WO2010123020A1 - 水素発生剤パッケージ、その製造方法及び水素発生方法 - Google Patents
水素発生剤パッケージ、その製造方法及び水素発生方法 Download PDFInfo
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- WO2010123020A1 WO2010123020A1 PCT/JP2010/057040 JP2010057040W WO2010123020A1 WO 2010123020 A1 WO2010123020 A1 WO 2010123020A1 JP 2010057040 W JP2010057040 W JP 2010057040W WO 2010123020 A1 WO2010123020 A1 WO 2010123020A1
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- hydrogen
- generating agent
- hydrogen generating
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D71/00—Bundles of articles held together by packaging elements for convenience of storage or transport, e.g. portable segregating carrier for plural receptacles such as beer cans or pop bottles; Bales of material
- B65D71/06—Packaging elements holding or encircling completely or almost completely the bundle of articles, e.g. wrappers
- B65D71/08—Wrappers shrunk by heat or under tension, e.g. stretch films or films tensioned by compressed articles
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
- H01M8/04208—Cartridges, cryogenic media or cryogenic reservoirs
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
- H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a hydrogen generating package in which a hydrogen generating agent that reacts with a reaction liquid such as moisture to generate hydrogen gas is coated with a coating material, a manufacturing method thereof, and a hydrogen generating method, and particularly supplies hydrogen to a fuel cell. It is useful as a technique for
- 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.
- Patent Document 3 discloses a hydrogen generation apparatus in which a hydrogen generating agent is accommodated in each of the accommodating spaces at a filling rate that makes it difficult for the reaction liquid to enter due to expansion of the hydrogen generating agent when the reaction is almost completed. It is disclosed. 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.
- Patent Document 3 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.
- an object of the present invention is to provide a hydrogen generator package, a method for producing the same, and a method for generating hydrogen, which have high stability and reproducibility of the hydrogen generation reaction, and are preferably less susceptible to changes in environmental temperature.
- the inventors of the present invention have intensively studied to achieve the above object, and it is possible to increase the stability and reproducibility of the hydrogen generation reaction by providing a coating material that restrains the periphery of the hydrogen generating agent and allows deformation. As a result, the present invention has been completed.
- the hydrogen generating agent package of the present invention is characterized by comprising a hydrogen generating agent and a covering material that restrains the periphery of the hydrogen generating agent and allows deformation.
- the covering material that restrains the periphery of the hydrogen generating agent and allows deformation is provided, when the hydrogen generating agent reacts with the reaction liquid such as water and expands, Since heterogeneity does not easily occur, the reaction rate is easily stabilized and the reproducibility of the reaction is also improved.
- the surroundings of the hydrogen generating agent are constrained by a coating material that allows deformation, it is difficult to hinder the progress of the reaction due to excessive restraint. As a result, it is possible to provide a hydrogen generating agent package with high stability and reproducibility of the hydrogen generating reaction.
- the coating material is preferably a heat-shrinkable coating material.
- a heat-shrinkable coating material when 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 becomes larger and the reaction solution is prevented from entering. 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.
- the hydrogen generator can be restrained in an appropriate and uniform manner simply by heat-shrinking the coating material when coating the hydrogen generating agent, compared to other coating materials. This is advantageous from the viewpoint of the manufacturing process.
- the heat-shrinkable covering 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.
- the covering material is a tubular heat-shrinkable covering material (for example, a heat-shrinkable tube), holds the hydrogen generating agent inside the heat-shrinkable covering material, and is heat-shrinked. It is preferable to hold the lid at the end of the covering material. By holding the lid at the end of the heat-shrinkable covering material using a cylindrical heat-shrinkable covering material, the sealing effect at the end is enhanced, and the stability and reproducibility of the hydrogen generation reaction is higher. It will be a thing. Further, the hydrogen generating agent can be restrained moderately and uniformly by the coating material in a simple process by heat shrinkage.
- the hydrogen generating agent contains a granular hydrogen generating substance in a resin base material.
- a hydrogen generating agent is a particularly preferable hydrogen generating agent in the present invention because the reaction of the hydrogen generating substance is suppressed to some extent and the reaction is suppressed by suppressing the ingress of the reaction solution.
- a water absorbing body partially in contact with the hydrogen generating agent is further provided, and the covering material covers at least the periphery of the contact portion so that a contact portion between the water absorbing body and the hydrogen generating agent is in close contact with each other. It is preferable.
- the reaction liquid is supplied by bringing the water absorbent into contact with the hydrogen generator, the reaction liquid is supplied via the water absorbent, so that a relatively stable reaction liquid can be supplied. The contact state tends to become unstable.
- the water absorber and the hydrogen generator are generated by covering the water absorber and the hydrogen generator with a covering material that restricts the periphery and allows deformation so that the contact portion is in close contact. Since the contact state with the agent is stabilized, the stability and reproducibility of the hydrogen generation reaction become better.
- the method for producing a hydrogen generating agent package of the present invention includes a step of heat shrinking the covering material in a state where the hydrogen generating agent is disposed inside the cylindrical heat shrinkable covering material.
- a cylindrical heat-shrinkable coating material is used to heat-shrink, so that the hydrogen generating agent can be restrained appropriately and uniformly by the coating material in a simple process, Since this allows deformation, it is possible to obtain a hydrogen generating agent package that has high stability and reproducibility of the hydrogen generation reaction and is hardly affected by changes in the environmental temperature.
- the hydrogen generation method of the present invention is characterized in that hydrogen is generated by supplying a reaction solution to the hydrogen generator using any of the hydrogen generator packages described above. According to the hydrogen generation method of the present invention, since the hydrogen generator package of the present invention is used, the hydrogen generation reaction is highly stable and reproducible due to the effects described above, and is less susceptible to changes in environmental temperature. Become a method.
- a water absorbing body partially in contact with the hydrogen generating agent is further provided, and the covering material covers at least the periphery of the contact portion so that a contact portion between the water absorbing body and the hydrogen generating agent is in close contact with each other.
- a hydrogen generator package coated with a coating material that restrains the periphery and allows deformation so that the contact portion between the water absorber and the hydrogen generator is in close contact Since the contact state with the hydrogen generating agent is stabilized, the stability and reproducibility of the hydrogen generating reaction become better.
- the perspective view which shows the example of the hydrogen generating agent package of this invention Sectional drawing which shows the other example of the hydrogen generating agent package of this invention Sectional drawing which shows the other example of the hydrogen generating agent package of this invention
- Another example of the hydrogen generator package of the present invention Sectional drawing of the other example of the hydrogen generating agent package of this invention
- contraction characteristic of the heat shrinkable tube used in the Example The graph which shows the time-dependent change of the hydrogen generation rate (instantaneous flow rate) in Example 1.
- the hydrogen generating agent package of the present invention includes a hydrogen generating agent 1 and a covering material 2 that restrains the periphery of the hydrogen generating agent 1 and allows deformation.
- the shape of the coated hydrogen generating agent 1 may be any of a quadrangular prism, a cylinder, a plate, a rod, a rectangular parallelepiped, a cube, and the like.
- a hydrogen generating agent 1 having a quadrangular prism or cylindrical shape is used.
- the covering of the hydrogen generating agent 1 with the covering material 2 may be one in which a part of the side wall is exposed without covering the whole side wall of the hydrogen generating agent 1 as shown in FIG.
- the entire side wall of the hydrogen generating agent 1 may be covered and the bottom surface and part of the upper surface of the hydrogen generating agent 1 may be covered.
- covering material 2 may have the opening 2a for making it easy to discharge
- the hydrogen generating agent package of the present invention preferably further includes a water absorbing body 3 partly in contact with the hydrogen generating agent 1, and the covering material 2 includes the water absorbing body 3 and the hydrogen generating body. More preferably, at least the periphery of the contact portion 3a is coated so that the contact portion 3a with the agent 1 is in close contact. At that time, the water absorbent 3 and the hydrogen generating agent 1 may be in contact with each other as long as at least a part of the surface of the hydrogen generating agent 1 is in contact, but as shown in FIG. It is preferable that the hydrogen generating agent 1 and the water absorbent 3 are in contact with each other over almost the entire surface.
- the water absorbing body 3 can be provided on both the front and back sides of the hydrogen generating agent 1, and in FIG. 3A (b), one water absorbing body is extended upward, It is also possible to absorb water from both the upper and lower sides. Further, as shown in FIG. 3A (c), a structure in which a plurality of hydrogen generating agents 1 are provided and the water absorbent 3 is sandwiched therebetween may be employed. In addition, the extension part 3 b which is a part of the water absorbent 3 is extended to the outside of the covering material 2.
- water can be supplied from the middle part of the hydrogen generating agent 1 by taking out a part of the water absorbing body 3 from the opening 2a provided in the covering material 2, and the water absorbing body. It is also possible to adopt a structure in which hydrogen gas flows along the line 3 and is easily discharged.
- the water absorbing body 3 has a structure that is folded in half at the boundary between the wide portion and the narrow portion, and one end of the narrow portion is an extension portion. 3b.
- lids 4 at both end portions of the covering material 2.
- reaction liquid droplets such as water droplets condensed on the inner wall of the container
- such a lid body 4 also has a function as a guide for stably holding the hydrogen generating agent package in the container by the collar portion 4a.
- the lid 4 is integrated with the hydrogen generating agent package by, for example, a method in which the insertion portion 4b is press-fitted into the covering material 2 or the covering material 2 is thermally contracted while the insertion portion 4b is loosely inserted into the covering material 2. be able to.
- a structure may be used in which the end of the hydrogen generating agent 1 is inserted into the recess 4d using the lid 4 having the recess 4d. Thereby, it can restrain that the edge part of the hydrogen generating agent 1 expand
- the lid 4 having the recess 4d a structure capable of restraining the entire circumference of the end portion of the hydrogen generating agent 1 (four surfaces when the end portion is rectangular), or restraining two surfaces of the end portion. Possible structures are listed.
- 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.
- 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.
- 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.
- 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.
- 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 reaction product calcium hydroxide
- the content of the hydrogen generating substance is preferably 60% by weight or more in the hydrogen generating agent, but from the viewpoint of collapsing the resin base material during the reaction while maintaining the shape retention, 60 to 90% in the hydrogen generating agent. % By weight is preferable, and 70 to 85% by weight is more preferable.
- the average particle size of the particulate hydrogen generating material is preferably 1 to 100 ⁇ m, more preferably 6 to 30 ⁇ m, and even more preferably 8 to 10 ⁇ m from the viewpoint of appropriately controlling dispersibility in the resin and reaction.
- the content of the hydrogen generating substance is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, and more preferably 0 to 5% by weight in the hydrogen generating agent. Is more preferable.
- the hydrogen generating material is bound with resin as a binder, or hydrogen generating materials such as particulate Is preferably tableted by press molding.
- 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.
- 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.
- the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylic resin, fluororesin, polyester, and polyamide.
- the heat resistant resin include aromatic polyimide, polyamide, and polyester.
- thermosetting resin examples include an epoxy resin, an unsaturated polyester resin, a phenol resin, an amino resin, a polyurethane resin, a silicone resin, and a thermosetting polyimide resin.
- an epoxy resin is preferable from a viewpoint that the resin base material has moderate disintegration during the hydrogen generation reaction.
- 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. More preferred is 30% by weight.
- the hydrogen generating agent used may contain other components such as a catalyst and a filler as optional components other than the above components.
- a catalyst an alkali compound such as sodium hydroxide, potassium hydroxide, calcium hydroxide is also effective in addition to the metal catalyst for the hydrogen generator.
- hydrogen generating substances such as calcium hydride may generate hydrogen during mixing or reaction with the resin, resulting in vacancies.
- 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.
- 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.
- the step of curing the mixture is performed under pressure.
- the pressurizing condition for pressurization is preferably 1 to 100 MPa, more preferably 2 to 50 MPa, and more preferably 5 to 30 MPa from the viewpoint of reducing the porosity of the hydrogen generating agent in consideration of the manufacturing equipment and manufacturing cost. Is more preferable.
- a press mold or the like can be used for pressurization.
- thermoplastic resin when 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.
- a method of mixing and hardening calcium hydride in a softened precursor and then curing as in the case of a thermoplastic resin can 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.
- 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.
- the covering material include a plastically deformable resin tube and a resin base adhesive tape.
- the heat-shrinkable tube generally has a property that enables elastic deformation or plastic deformation before the shrinkage is completed.
- heat shrinkable tubes such as vinyl chloride, polyvinylidene fluoride, ethylene propylene rubber, neoprene, polyolefin and the like 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 ⁇ m to 5 mm.
- the thickness is preferably 10 to 3000 ⁇ m, more preferably 100 to 2000 ⁇ m, from the viewpoint of obtaining an appropriate binding force. .
- the hydrogen generating agent when the water absorbing body is provided, the hydrogen generating agent is partially in contact.
- 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 absorbent 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 hydrogen generating agent package of the present invention can be manufactured by covering a molded hydrogen generating agent with a covering material of a size that restrains the periphery thereof. At that time, for example, it is necessary to coat the hydrogen generating agent while expanding the diameter of the resin tube or the like, but by applying heat using a heat shrinkable tube, the covering material can be easily constrained around the hydrogen generating agent. It is possible to cover.
- the manufacturing method of the present invention uses such a heat-shrinkable coating material, and heats the coating material in a state where a hydrogen generating agent is disposed inside the cylindrical heat-shrinkable coating material. It includes a step of shrinking. When arranging the hydrogen generating agent, it is preferable to mold it in advance.
- the inner diameter of the coating 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.
- 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 generating agent during the reaction. Further, it is preferable to use a heat-shrinkable coating material having a shrinkage rate of 20 to 95% within this temperature range, and more preferably 50 to 80%.
- the hydrogen generation method of the present invention is to generate hydrogen by supplying a reaction liquid to the hydrogen generator using the hydrogen generator package as described above.
- 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.
- 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.
- 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.
- the hydrogen generator package of the present invention can simplify the device structure of the hydrogen generator, it is particularly effective when used in a fuel cell hydrogen supply device for a form device.
- This mixture was applied to the inside of the mold (10 mm ⁇ 32 mm ⁇ depth 4.3 mm), and dried and cured for about 60 minutes in a dryer (120 ° C. setting) with the upper surface pressed (pressure 10 MPa). .
- the obtained cured product had a thickness of 4.5 mm, a CaH 2 content of 75% by weight, and a porosity of 1%.
- Example 1 (Reproducibility test) Using the plate-shaped molded body of the hydrogen generating agent obtained in Production Example 1, a part of the filter paper is brought into contact with the substantially entire surface (8 mm ⁇ 30 mm) region, and the remainder extends to the outside. A heat shrinkable tube (FEP type, inner diameter 10.6 mm, length 38 mm, thickness 300 ⁇ m) was covered. At this time, the inner diameter of the heat shrinkable tube was 115% of the outer diameter of the hydrogen generating agent. This is placed in an oven, heated at 150 ° C. for 10 minutes, and the heat shrinkable tube is shrunk, so that the hydrogen generator package covering the periphery so that the contact portion between the filter paper and the hydrogen generator is in close contact with each other. Produced. In addition, the shrinkage
- Example 1 Comparative Example 1 (Reproducibility test) In Example 1, when using the same hydrogen generating agent compact and filter paper to bring them into contact with each other in the same area, the same procedure as in Example 1 was performed except that both were bonded and fixed using an adhesive tape. Then, hydrogen generation reaction was performed using four packages. The result is shown in FIG. As shown in this figure, the four instantaneous flow rates vary widely, and the instantaneous flow rates are not stable, indicating that the stability and reproducibility of the hydrogen generation reaction are extremely low.
- Example 2 (test with changing ambient temperature, using FEP) Using the plate-shaped molded body of the hydrogen generating agent obtained in Production Example 1, a part of the filter paper is brought into contact with the substantially entire surface (8 mm ⁇ 30 mm) region, and the remainder extends to the outside. A heat shrinkable tube (FEP type, inner diameter 10.6 mm, length 38 mm, thickness 300 ⁇ m) was covered. At this time, the inner diameter of the heat shrinkable tube was 115% of the outer diameter of the hydrogen generating agent. This is placed in an oven, heated at 150 ° C. for 10 minutes, and the heat shrinkable tube is shrunk, so that the hydrogen generator package covering the periphery so that the contact portion between the filter paper and the hydrogen generator is in close contact with each other. Produced. In addition, the shrinkage
- a hydrogen generation reaction was performed in a thermostat set at room temperature, 40 ° C., 50 ° C., and 60 ° C., respectively. That is, with the hydrogen generator package standing vertically, a part of the filter paper extended to the outside is immersed in water in the container, and water is supplied from the container to the molded body through the filter paper, and hydrogen is supplied for about 1 hour.
- a developmental reaction was performed. The result is shown in FIG. As shown in this figure, it was found that the flow rate was almost the same at all environmental temperatures, and it was difficult to be affected by changes in the environmental temperature.
- Example 3 (example using no water absorbent)
- Example 1 is the same as Example 1 except that the hydrogen generator molded body was covered with a heat-shrinkable tube without using filter paper, both ends were sealed, and a 3 mm ⁇ opening was provided in the center. Similarly, a hydrogen generator package was produced. Two hydrogen generator packages were separately used and immersed in water in a container so that the whole was below the surface of the water, water was supplied to the molded body from the opening, and each hydrogen generation reaction was performed for about 90 minutes. . The result is shown in FIG. As shown in this figure, it was found that even when no water absorbent was present, the two flowed at substantially the same instantaneous flow rate, and the hydrogen generation reaction was highly stable and reproducible.
- Example 4 (Change of heat shrinkable tube type) The following three types were used as heat-shrinkable tubes.
- H-150K (Aisin International Co., Ltd.): shrinkage temperature 150 ° C., shrinkage ratio 2: 1, material vinylidene fluoride resin, inner diameter before shrinkage 9.5 mm, inner diameter after shrinkage (maximum) 4.8 mm, wall thickness (minimum) 0.
- H-1 (Aisin International Co., Ltd.): Shrinkage temperature 80-100 ° C, Shrinkage ratio 2: 1, Material polyolefin, Inner diameter before shrinking 9.9mm, Inner diameter after shrinkage (maximum) 4.5mm, Wall thickness (minimum) 0.56mm , Hishi (Mitsubishi Resin Co., Ltd.): shrinkage temperature 50- ° C., shrinkage ratio 2: 1, material polyvinyl chloride, inner diameter 9.0 mm before shrinkage, wall thickness 0.07 mm.
- a filter paper (9 mm ⁇ 37 mm ⁇ 3.4 mm) was applied to the entire surface area (9 mm ⁇ 37 mm).
- the center part of width 9mm x length 125mm x thickness 0.2mm is contacted, and both ends of the molded body are sandwiched between U-shaped lids so that both sides of the remaining part extend to the outside.
- a heat-shrinkable tube that was slightly longer than the body was covered. This is placed in an oven and heated at each shrinkage temperature for 10 minutes to shrink the heat shrink tube so that the lid is held at both ends so that the contact portion between the filter paper and the hydrogen generator is in close contact.
- a hydrogen generator package with a coating on the periphery was prepared.
- a hydrogen generation reaction was performed as follows. That is, in a thermostatic chamber at 30 ° C., the hydrogen generator package is placed in a vertical position in a container, and a part of the filter paper extending to the outside is immersed in water (2.3 mL) in the container. Then, water was supplied from the container to the molded body, and a hydrogen generation reaction was performed for about 1 hour. The result is shown in FIG. In addition, the result of hydrogen generation reaction at the time of winding the waterproof tape which uses a urethane film as a base material, and coat
- Example 5 Inner diameter change of heat shrinkable tube
- Example 4 instead of using H-150K with an inner diameter of 9.5 mm before shrinkage, an inner diameter before shrinkage of the same material and shrinkage ratio of 12.7 mm (inner diameter after shrinkage (maximum) 6.4 mm, wall thickness (minimum) 0. 3 mm), and an inner diameter before shrinkage of 19.1 mm (inner diameter after shrinkage (maximum) 9.5 mm, wall thickness (minimum) 0.41 mm) under the same conditions as in Example 4, Hydrogen generation reaction was performed for 1 hour. The result is shown in FIG.
- Example 6 (Change of shrinkage rate of heat-shrinkable tube)
- H-1 having a shrinkage ratio of 2: 1
- H-2 having the same shrinkage ratio of 3: 1 and the same material and inner diameter (Aisin International)
- shrinkage temperature 80 to 100 ° C., polyolefin material
- shrinkage A hydrogen generation reaction was performed for about 1 hour under the same conditions as in Example 4 except that a front inner diameter of 9.9 mm, a post-shrinkage inner diameter (maximum) of 3 mm, and a wall thickness (minimum) of 0.75 mm) were used.
- the results are shown in FIG. 11 together with the results of H-150K and H-1.
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Abstract
Description
なお、熱可塑性樹脂としては、ポリエチレン、ポリプロピレン、ポリスチレン、アクリル樹脂、フッ素樹脂、ポリエステル、ポリアミドなどが挙げられる。また、耐熱性樹脂としては、芳香族系のポリイミド、ポリアミド、ポリエステルなどが挙げられる。
走査型電子顕微鏡(SEM)を用いて撮影した写真から、平均的な粒子径を有するものを選び出し、その長径と短径とを平均して求めた。
実際に測定したサンプルの体積と、実際に測定したサンプルの質量を材料自身の密度で除して算出した体積との差として空孔体積を算出し、次式により空孔率(%)を求めた。空孔率(%)=空孔体積/全体積×100
製造例1(水素発生剤の製造)
未硬化のエポキシ樹脂(ジャパンエポキシレジン(株)製、jER828)11.7gにCaH2(和光純薬社製、平均粒径10μm)37.6gを添加して撹拌後、更にジシアンジアミド系硬化剤(ジャパンエポキシレジン(株)製、DICY7)0.7g、変性脂肪族(3級アミン)硬化促進剤(ジャパンエポキシレジン(株)製、3010、トリスジメチルアミノメチルフェノール)0.12gを添加して撹拌した。
製造例1で得られた板状の水素発生剤の成形体を用いて、表面の略全体(8mm×30mm)の領域に濾紙の一部を接触させ、残部が外部に延出するように、熱収縮チューブ(FEPタイプ、内径10.6mm、長さ38mm、厚み300μm)を被せた。このとき、熱収縮チューブの内径は、水素発生剤の外径の115%であった。これをオーブン中に置いて、150℃で10分間加熱を行って、熱収縮チューブを収縮させることで、濾紙と水素発生剤との接触部が密着するように周囲を被覆した水素発生剤パッケージを作製した。なお、用いた熱収縮チューブの収縮特性を、図4に示す。
実施例1において、同じ水素発生剤の成形体と濾紙を用いて、同じ面積で両者を接触させる際に、粘着テープを用いて両者を貼り合わせて固定したこと以外は、実施例1と同様にして、4つのパッケージを用いて水素発生反応を行った。その結果を、図6に示す。この図が示すように、4つの瞬時流量が大きくばらついており、また、瞬時流量も安定しておらず、水素発生反応の安定性と再現性が極めて低いことが分かった。
製造例1で得られた板状の水素発生剤の成形体を用いて、表面の略全体(8mm×30mm)の領域に濾紙の一部を接触させ、残部が外部に延出するように、熱収縮チューブ(FEPタイプ、内径10.6mm、長さ38mm、厚み300μm)を被せた。このとき、熱収縮チューブの内径は、水素発生剤の外径の115%であった。これをオーブン中に置いて、150℃で10分間加熱を行って、熱収縮チューブを収縮させることで、濾紙と水素発生剤との接触部が密着するように周囲を被覆した水素発生剤パッケージを作製した。なお、用いた熱収縮チューブの収縮特性を、図4に示す。
実施例1において、濾紙を使用せずに水素発生剤の成形体を熱収縮チューブで被覆し、その両端部を封止して中央に3mmφの開孔を設けたこと以外は、実施例1と同様にして、水素発生剤パッケージを作製した。この水素発生剤パッケージを2つ別々に用いて、全体が水面下になるように容器内の水に浸して、開孔から成形体に水を供給し、それぞれ約90分間水素発生反応を行った。その結果を、図8に示す。この図が示すように、吸水体が存在しない場合でも、2つとも略同じ瞬時流量で推移しており、水素発生反応の安定性と再現性が高いことが分かった。
熱収縮チューブとして、下記の3種を使用した。
H-150K(エイシンインターナショナル社):収縮温度150℃、収縮率2:1、材質フッ化ビニリデン樹脂、収縮前内径9.5mm、収縮後内径(最大)4.8mm、肉厚(最小)0.3mm、
H-1(エイシンインターナショナル社):収縮温度80~100℃、収縮率2:1、材質ポリオレフィン、収縮前内径9.9mm、収縮後内径(最大)4.5mm、肉厚(最小)0.56mm、
ヒシ(三菱樹脂社製):収縮温度50~℃、収縮率2:1、材質ポリ塩化ビニル、収縮前内径9.0mm、肉厚0.07mm。
実施例4において、収縮前内径9.5mmのH-150Kを用いる代わりに、同じ材質と収縮率の収縮前内径12.7mm(収縮後内径(最大)6.4mm、肉厚(最小)0.3mm)のものと、収縮前内径19.1mm(収縮後内径(最大)9.5mm、肉厚(最小)0.41mm)のものとを用いたこと以外は実施例4と同じ条件で、約1時間水素発生反応を行った。その結果を、図10に示す。
実施例4において、収縮率2:1のH-1を用いる代わりに、収縮率3:1で同じ材質と内径のH-2(エイシンインターナショナル社)、収縮温度80~100℃、材質ポリオレフィン、収縮前内径9.9mm、収縮後内径(最大)3mm、肉厚(最小)0.75mm)を用いたこと以外は実施例4と同じ条件で、約1時間水素発生反応を行った。その結果を、H-150K及びH-1の結果と共に、図11に示す。
2 被覆材
2a 開孔
3 吸水体
3a 接触部
3b 延出部
4 蓋体
Claims (8)
- 水素発生剤と、その水素発生剤の周囲を拘束しかつ変形を許容する被覆材とを備える水素発生剤パッケージ。
- 前記被覆材は、熱収縮性の被覆材である請求項1に記載の水素発生剤パッケージ。
- 前記被覆材は、筒状で熱収縮性の被覆材であり、熱収縮した被覆材の内部に水素発生剤を保持すると共に、熱収縮した被覆材の端部に蓋体を保持している請求項2に記載の水素発生剤パッケージ。
- 前記水素発生剤は、樹脂の母材中に粒状の水素発生物質を含有するものである請求項1~3いずれかに記載の水素発生剤パッケージ。
- 前記水素発生剤と一部が接触した吸水体を更に備え、前記被覆材はその吸水体と前記水素発生剤との接触部が密着するように少なくとも前記接触部の周囲を被覆してある請求項1~4いずれかに記載の水素発生剤パッケージ。
- 筒状で熱収縮性の被覆材の内側に、水素発生剤を配置した状態で、前記被覆材を熱収縮させる工程を含む水素発生剤パッケージの製造方法。
- 請求項1~5いずれかに記載の水素発生剤パッケージを用いて、前記水素発生剤に反応液を供給して水素を発生させる水素発生方法。
- 請求項5に記載の水素発生剤パッケージを用いて、その吸水体を介して前記水素発生剤に反応液を供給して水素を発生させる水素発生方法。
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KR1020117026848A KR101367684B1 (ko) | 2009-04-22 | 2010-04-21 | 수소발생제 패키지와 그 제조 방법 및 수소발생방법 |
EP10767077.0A EP2423161A4 (en) | 2009-04-22 | 2010-04-21 | CONDITIONING HYDROGEN GENERATING AGENT, PROCESS FOR PRODUCING THE SAME, AND METHOD FOR GENERATING HYDROGEN |
CN201080016263.1A CN102387986B (zh) | 2009-04-22 | 2010-04-21 | 制氢剂封装物、其制造方法以及制氢方法 |
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CN110217756B (zh) * | 2019-06-28 | 2022-09-20 | 桂林电子科技大学 | 一种碳负载铋的铝基复合制氢材料的制备方法及应用 |
US11820568B2 (en) * | 2020-12-16 | 2023-11-21 | Steris Corporation | Fluorinated shrink wrap for surgical item identification tags |
CN113414382A (zh) * | 2021-06-09 | 2021-09-21 | 南京清研工程科技有限公司 | 一种用于制氢的阻燃型铝基复合材料及其制备方法 |
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