thus, when the hydrogen generation layer is divided into a plurality of sections, hydrogen can be generated and stopped for each section. For example, when hydrogen gas is supplied to the fuel cell, the battery is easily turned on and off. .

  Moreover, it is preferable that the said hydrogen generating layer is a porous layer containing a granular hydrogen generating agent and resin, and it is what was laminated | stacked and integrated with the water absorbing sheet | seat by coating. Since the hydrogen generation layer has a porous structure, the permeability of the reaction solution is good, and the use of a resin causes the porous structure to collapse appropriately and the reaction proceeds easily throughout the reaction. The rate is easily obtained. Furthermore, since it is laminated and integrated with the water-absorbent sheet by coating, the permeation at the interface becomes more uniform and a more uniform reaction can be performed. Furthermore, what was laminated and integrated with the water-absorbent sheet by coating can be manufactured by a continuous process, and thus has excellent mass productivity.

  Moreover, it is preferable that a hydrophobic porous membrane is provided on the surface of the hydrogen generation layer. By providing the hydrophobic porous membrane, it is possible to prevent water from scattering while allowing hydrogen gas to permeate, and to effectively use water.

  The resin is preferably a thermosetting resin. By using a thermosetting resin, even if reaction heat is generated, the porous structure is less likely to be clogged, and the reaction is more likely to proceed as a whole, so that a sufficient reaction rate is easily obtained.

  It is preferably made porous by bubbles. In the porous structure generated by the bubbles, the boundary wall between the bubble cells tends to be thin, and the reaction easily proceeds to the whole while it is appropriately collapsed.

Moreover, it is preferable that the density of the said hydrogen generation layer is 0.1-1.2 g / cm < ³ >. By having a density in this range, the permeability of the reaction solution becomes appropriate, and the handleability becomes better.

  On the other hand, the pleated hydrogen generator of the present invention is obtained by alternately bending the sheet-like hydrogen generator described above. According to the pleated hydrogen generator of the present invention, due to the operational effects of the sheet-like hydrogen generator of the present invention as described above, the handleability is good, and the reaction with the reaction solution is gradually advanced to further increase the hydrogen generation rate. It becomes constant and the reaction rate is sufficiently high. In addition to this, in particular, with the inner surface as the water absorbent sheet, gradually infiltrate the reaction solution along the surface of the water absorbent sheet from the valley side (inner side) to the mountain side (outer side) of the alternately folded pleats. Thus, the reaction solution sequentially permeates along the surface of the hydrogen generation layer, and the reaction between the reaction solution and the hydrogen generating agent can be gradually advanced. At that time, the generated hydrogen gas passes between the hydrogen generation layers and can be released without resistance from the valley side to the mountain side. For this reason, a pleated type hydrogen generating agent can be arrange | positioned in a container with sufficient thickness with respect to an area, and hydrogen gas can be efficiently supplied to the outer side at a substantially constant speed.

  In the above, it is preferable that the sheet-like hydrogen generating agent bent alternately is retained in a cylindrical shape. By holding the pleated hydrogen generating agent in a cylindrical shape, the hydrogen gas can be supplied over the entire circumference by supplying the reaction liquid from the hollow portion.

  On the other hand, the method for producing a sheet-like hydrogen generator of the present invention includes a step of forming a hydrogen generation layer by applying a mixture of a hydrogen generator and a resin onto a water absorbent sheet and then solidifying the resin. It is characterized by that. According to the production method of the present invention, by a simple method, a sheet-like hydrogen generator having good handleability, gradually progressing the reaction with the reaction solution to make the hydrogen generation rate more constant, and having a sufficiently high reaction rate. Can be manufactured.

  Moreover, the preferable manufacturing method of the sheet-like hydrogen generator of the present invention is a method in which a mixture of a granular hydrogen generator and an uncured thermosetting resin is applied onto a water-absorbent sheet, and then the hydrogen generator is used. It includes a step of forming a porous layer by curing a thermosetting resin while generating hydrogen gas. According to this production method, a simple method of mixing and foaming and curing a hydrogen generating agent and a thermosetting resin forms a porous layer capable of generating appropriate hydrogen just by contacting with the reaction solution. It is possible to produce a sheet-like hydrogen generator that has good handleability, can generate hydrogen appropriately by contacting with the reaction solution, and has a sufficiently high reaction rate.

  In the above, it is preferable that after coating on the water-absorbent sheet, a hydrophobic porous film is laminated and cured to be integrated with the porous layer. Thereby, a porous layer and a hydrophobic porous membrane can be integrated by a simple method.

  As shown in FIG. 1, the sheet-like hydrogen generator of the present invention is such that a hydrogen generation layer 2 containing a hydrogen generator and a resin is formed on a water absorbent sheet 1. The hydrogen generation layer 2 and the water absorbent sheet 1 may be adhered on the entire surface or may be partially adhered. The hydrogen generation layer 2 may be formed in a plurality of sections on the single water absorbent sheet 1. Examples of the shape of each segment include a dot shape, a shape segmented by slits, and other pattern shapes. In addition, as shown in FIG. 2, the surface of the hydrogen generation layer 2 may be provided with a hydrophobic porous membrane 3, or the surface of the hydrogen generation layer 2 may be provided with a water absorbent sheet 1.

  Examples of the method of adhesion between the hydrogen generation layer 2 and the water absorbent sheet 1 include adhesion using an adhesive, a pressure-sensitive adhesive, etc., thermocompression bonding, thermal fusion, and lamination integration by coating. From the viewpoint of water permeability, a laminate integrated by coating is preferable. Similarly, the hydrogen generation layer 2 and the hydrophobic porous membrane 3 can be attached.

  The water-absorbent sheet is a sheet-like material having water absorption, and examples thereof include a sheet formed into a porous shape using a hydrophilic material. Specifically, for example, water-absorbing nonwoven fabric, water-absorbing woven fabric, water-absorbing paper, filter paper and the like are preferable. Furthermore, these can be used in combination or in combination with a water absorbent resin. In addition, the water absorbing sheet may be a roll of a long object.

The thickness of the water-absorbent sheet is preferably from 0.15 to 0.7 mm, more preferably from 0.2 to 0.4 mm, from the viewpoint of maintaining strength and moderate in-plane permeability. The density of the water absorbent sheet is preferably 0.2 to 0.7 g / cm ^{3 and} more preferably 0.4 to 0.6 g / cm ³ from the viewpoint of making the in-plane permeability moderate.

  The water-absorbing sheet may be provided only on one side of the hydrogen generation layer, but can also be provided on both sides. In the case where the water absorbent sheet is provided on both sides, it can be produced by coating the raw material of the hydrogen generation layer on any of the water absorbent sheets and then further laminating the water absorbent sheet on the upper surface thereof. It is also possible to laminate a hydrophobic porous film on the upper surface after applying the raw material for the hydrogen generation layer.

  The hydrogen generation layer contains a hydrogen generator and a resin, and is provided as a porous layer or a non-porous layer. In the case of a non-porous layer or a porous layer having a low porosity, it is preferable to mainly use a water-soluble resin.

  The hydrogen generation layer is preferably a porous layer from the viewpoint of reliably infiltrating water. In particular, the hydrogen generation layer is a porous layer containing a granular hydrogen generator and a resin and absorbs water by coating. It is preferable that it is laminated and integrated with the conductive sheet.

  A hydrogen generator reacts with a reaction liquid such as water to generate hydrogen gas, and the present invention is particularly suitable for a highly reactive hydrogen generator from the viewpoint of improving the handleability of the hydrogen generator. It is valid. However, it is also possible to use a less reactive hydrogen generator.

  Examples of the highly reactive hydrogen generator include calcium hydride, lithium hydride, potassium hydride, sodium borohydride, potassium borohydride, lithium aluminum hydride, sodium aluminum hydride, or magnesium hydride. And those containing a metal hydride compound such as All of these compounds are known to react rapidly or explosively with water to generate hydrogen gas, and all show reactivity with water higher than magnesium hydride.

  Moreover, you may contain metals, such as aluminum, iron, magnesium, and calcium, metal hydrogen complex compounds other than the above, as hydrogen generating agents other than the said compound. A plurality of metal hydride compounds, metals, and metal hydride complex compounds can be used in combination, or they can be used in combination. When a compound is used in combination, it is preferable to include a compound that facilitates the formation of pores by bubbles. As such a compound, calcium hydride is particularly preferable.

  The average particle size of the granular hydrogen generator is preferably 1 to 100 μm, more preferably 6 to 30 μm, and still more preferably 8 to 10 μm from the viewpoint of controlling dispersibility and reactivity in the porous body.

  The content of the hydrogen generating agent is preferably 10 to 60% by weight, and preferably 30 to 50% by weight in the porous body from the viewpoint of ensuring appropriate reactivity and a certain amount of hydrogen generation.

  Examples of the resin used for the porous layer include a thermosetting resin, a thermoplastic resin, and a heat resistant resin, and a thermosetting resin is preferable. 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 which can maintain a porous structure moderately during hydrogen generating reaction.

  Moreover, water-soluble resin and water-absorbing resin are mentioned as resin used for a non-porous layer. Examples of the water-soluble resin include methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, and polyethylene oxide. Examples of water-absorbing resins include cross-linked acrylate polymers, cross-linked vinyl alcohol-acrylate copolymers, cross-linked maleic anhydride grafted polyvinyl alcohol, and acrylate-methacrylate copolymers. Cross-linked product, cross-linked product of saponified product of methyl acrylate-vinyl acetate polymer, cross-linked product of starch-acrylate graft copolymer, cross-linked product of hydrolyzate of starch-acrylonitrile copolymer, starch-ethyl acrylate Examples include a cross-linked product of a saponified graft copolymer, a cross-linked product of carboxymethyl cellulose, and the like.

  The content of the resin is preferably 30 to 90% by weight, and preferably 50 to 70% by weight in the hydrogen generation layer, from the viewpoint of securing an appropriate shape retention and a certain amount of hydrogen generation.

  The sheet-like hydrogen generator of the present invention may contain other components such as a catalyst, a filler, and a foaming agent 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. Further, it may contain a low molecular solid acid such as fumaric acid, a polymer solid acid such as polyacrylic acid, an inorganic acid such as boric acid, and the like.

  Examples of the foaming agent include a liquid that is phase-separated and dispersed in an uncured thermosetting resin and vaporizes at the reaction temperature of the thermosetting resin. It is also possible to add a small amount of a reaction solution that reacts with the hydrogen generator to generate hydrogen gas to the uncured thermosetting resin. Examples of such a reaction solution include water, an aqueous acid solution, and an alkaline aqueous solution.

  The sheet-like hydrogen generator of the present invention preferably has a porous structure by bubbles (foaming), sintering, or phase separation, but more preferably has a porous structure by bubbles. Is. The bubbles for making the pores may be generated by a foaming agent, but are preferably hydrogen gas generated from a hydrogen generating agent.

  That is, when the sheet-like hydrogen generator of the present invention has a porous layer, after mixing a granular hydrogen generator and an uncured thermosetting resin, thermosetting while generating hydrogen gas from the hydrogen generator. It is preferable to manufacture by the manufacturing method including the process of hardening an electroconductive resin. Further, after applying a mixture of a granular hydrogen generator and an uncured thermosetting resin on the water absorbent sheet, the thermosetting resin is cured while generating hydrogen gas from the hydrogen generator. More preferably, the method includes a step of forming a porous layer.

If the sheet-like hydrogen generator of the present invention has a porous layer, it is preferable that a density of 0.1~1.2g / cm ^3, more preferably from 0.2 to 0.9 g / cm ³ 0.3 to 0.5 g / cm ³ is more preferable. By having a density in this range, the permeability of the reaction solution becomes appropriate, and the handleability becomes better. Such a density can be controlled by, for example, the amount of hydrogen gas generated.

  Further, the bubble diameter of the porous layer is preferably from 0.1 to 2 mm, more preferably from 0.5 to 1 mm, from the viewpoint of appropriately controlling the permeability of the reaction solution. Such a bubble diameter can be controlled by, for example, the amount of hydrogen gas generated. In order to control the bubble diameter and density, the thermosetting resin may be cured under pressure.

  In the production method of the present invention, in order to generate hydrogen gas from the hydrogen generator, a method of adding a small amount of a reaction solution to an uncured thermosetting resin in advance, or a reaction contained in an uncured thermosetting resin Although a method using a liquid is also possible, a method in which hydrogen gas is desorbed from a hydrogen generating agent (in the case of a metal hydride compound) by heating for a curing reaction is preferable.

  The temperature at which hydrogen gas is desorbed from the hydrogen generator varies depending on the type of metal hydride compound, but is preferably 50 to 250 ° C, more preferably 80 to 200 ° C. That is, it is preferable to select a temperature within this range as the curing temperature of the uncured thermosetting resin. It is also possible to change the generation temperature of hydrogen gas and the curing temperature.

  The thickness of the porous layer obtained as described above is preferably 0.3 to 3 mm, and more preferably 0.5 to 2 mm, from the viewpoint of allowing water and the like to permeate sufficiently and uniformly to perform a uniform reaction.

  Next, a manufacturing method when the hydrogen generation layer is a non-porous layer will be described. In that case, after mixing and heating the granular hydrogen generator and water-soluble resin, a method of extruding it into a sheet or applying it to a substrate and cooling it, or a method of cooling the granular hydrogen generator, water-soluble resin and resin A non-porous layer can be formed by a manufacturing method in which a water solvent is mixed to obtain a dispersion, which is then extruded into a sheet or coated onto a substrate and dried. At that time, it is more preferable that the melt is directly laminated on the water-absorbent sheet and cooled, or the dispersion is coated on the water-absorbent sheet and then dried.

  Examples of the non-aqueous solvent include aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide.

  The thickness of the non-porous layer obtained as described above is preferably 0.5 to 2 mm, more preferably 1.0 to 1.5 mm, from the viewpoint of sufficiently and uniformly infiltrating water and the like to perform a uniform reaction. preferable.

  In the sheet-like hydrogen generator of the present invention, it may be preferable to provide a hydrophobic porous film on the other surface of the water-absorbent sheet, regardless of whether the hydrogen generation layer is a porous layer or a non-porous layer. . In that case, it is preferable that after coating on the water-absorbent sheet, a hydrophobic porous film is laminated and cured, and integrated with the porous layer.

  The hydrophobic porous membrane can be used for the purpose of permeating hydrogen gas without releasing moisture such as mist. Therefore, the pore diameter of the hydrophobic porous membrane is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

  Examples of the material for the hydrophobic porous membrane include fluorine-based resin, polyolefin-based resin, polyethersulfone, and polysulfone. Of these, fluorine resins such as polytetrafluoroethylene and polyolefin resins such as polypropylene are preferable.

  Further, the sheet-like hydrogen generator of the present invention may be packaged by enclosing it in a water-absorbent sheet or a hydrophobic porous membrane. For example, when packaging using a hydrophobic porous membrane, the sheet-like hydrogen generator is placed in an envelope-like hydrophobic porous membrane and sealed with a water supply pipe communicating with the inside. It is preferable to package.

  As shown in FIG. 3, the pleated hydrogen generator of the present invention includes a sheet-like hydrogen generator of the present invention as described above, that is, a hydrogen generating layer 2 containing a hydrogen generator and a resin. The sheet-like hydrogen generator formed on the top is alternately bent. The sheet-like hydrogen generating agent may be one in which a hydrophobic porous membrane 3 is provided on the surface of the hydrogen generating layer 2.

  The pleated hydrogen generator of the present invention can be held in a box shape such as a cube or a rectangular parallelepiped. However, as shown in FIG. 4, the sheet-like hydrogen generator bent alternately is held in a cylindrical shape. It is also possible. When the shape is retained in a cylindrical shape, the ends in the circumferential direction of the pleats may be bonded or not. The shape of the outer periphery in the case of retaining the shape of a cylinder is not limited to a circle as shown in FIG.

  In the case of pleat folding the sheet-like hydrogen generator, it is preferable that the raw material for the hydrogen generation layer is applied to a planar water-absorbing sheet and then pleated before curing to maintain the pleated shape. In that case, it is preferable to laminate a water-absorbent sheet or a hydrophobic porous film on the upper surface of the hydrogen generation layer so that the pleat ridges do not adhere to each other.

  The method for using the sheet-like hydrogen generator of the present invention is to generate hydrogen by bringing the sheet-like hydrogen generator and the reaction solution into contact with each other as described above. 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 addition, the supply of the reaction liquid is performed from the water absorbent sheet side, and further penetrates into the hydrogen generation layer. The reaction liquid is preferably supplied from the end side of the water-absorbent sheet, but can be supplied so as to spread from the center to the outside.

  Further, in the case of the pleated hydrogen generating agent, it can be supplied from the end face in the axial direction, but can also be supplied so as to gradually absorb water from the water-absorbent sheet in the valley to the peak. Thus, it becomes possible to adjust the speed | velocity | rate of the hydrogen gas to generate | occur | produce by absorbing water gradually in a water absorbing sheet.

  Since the sheet-like hydrogen generating agent of the present invention can simplify the device structure of the hydrogen generating device, it is particularly effective when used in a hydrogen supply device of a fuel cell for a form device.

  Examples and the like specifically showing the configuration and effects of the present invention will be described below. In addition, the evaluation item in an Example etc. measured as follows.

(1) Average particle diameter From the photograph image | photographed using the scanning electron microscope (SEM), what has average particle diameter was selected, and the long diameter and the short diameter were averaged and calculated | required.

(2) Density The mass of the sample was measured, and the density was determined by dividing the mass by the volume measured from the dimensions of each side.

Example 1
Epoxy resin (manufactured by ThreeBond Co., 2225G) and a hydrogen generator (CaH ₂ , manufactured by Kemetal Co., average particle size 10 μm) are mixed in a weight ratio of epoxy resin: CaH ₂ = 1: 1 with a stirrer (2000 rpm × 1 Min + 2200 rpm × 1 min). Contains a hydrogen generator obtained by placing a filter paper (5C type, manufactured by Toyo Roshi Kaisha, Ltd.) with a thickness of 0.2 mm and a density of 0.61 g / cm ^{3 on} the bottom of a 30 × 50 × 0.5 mm sample mold and using a spatula Resin was applied. Further, the same filter paper was placed on top of the hydrogen generator-containing resin to form a sandwich type. Thereafter, drying was performed at 120 ° C. for 20 minutes to cure the resin. As a finish, extra filter paper (part of the filter paper not in contact with the hydrogen generator-containing resin) was cut out to produce a sheet-like hydrogen generator (finished size: 30 × 50 × about 1 mm).

The obtained hydrogen generating layer of the sheet-like hydrogen generating agent was a porous layer having a structure made porous by bubbles, and the thickness of the portion was 1.0 mm and the density was 0.4 g / cm ³ . .

  Using this sheet-like hydrogen generator, the edge (30 mm side) is immersed in water in a beaker having a bottom surface diameter of 32 mm so that the angle with respect to the water surface is 90 °, and water is gradually absorbed into the filter paper. Then, hydrogen was generated. The change over time in the amount of hydrogen generated at that time was measured with a mass flow meter. As a result, there was no rapid hydrogen generation in the initial stage, and the hydrogen generation rate was almost constant from 5 minutes to 30 minutes after the start of the reaction (reaction rate was about 100%).

Example 2
In Example 1, except that the weight ratio is changed to epoxy resin: CaH ₂ = 1: 0.54, the density is 0.2 g / cm ³ and the structure has a porous structure with bubbles. A sheet-like hydrogen generator having a layer was obtained. When the obtained sheet-like hydrogen generator was evaluated in the same manner as in Example 1, as in Example 1, there was no sudden hydrogen generation at the initial stage, and it was almost constant from 5 minutes to 30 minutes after the start of the reaction. The hydrogen generation rate.

Example 3
Uniform mixing of polyethylene glycol (molecular weight 20,000), which is a water-soluble polymer, and 0.8 g of sodium borohydride (added with 4% by weight of nickel chloride as a catalyst) while heating to 60 ° C and melting. Then, it was placed in a mold and cooled to obtain a sheet having a thickness of 1 mm. This sheet is laminated with a filter paper having a thickness of 0.2 mm and a density of 0.61 g / cm ³ (5C type, manufactured by Toyo Roshi Kaisha, Ltd.), and is pressure-bonded while being heated to 80 ° C. to form a sheet-like hydrogen generator having a thickness of 1.5 mm. Got. Using the obtained sheet-like hydrogen generator, 2 mL of water was absorbed at once to generate hydrogen. FIG. 5 shows the results of measuring the change over time in the amount of hydrogen generated at that time. As a result, as in Example 1, there was no rapid hydrogen generation in the initial stage, and the hydrogen generation rate was almost constant from 140 minutes after the start of the reaction.

Example 4
Using the two sheet-like hydrogen generators prepared in Example 1, this molded product was put into a bag of a vapor permeable membrane (Mitsubishi Resin Co., Ltd. Excepol), and 1.2 cc of water was directly added. Watered and sealed. FIG. 6 shows the results of measuring the change over time in the hydrogen generation amount at that time. As a result, there was no rapid hydrogen generation in the initial stage, and the hydrogen generation rate was almost constant from immediately after the start of the reaction to 60 minutes later.

Comparative Example 1
Epoxy resin (manufactured by ThreeBond Co., 2225G) and a hydrogen generator (CaH ₂ , manufactured by Kemetal Co., average particle size 10 μm) are mixed in a weight ratio of epoxy resin: CaH ₂ = 1: 1 with a stirrer (2000 rpm × 1 Min + 2200 rpm × 1 min). Using this, two compacts having a size of 50 mm × 35 mm × 0.5 mm (thickness) were produced in the mold. This molded body was put into a bag of a vapor permeable membrane (manufactured by Mitsubishi Plastics Co., Ltd., Expaul), and directly sealed with 1.2 cc of water. FIG. 6 shows the results of measuring the change over time in the hydrogen generation amount at that time. As a result, rapid hydrogen generation occurred in the initial stage, and hydrogen generation almost stopped 30 minutes after the start of the reaction.

Sectional drawing which shows an example of the sheet-like hydrogen generating agent of this invention Sectional drawing which shows the other example of the sheet-like hydrogen generator of this invention Sectional drawing which shows an example of the pleated type hydrogen generating agent of this invention Sectional drawing which shows the other example of the pleated type hydrogen generating agent of this invention The graph which shows the time-dependent change of the generation flow rate of hydrogen gas and the total hydrogen generation amount in Example 3 The graph which shows the time-dependent change of the generation | occurrence | production flow rate of the hydrogen gas in Example 4 and Comparative Example 1.

Explanation of symbols

1 Water-absorbing sheet 2 Hydrogen generation layer (porous layer)
3 Hydrophobic porous membrane

Claims (12)

  A sheet-like hydrogen generator in which a hydrogen generation layer containing a hydrogen generator and a resin is formed on a water absorbent sheet.   The sheet-like hydrogen generating agent according to claim 1, wherein the hydrogen generating layer is formed by being divided into a plurality of sections on one water absorbent sheet.   The sheet-like hydrogen generating agent according to claim 1 or 2, wherein the hydrogen generating layer is a porous layer containing a granular hydrogen generating agent and a resin, and is laminated and integrated with a water absorbent sheet by coating.   The sheet-like hydrogen generator according to any one of claims 1 to 3, wherein a hydrophobic porous film is provided on the surface of the hydrogen generation layer.   The sheet-like hydrogen generator according to any one of claims 1 to 4, wherein the resin is a thermosetting resin.   The sheet-like hydrogen generator according to any one of claims 3 to 5, which has been made porous by bubbles. The density of the said hydrogen generation layer is 0.1-1.2 g / cm < ³ >, The sheet-like hydrogen generator in any one of Claims 3-6.   A pleated hydrogen generator obtained by alternately bending the sheet-like hydrogen generator according to claim 1.   The pleated hydrogen generator according to claim 8, wherein the sheet-like hydrogen generator bent alternately is retained in a cylindrical shape.   A method for producing a sheet-like hydrogen generator comprising a step of coating a mixture of a hydrogen generator and a resin on a water-absorbent sheet and then solidifying the resin to form a hydrogen generation layer.   A mixture of a granular hydrogen generator and an uncured thermosetting resin is coated on a water-absorbent sheet, and then the thermosetting resin is cured while generating hydrogen gas from the hydrogen generator to make the porous material porous. The manufacturing method of the sheet-like hydrogen generating agent including the process of forming a layer.   The method for producing a sheet-like hydrogen generator according to claim 10 or 11, wherein after coating on a water-absorbent sheet, a hydrophobic porous membrane is laminated and cured, and integrated with the porous layer.

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