WO2024043197A1 - Générateur d'hydrogène - Google Patents

Générateur d'hydrogène Download PDF

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Publication number
WO2024043197A1
WO2024043197A1 PCT/JP2023/029910 JP2023029910W WO2024043197A1 WO 2024043197 A1 WO2024043197 A1 WO 2024043197A1 JP 2023029910 W JP2023029910 W JP 2023029910W WO 2024043197 A1 WO2024043197 A1 WO 2024043197A1
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Prior art keywords
hydrogen
cyclic olefin
hydrogen generating
magnesium hydride
weight
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PCT/JP2023/029910
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English (en)
Japanese (ja)
Inventor
侑太郎 澤田
直樹 東
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東洋アルミニウム株式会社
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Publication of WO2024043197A1 publication Critical patent/WO2024043197A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
    • 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

Definitions

  • the present invention relates to a novel hydrogen generator.
  • a hydrogen generating agent for hydrogenating a liquid contained in a container and a hydrogen generating method using the same in which the hydrogen generating component is 1 to 40% by weight based on the total amount. of magnesium, the average particle size of the hydrogen generating agent is within the range of 1 ⁇ m to 20 mm, and the amount of water that permeates from the outside to all or part of the surface of the core material of the hydrogen generating agent.
  • a hydrogen generator has been proposed that is characterized by being provided with a moisture adjustment layer for controlling the water content (Patent Document 1).
  • the hydrogen generator in order to obtain an oxidation-suppressing effect that is beneficial to the human body in beverages or foods to which hydrogen is supplied, it is desirable to design the hydrogen generator so that the saturated hydrogen concentration is approximately 1.6 ppm. .
  • the saturated hydrogen concentration is approximately 1.6 ppm.
  • moisture present in the natural environment such as the atmosphere and hydrogen generators may The reaction proceeds and hydrogen generation progresses, making it impossible to obtain the desired amount of hydrogen generation during actual use.
  • the main object of the present invention is to provide a hydrogen generator that can generate a required amount of hydrogen when desired even when stored for a relatively long period of time.
  • a hydrogen generating body comprising a molded body in which hydrogen generating particles that generate hydrogen upon contact with water are dispersed in a matrix, and a protective layer formed on the surface of the molded body, (1)
  • the matrix contains a resin component and substantially contains neither a cyclic olefin copolymer nor a cyclic olefin polymer, (2) the protective layer includes at least one of a cyclic olefin copolymer and a cyclic olefin polymer; (3) the content of hydrogen generating particles in the molded body is 0.1 to 45% by weight;
  • a hydrogen generator characterized by: 2. 2.
  • the hydrogen generating body according to item 1 wherein the shaped body has a substantially spherical shape or a substantially sheet-like shape. 3. 2. The hydrogen generator according to item 1, wherein the total content of at least one of the cyclic olefin copolymer and the cyclic olefin polymer in the protective layer is 50 to 100% by weight. 4. 2. The hydrogen generator according to item 1, wherein the resin component is at least one of a thermoplastic resin and a thermosetting resin. 5. The hydrogen generating particles are one type selected from the group consisting of (a) metal hydride particles, (b) metal magnesium particles, (c) metal aluminum particles, and (d) alloy particles containing at least one of magnesium and aluminum. or 2 or more types of hydrogen generators according to item 1 above. 6. 2. The hydrogen generating body according to item 1, wherein the molded body is laminated on the surface of a core material that does not contain hydrogen generating particles.
  • when hydrogen is desired refers to, but is not limited to, for example, from the time when a hydrogen generator is brought into contact with a hydrogen supply destination such as a beverage or food and starts supplying hydrogen to the hydrogen supply destination. , a period of about two days thereafter is desirable.
  • "obtaining the necessary amount of hydrogen generation in a short time” means supplying a total of 1.8 mL or more of hydrogen to 100 mL of water in 2 days immediately after manufacturing the conventional hydrogen generator. It was designed based on the configuration (including the size of the hydrogen generating body and the content of hydrogen generating particles). In the present invention, it is desirable that the value be equal to or higher than this standard.
  • the required hydrogen generation amount is 0.5 mL in two days. If drinking water is 100 mL, the required amount of hydrogen generation will be 1.8 mL in 2 days. If drinking water is 3L, the required amount of hydrogen generation will be 54mL in 2 days. If a 13L pail contains 13L of medical water, the required hydrogen generation amount will be 230mL in 2 days. Note that these numerical values are merely examples, and the present invention is not necessarily limited to these numerical values.
  • the hydrogen generating body of the present invention has the surface of the molded product containing hydrogen generating particles covered with a specific protective layer containing a cyclic olefin copolymer and/or a cyclic olefin polymer, which may cause water vapor or odor. It has high barrier properties against chemical substances, etc., and odors, harmful substances, etc. do not easily transfer to the hydrogen generator even if stored for a long period of time. Moreover, the protective layer can effectively suppress hydrogen generation at unexpected timing.
  • FIG. 1 It is an image diagram (sectional view) which shows the structural example of the hydrogen generating body of this invention.
  • 2 is a schematic diagram showing a test method for a hydrogen generation amount test in Test Example 1.
  • FIG. 1 is a schematic diagram showing a test method for a hydrogen generation amount test in Test Example 1.
  • the hydrogen generating body of the present invention comprises a molded body in which hydrogen generating particles that generate hydrogen upon contact with water are dispersed in a matrix (the molded body of the present invention), and a molded body formed on the surface of the molded body.
  • a hydrogen generator comprising a protective layer, (1) The matrix contains a resin component and substantially contains neither a cyclic olefin copolymer nor a cyclic olefin polymer, (2) the protective layer includes at least one of a cyclic olefin copolymer and a cyclic olefin polymer; (3) the content of hydrogen generating particles in the molded body is 0.1 to 45% by weight; It is characterized by
  • hydrogen is used as a term having the same meaning as molecular hydrogen (hydrogen gas) unless otherwise specified.
  • the hydrogen-generating particles are not particularly limited as long as they generate hydrogen upon contact with water.
  • the water may be liquid water or water vapor. Further, the water may be anything containing water (H 2 O), and may be any of pure water, an aqueous solution, an aqueous dispersion, and the like.
  • Examples of hydrogen generating particles include magnesium hydride, calcium hydride, barium hydride, beryllium hydride, strontium hydride, lithium hydride, sodium hydride, sodium borohydride, lithium sodium hydride, silicon hydride, etc.
  • examples include simple metals such as magnesium and aluminum, or alloys containing them. These can be used alone or in combination of two or more. Further, since metals such as aluminum and magnesium react with water to form an oxide film, an alkaline component such as calcium hydroxide or an acid component such as ammonium sulfate may be added.
  • the hydrogen generating particles are usually in the form of powder, and their size is not particularly limited, but generally the volume average particle diameter is preferably 1 to 100 ⁇ m, particularly preferably 10 to 50 ⁇ m.
  • the volume average particle diameter is less than 1 ⁇ m, the hydrogen generating particles tend to aggregate with each other, and the dispersibility in the matrix may decrease. Moreover, if it exceeds 100 ⁇ m, the hydrogen generating particles will become heavy, so there is a risk that the dispersibility in the matrix will become low.
  • the volume average particle diameter of the hydrogen generating particles is a value obtained by calculating the average particle diameter D50 (50% particle diameter) from the volume cumulative particle size distribution of a group of hydrogen generating particles measured by laser diffraction.
  • the content of hydrogen generating particles in the molded article of the present invention is not limited, but is usually 0.1 to 45% by weight, preferably 1 to 40% by weight, and within 2 days from the start of use. Since the amount of hydrogen generated per 1 g of hydrogen generating particles (eg, magnesium hydride, etc.) is the most efficient, it is most preferable to set the amount to 1 to 9% by weight. Therefore, it is also possible to set it within the range of 2 to 9% by weight, for example. If the content is less than 0.1% by weight, there is a risk that sufficient hydrogen will not be generated. On the other hand, if the content exceeds 45% by weight, there is a risk that the hydrogen generating particles and the resin etc.
  • the amount of hydrogen generated per 1 g of hydrogen generating particles eg, magnesium hydride, etc.
  • the labyrinth effect slows down the entry of moisture into the hydrogen generating body, making it difficult for the hydrogen generating particles to react with water, making it impossible to obtain a predetermined amount of hydrogen generation after storage.
  • the intrusion of moisture into the hydrogen generating body is stopped, there will be a large amount of unreacted hydrogen generating body in the first place, which may be disadvantageous in terms of cost.
  • the matrix in the molded article of the present invention primarily has the function of supporting and fixing the hydrogen generating particles.
  • the content of the matrix in the molded article of the present invention can generally be about 55 to 99.9% by weight, particularly preferably about 60 to 99.9% by weight, and more preferably about 91 to 99.9% by weight. It is more preferable to express it in % by weight. Therefore, it can be set to about 80 to 95% by weight, for example.
  • composition of the matrix a composition containing a resin component and substantially containing neither a cyclic olefin copolymer nor a cyclic olefin polymer is adopted. That is, a composition containing a cyclic olefin copolymer and a resin component other than the cyclic olefin polymer (hereinafter also referred to as "matrix resin component”) is employed.
  • matrix resin component a composition containing a cyclic olefin copolymer and a resin component other than the cyclic olefin polymer.
  • substantially free means that the content is such that it does not prevent the molded article of the present invention from permeating into water, and is preferably 0.1% by weight or less, with 0% by weight being particularly preferred. preferable.
  • the matrix resin component at least one of a thermoplastic resin and a thermosetting resin can be used.
  • thermoplastic resin examples include at least one of acrylic resin, polystyrene resin, ABS resin, vinyl chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polycarbonate, polyacetal resin, and fluororesin.
  • thermosetting resin examples include at least one of phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyester resins, polyurethane resins, diallyl phthalate resins, silicone resins, and alkyd resins.
  • copolymers containing combinations of monomers that can constitute each of the above resins, modified resins of the above resins, etc. can be used.
  • the matrix preferably has a higher water vapor permeability than the protective layer from the viewpoint of the amount of hydrogen generated. If the water vapor permeability of the matrix is lower than that of the protective layer, it will be difficult for water or water vapor to penetrate, making it impossible to react efficiently with the hydrogen-generating particles, and it will take time to obtain enough hydrogen to satisfy the hydrogen saturation concentration. There is a possibility that it will be necessary.
  • water vapor permeability of the matrix higher than that of the protective layer, water and hydrogen particles can react efficiently, so there is no need to add more expensive hydrogen generating particles than necessary, which is advantageous in terms of the cost of the hydrogen generator. It can be.
  • the above relationship between the water vapor permeability of the matrix and the protective layer can be appropriately controlled, for example, by changing the type of matrix resin component, the thickness of the protective layer, etc., as described later.
  • the matrix resin component is preferably at least one of polyolefin resins, polyester resins, polyamide resins, etc., and particularly preferably at least one of polyethylene resins and polyamide resins.
  • at least one of low-density polyethylene resin (LDPE) and polyamide resin allows water to more reliably contact the hydrogen generating particles in the molded article of the present invention when the hydrogen generating body of the present invention is placed in water. , the desired hydrogen generation effect can be obtained.
  • LDPE low-density polyethylene resin
  • the matrix may contain other additives as long as they do not impede the effects of the present invention.
  • additives include adhesives, fragrances, fillers, antioxidants, tackifiers, antiblocking agents, colorants, thickeners, and the like.
  • the content (total content) of these additives may be approximately 0 to 5% by weight in the matrix, but is not limited thereto.
  • the content of the impregnant in the matrix is preferably less than 1% by weight, since this makes it difficult for variations in the concentrations of the matrix resin component and the hydrogen generating particles to occur.
  • the hydrogen generating body of the present invention is a molded article having a certain shape.
  • the molded products of the present invention include molded products formed by general molding methods, as well as three-dimensional solids such as coating films formed by coating, granules formed by granulation, etc. It includes any form of solid matter. This makes it possible, for example, to improve the efficiency of hydrogen generation, to combine it with other materials, to laminate it into other articles, etc.
  • the molded article of the present invention substantially does not contain a cyclic olefin copolymer and/or a cyclic olefin polymer, so water can penetrate into the molded article of the present invention relatively easily. Therefore, when the hydrogen generator is placed in water, the water that has penetrated the protective layer will penetrate well into the molded article of the present invention, making it possible to obtain a sufficient amount of hydrogen generation in a short time when needed. .
  • the shape of the molded article of the present invention is not limited and can be appropriately set depending on its purpose, place of use, etc.
  • approximately sheet shapes approximately film-like to approximately plate-like shapes
  • approximately prismatic shapes approximately cylindrical shapes
  • approximately donut shapes approximately powder shapes (granules, flakes, etc.), and combinations of these shapes.
  • Any shape etc. can be adopted. Therefore, for example, it can be made into a shape having design characteristics such as animals and plants, character characters, vehicles, etc.
  • the molded article of the present invention may be either hollow or solid.
  • the size of the molded article of the present invention is also not particularly limited, and can be adjusted as appropriate depending on its usage.
  • the diameter can be set within a range of about 5 to 100 mm, but the diameter is not limited to this.
  • the thickness is usually about 10 to 150 ⁇ m, so that hydrogen can be efficiently supplied to the hydrogen supply destination without excess or deficiency.
  • the protective layer is a layer that protects the molded article of the present invention (particularly the matrix), and the presence of the protective layer can more effectively prevent hydrogen generating particles from falling off.
  • the protective layer although not limited to, a composition containing a cyclic olefin copolymer and/or a cyclic olefin polymer (hereinafter also referred to as "first resin component") as a main component is preferably employed. I can do it.
  • the main component here refers to a component in which the total content of cyclic olefin copolymer and/or cyclic olefin polymer is in the range of 50% by weight or more and 100% by weight or less of the resin components constituting the protective layer. means. Therefore, it can be set to 60 to 95% by weight, for example.
  • the protective layer does not contain hydrogen generating particles.
  • the cyclic olefin copolymer is a copolymer of a cyclic olefin and an ⁇ -olefin, and may itself be a known compound. Alternatively, it may be synthesized by a known manufacturing method.
  • Examples of the cyclic olefin include norbornene, 5-methyl-bicyclo[2. 2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5,5- Dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene ene, 5-octadecyl-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1] Hept-2-ene, 5-methyl-bicyclo[2. 2.1] hept-2-ene and the like.
  • Examples of the ⁇ -olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4 -Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, and the like.
  • a copolymer of norbornene (cyclic olefin) and ethylene ( ⁇ -olefin) can be suitably used.
  • Such a copolymer can be represented by the following general formula.
  • R 1 to R 4 are the same or different from each other and represent a hydrogen atom or a hydrocarbon group.
  • x and y are the same or different from each other and represent the number of repeats of each monomer unit.
  • a cyclic olefin copolymer having a cyclic olefin content of about 20 to 50 mol% can be used, but is not limited thereto.
  • commercially available products can also be used as the cyclic olefin copolymer.
  • Commercially available products include various products such as “TOPAS” (manufactured by Polyplastics Co., Ltd.), “APEL” (manufactured by Mitsui Chemicals Co., Ltd.), and “ZEONOR” (manufactured by Nippon Zeon Co., Ltd.). You can also use
  • a cyclic olefin polymer is a polymer of cyclic olefins. This polymer includes polymers of cyclic olefins that are the same or different from each other, hydrogenated polymers thereof, and the like. Examples of the cyclic olefin include the cyclic olefins shown above.
  • cyclic olefin polymer known or commercially available ones can be used.
  • various products such as the product name "ZEONEX T62R” (manufactured by Nippon Zeon Co., Ltd.) can also be used.
  • the content of the first resin component in the protective layer is not limited, but from the viewpoint of long-term storage, etc., it is usually preferably in the range of about 50 to 100% by weight in total. Therefore, it can be set to about 60 to 98% by weight, for example.
  • the content of the first resin component in the protective layer is less than 50% by weight, the amount of adsorption of unnecessary components such as odor components increases, and the effect of long-term storage properties may not be obtained.
  • the content of the first resin component in the protective layer is more preferably 70 to 100% by weight, and most preferably 95 to 100% by weight.
  • the protective layer may contain resin components other than the cyclic olefin copolymer and the cyclic olefin polymer (hereinafter also referred to as "second resin component" unless otherwise specified) within a range that does not impede the effects of the present invention. ) may be included.
  • the second resin component may be either a thermoplastic resin or a thermosetting resin.
  • the content of the second resin component in the protective layer is, for example, about 0 to 50% by weight, and can be in the range of about 0 to 30% by weight, but is not limited thereto.
  • thermoplastic resin examples include at least one of acrylic resin, polystyrene resin, ABS resin, vinyl chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polycarbonate resin, polyacetal resin, and fluororesin.
  • thermosetting resin examples include at least one of phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyester resins, polyurethane resins, diallyl phthalate resins, silicone resins, and alkyd resins.
  • copolymers containing combinations of monomers that can constitute each of the above resins, modified resins of the above resins, etc. can be used. These can also be used alone or in combination of two or more.
  • the thickness of the protective layer is not limited, but it is usually preferably about 0.1 to 500 ⁇ m, more preferably 1 to 50 ⁇ m, and most preferably 1 to 5 ⁇ m. If the thickness is less than 0.1 ⁇ m, the matrix may not be sufficiently protected. Moreover, when it exceeds 500 ⁇ m, the barrier properties are too high, making it difficult for water to penetrate, and there is a possibility that hydrogen will not be sufficiently generated.
  • any additives can be mixed in the protective layer as long as they do not impede the effects of the present invention.
  • examples include adhesives, fragrances, fillers, antioxidants, tackifiers, antiblocking agents, colorants, thickeners, and the like.
  • the total content of these additives can be, for example, 0 to 5% by weight, but is not limited thereto.
  • the hydrogen generating body of the present invention has a protective layer formed on the surface of the molded product of the present invention, but if necessary, other members may be laminated on the surface of the molded product of the present invention, or other members may be formed on the surface of the molded product of the present invention.
  • the molded article of the present invention may be laminated on the substrate. Any of these forms is included in the hydrogen generator of the present invention. Here, there are no limitations on the material, form, function, etc. of the other members, and any member can be employed.
  • the material of the other members may be, for example, resin, rubber, metal, ceramics, stone, glass, fibrous material, paper, or the like. Therefore, when the molded article of the present invention is substantially sheet-like, other members may be selected from the group consisting of paper, metal cans, metal plates, metal foils, metal vapor deposited films, nonwoven fabrics, cloth, and resins. Seeds or two or more types of materials (especially sheet-like materials) can be suitably used as other members.
  • any form such as raw materials, semi-finished products, final products, etc. can be applied. Therefore, it is also possible, for example, to arrange the molded article of the present invention inside a final product (such as a container).
  • a) a member that supports and fixes the molded article of the present invention b) a member that protects, supports, and fixes the molded article of the present invention, etc. can be applied.
  • a core material base material
  • the molded article of the present invention is laminated on the surface of the core material. can.
  • the core material will be explained in more detail.
  • Core Material A configuration in which a core material is used as a support member of the molded article of the present invention and the molded article of the present invention is laminated on the surface of the core material can also be adopted as an embodiment of the hydrogen generating body of the present invention.
  • a core material By providing the hydrogen generating body of the present invention with a core material, physical strengths such as elasticity and rigidity can be changed. Further, it is also possible to give the hydrogen generator a desired shape.
  • the material of the core material is not particularly limited, and any of organic materials, inorganic materials, or composite materials thereof can be employed. Note that in the present invention, the core material is made of a material that does not contain hydrogen generating particles.
  • organic materials include, for example, when the resin constituting the core material is solid, polyolefin resins such as polyethylene and polypropylene, styrene resins, vinyl chloride resins, polyester resins such as polyethylene terephthalate, polyamide resins, polyethylene glycol, and polyethylene oxide.
  • polyolefin resins such as polyethylene and polypropylene
  • styrene resins vinyl chloride resins
  • polyester resins such as polyethylene terephthalate
  • polyamide resins polyethylene glycol
  • polyethylene oxide polyethylene oxide
  • the core material is in the form of a film, a solvent or the like may be added in addition to the above-mentioned resins, if necessary.
  • the inorganic material one or more kinds selected from, for example, glass, ceramics, metal, and stone can be used.
  • the density of the entire hydrogen generating body can be changed as appropriate.
  • the hydrogen generator when supplying molecular hydrogen to a liquid, the hydrogen generator can be submerged or floated in the liquid.
  • the shape of the core material can be appropriately set depending on, for example, the desired shape of the hydrogen generating body. That is, the shape can be the same (similar) or similar to the desired shape of the hydrogen generating body. For example, when the hydrogen generator is approximately spherical, the core material may also be approximately spherical. For example, when the hydrogen generating body is in the form of a sheet, the core material may also be in the form of a sheet.
  • the proportion of the core material in the hydrogen generating body of the present invention can be, for example, in the range of about 5 to 90% by volume of the hydrogen generating body, but is not limited thereto.
  • the method for producing a hydrogen generating body of the present invention is not particularly limited as long as a hydrogen generating body having the above structure can be obtained, but it can be suitably produced by, for example, the following method. That is, a method for producing a material that generates hydrogen upon contact with water, (1) A step of preparing a mixture containing a) hydrogen-generating particles that can react with water to generate hydrogen, and b) a resin component containing neither a cyclic olefin copolymer nor a cyclic olefin polymer (mixing step) ), (2) a step of obtaining a molded object by molding the mixture (molding step); and (3) a step of forming a protective layer containing at least one of a cyclic olefin copolymer and a cyclic olefin polymer on the surface of the molded object. (Protective layer formation process)
  • the hydrogen generating body of the present invention can be suitably produced by a production method
  • a mixture containing a) hydrogen-generating particles that can react with water to generate hydrogen, and b) a resin component that substantially does not contain either a cyclic olefin copolymer or a cyclic olefin polymer is prepared.
  • the mixing step it is preferable to prepare the mixture from a melt-kneaded product.
  • the resin component, hydrogen generating particles, etc. can be mixed more reliably and uniformly.
  • additives, etc. to be blended into the mixture those exemplified as the matrix resin component etc. explained above can be used.
  • the resin component contained in the mixture may be melted, and the method is not particularly limited.
  • the method is not particularly limited.
  • the molten resin component and hydrogen generating particles are kneaded, and the hydrogen generating particles are uniformly distributed in the matrix.
  • a melt-kneaded product in which are dispersed can be obtained.
  • the kneading may be carried out using, for example, a single-screw extruder or a twin-screw extruder, but a twin-screw extruder is particularly suitable because of its good dispersion efficiency.
  • the twin-screw extruder a commercially available device can also be used, and for example, "Omega 25" manufactured by STEER can be suitably used.
  • the form of the mixture obtained in the mixing step is not limited, and for example, a) a compound form in which a plurality of hydrogen generating particles are contained in the raw material, b) the surface of one hydrogen generating particle is covered with the raw material.
  • the coated particles may have any form.
  • melt-kneaded product may be once cooled as described above to produce a compound or the like, but it is also possible to proceed to the molding step in the molten state as it is. Thereby, the molded article of the present invention can be produced more efficiently.
  • a molded body is obtained by molding the mixture. In this way, the molded article of the present invention can be obtained.
  • the molding method may be appropriately selected depending on, for example, the form of the hydrogen generating body, its use, etc.
  • a known method for molding a resin molded article for example, injection molding, extrusion molding, blow molding, calender molding, etc. can be employed, and injection molding is particularly preferred for molding a uniform shape.
  • injection molding the mixture is poured into a heated cylinder, melted and kneaded by rotating a screw inside the cylinder, and then cooled in a mold of a predetermined shape to produce molded products of various shapes. be able to.
  • the molding machine in this case is not limited, and may be any one of a single screw extruder, a twin screw extruder, and the like.
  • the mixture is poured into a heated cylinder, turned into a melt by rotating a screw provided inside the cylinder, and then the melt flowing out of the die is cooled with a cooling roll to form a film shape. Molded objects can be produced.
  • a core material may be prepared prior to the molding process, and the above mixture may be formed into a film on the surface of the core material.
  • a film forming method is not particularly limited, and may be, for example, a coating method using a coating liquid containing the above mixture, or a coating method using a melt obtained by melting the above mixture.
  • the coating method is not particularly limited, and examples include roll coating, gravure coating, bar coater, doctor blade coating, comma coater, spray coating, brush coating, as well as known methods such as blow molding, injection molding, extrusion molding, and two-color molding.
  • a coating film of the above mixture can be formed on the surface of the core material by the method.
  • a protective layer containing at least one of a cyclic olefin copolymer and a cyclic olefin polymer is formed on the surface of the molded article.
  • the formation of the protective layer can be suitably carried out by applying a coating liquid or a melt containing components capable of forming the protective layer to the surface of the molded article of the present invention.
  • a coating liquid or a melt containing components capable of forming the protective layer to the surface of the molded article of the present invention.
  • the cyclic olefin copolymer, cyclic olefin polymer, additives, etc. contained in the coating liquid or melt those explained above can be used.
  • the coating liquid can be prepared by dissolving or dispersing components that can constitute the protective layer in a solvent.
  • the solution is preferably a solution in which a resin component including at least the first resin component is dissolved.
  • solvents include, but are not limited to, water, as well as ethanol, methanol, cyclohexane, toluene, acetone, isopropyl alcohol (IPA), propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal pentane, and normal hexane.
  • IPA isopropyl alcohol
  • hexyl alcohol methyl ethyl ketone, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, isopentyl acetate, n-butyl acetate, n-propyl acetate, n-pentyl acetate (also known as n-amyl acetate), cyclohexane, isobutyl Alcohol, isopropyl alcohol, isopentyl alcohol, ethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, ortho-dichlorobenzene, xylene, cresol, chlorobenzene , cyclohexanol, cyclohexanone, N,N-dimethylformamide, te
  • the solid content concentration of the coating liquid can be appropriately set, for example, taking into account the coating properties, and can be, for example, in the range of about 5 to 60% by mass, but is not limited thereto.
  • the method for preparing the coating liquid is not particularly limited, and it can be obtained, for example, by adding a cyclic olefin copolymer or the like to a solvent and mixing. Furthermore, the order of addition of each component is not particularly limited.
  • the coating method is not particularly limited as long as it can form a coating film with the coating liquid on the surface of the molded article of the present invention.
  • roll coating various types of gravure coating, bar coater, doctor blade coating, comma coater, spray coating, brush coating, etc. can be employed.
  • the drying conditions can be appropriately set depending on, for example, the type of solvent, the amount of coating, and the like.
  • the temperature can be set, for example, in the range of 50 to 150°C, but is not limited thereto.
  • the drying time can be, for example, in the range of 5 seconds to 120 minutes, but is not limited thereto.
  • the melt can be prepared, for example, by heat-melting a mixture containing components that can constitute the protective layer.
  • the coating method using the melt is not particularly limited, and the protective layer can be formed on the surface of the molded article of the present invention by known methods such as blow molding, injection molding, extrusion molding, and two-color molding.
  • the molding step and this step may be performed simultaneously.
  • the hydrogen generator of the present invention can be used in the same manner as known hydrogen generators. In particular, it is desirable that the surface of the hydrogen generator of the present invention be placed in direct contact with an object to which hydrogen is to be supplied (particularly water or a material containing water).
  • a hydrogen generation container using the hydrogen generator of the present invention, it may be placed in the container so as to be in contact with the water or aqueous solution in the container. Further, when used by pasting it on a hydrogen supply destination, for example, the hydrogen generating body of the present invention may be pasted so as to be in direct contact with the object (article) to which hydrogen is supplied. Thereby, the hydrogen generated from the surface of the hydrogen generating body of the present invention can be supplied to the hydrogen supply destination.
  • the object to which the generated hydrogen is utilized may be any object to which hydrogen is supplied through direct or indirect contact with the hydrogen generator of the present invention. Particularly preferred are those whose physical properties can be maintained or improved by the action of hydrogen (for example, reduction action).
  • the hydrogen supply destination may be water or a liquid containing water, or may be a solid or gas containing water.
  • the hydrogen supply destination may be any of pure water, an aqueous solution, an aqueous dispersion, and the like.
  • Hydrogen can be supplied to, for example, a) foodstuffs such as beverages, meat, seafood, vegetables, and fruits; b) processed foods made from the above ingredients, as well as fresh flowers, fungi, bacteria, plant seeds, and blood transfusions. Examples include blood, infusions, bath water, washing water, detergents, air, wound dressings, cosmetics, diapers, pet drinks, aquarium water, microorganisms, soil, feed or feed, indoor space, the human body, animals, plants, etc. It will be done. These can serve as both a hydrogen supply destination and a moisture supply source to the hydrogen generator, but the moisture supply source and the hydrogen supply destination may be different. In particular, the hydrogen supply destination is preferably a moisture supply source to the hydrogen generator.
  • Hydrogen can be added to the hydrogen supply destination by wrapping or packaging the hydrogen generator in a substantially spherical or sheet shape in advance, or in the case of a liquid, by introducing a substantially spherical hydrogen generator in advance. can.
  • FIG. 1 an example of the cross-sectional structure of a hydrogen generating body having a substantially spherical shaped body of the present invention is shown in FIG.
  • the embodiment of the hydrogen generating body of the present invention is particularly, but not limited to, a part or all of the protective layer as the outermost layer, and a lower layer directly in contact with the protective layer.
  • a configuration in which the molded article of the present invention is arranged can be cited as a preferred embodiment.
  • a configuration in which part or all of the molded article of the present invention is the outermost layer can also be adopted.
  • the molded product of the present invention has a substantially spherical shape, and has a structure in which hydrogen generating particles are dispersed in a matrix containing (low density polyethylene (LDPE)) as a resin component.
  • a protective layer containing a cyclic olefin copolymer is formed on part or all of its surface.
  • the matrix containing a cyclic olefin copolymer is abbreviated as "COC”.
  • the molded article of the present invention is laminated on the surface of the core material, and a protective layer containing a cyclic olefin copolymer is formed on part or all of the surface of the molded article of the present invention.
  • the molded article of the present invention has a hollow, substantially spherical shape, and has a structure in which hydrogen generating particles are dispersed in a matrix containing a resin component other than a cyclic olefin copolymer.
  • hydrogen generating particles can be unevenly distributed in large numbers near the surface of the hydrogen generating body, and as a result, the amount of hydrogen generating particles used can be relatively reduced. Even if the amount is small, it is advantageous in that the desired hydrogen generation performance can be obtained.
  • Example 1 Magnesium hydride powder (manufactured by BioCoke Giken Co., Ltd., volume average particle diameter (D50) 15 ⁇ m) was kneaded in a molten state into commercially available low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LJ803) melted at 190 ° C. A compound containing magnesium hydride was prepared. The proportions were 97% by weight of low density polyethylene and 3% by weight of magnesium hydride powder.
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball.
  • a ball containing magnesium hydride powder was produced.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • a coating agent of a cyclic olefin copolymer (APEL6509T, manufactured by Mitsui Chemicals, Inc.) dissolved in toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was prepared, and the above magnesium hydride powder-containing balls were added to the coating agent.
  • the ball After immersion and drying at 120° C. for 10 minutes, the ball was again dipped in the coating agent and dried at 120° C. for 10 minutes to form a cyclic olefin copolymer layer with a dry thickness of 10 ⁇ m over the entire surface of the ball.
  • the nonvolatile content of the coating agent was 10% by weight.
  • Example 2 Magnesium hydride powder (manufactured by BioCoke Giken Co., Ltd., volume average particle diameter (D50) 15 ⁇ m) was kneaded in a molten state into commercially available polypropylene (Novatec PP MA3, manufactured by Nippon Polypropylene Co., Ltd.) melted at 190°C. A compound containing magnesium chloride was prepared. The proportions were 97% by weight of polypropylene and 3% by weight of magnesium hydride powder.
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball. This was molded to produce a ball containing magnesium hydride powder.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • a coating agent of a cyclic olefin copolymer (APEL6509T, manufactured by Mitsui Chemicals, Inc.) dissolved in toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was prepared, and the above magnesium hydride powder-containing balls were added to the coating agent.
  • the ball After immersion and drying at 120° C. for 10 minutes, the ball was again dipped in the coating agent and dried at 120° C. for 10 minutes to form a cyclic olefin copolymer layer with a dry thickness of 10 ⁇ m over the entire surface of the ball.
  • the nonvolatile content of the coating agent was 10% by weight.
  • the magnesium hydride powder is 3% by weight, and the hydrogen generating body as a whole is 1.5g, which is designed to supply 1.8mL or more of hydrogen per 100mL of water in 2 days. .
  • Example 3 Magnesium hydride powder (manufactured by BioCoke Giken Co., Ltd., volume average particle diameter (D50) 15 ⁇ m) was kneaded in a molten state into commercially available low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LJ803) melted at 190 ° C. A compound containing magnesium hydride was prepared. The proportions were 99% by weight of low density polyethylene and 1% by weight of magnesium hydride powder.
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball.
  • a ball containing magnesium hydride powder was produced.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • a coating agent of a cyclic olefin copolymer (APEL6509T, manufactured by Mitsui Chemicals, Inc.) dissolved in toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was prepared, and the above magnesium hydride powder-containing balls were added to the coating agent.
  • the ball After immersion and drying at 120° C. for 10 minutes, the ball was again dipped in the coating agent and dried at 120° C. for 10 minutes to form a cyclic olefin copolymer layer with a dry thickness of 10 ⁇ m over the entire surface of the ball.
  • the nonvolatile content of the coating agent was 10% by weight.
  • magnesium hydride powder and 1.5g of the hydrogen generator it is designed to supply more than 1.8mL of hydrogen per 100mL of water in 2 days. did.
  • Example 4 Magnesium hydride powder (manufactured by BioCoke Giken Co., Ltd., volume average particle diameter (D50) 15 ⁇ m) was kneaded in a molten state into commercially available low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LJ803) melted at 190 ° C. A compound containing magnesium hydride was prepared. The proportions were 91% by weight of low density polyethylene and 9% by weight of magnesium hydride powder.
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball.
  • a ball containing magnesium hydride powder was produced.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • a coating agent of a cyclic olefin copolymer (APEL6509T, manufactured by Mitsui Chemicals, Inc.) dissolved in toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was prepared, and the above magnesium hydride powder-containing balls were added to the coating agent.
  • the ball After immersion and drying at 120° C. for 10 minutes, the ball was again dipped in the coating agent and dried at 120° C. for 10 minutes to form a cyclic olefin copolymer layer with a dry thickness of 10 ⁇ m over the entire surface of the ball.
  • the nonvolatile content of the coating agent was 10% by weight.
  • Example 5 Magnesium hydride powder (manufactured by BioCoke Giken Co., Ltd., volume average particle diameter (D50) 15 ⁇ m) is kneaded in a molten state into commercially available low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LJ803) melted at 190 ° C. A magnesium hydride-containing compound was prepared by. The proportions were 60% by weight of low density polyethylene and 40% by weight of magnesium hydride powder.
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball.
  • a ball containing magnesium hydride powder was produced.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • a coating agent of a cyclic olefin copolymer (APEL6509T, manufactured by Mitsui Chemicals, Inc.) dissolved in toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was prepared, and the above magnesium hydride powder-containing balls were added to the coating agent.
  • the ball After immersion and drying at 120° C. for 10 minutes, the ball was again dipped in the coating agent and dried at 120° C. for 10 minutes to form a cyclic olefin copolymer layer with a dry thickness of 10 ⁇ m over the entire surface of the ball.
  • the nonvolatile content of the coating agent was 10% by weight.
  • magnesium hydride powder and 1.5g of the hydrogen generator it is designed to supply more than 1.8mL of hydrogen per 100mL of water in 2 days. did.
  • Example 6 Magnesium hydride powder (manufactured by BioCoke Giken Co., Ltd., volume average particle diameter (D50) 15 ⁇ m) was kneaded in a molten state into commercially available low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LJ803) melted at 190 ° C. A compound containing magnesium hydride was prepared. The proportions were 97% by weight of low density polyethylene and 3% by weight of magnesium hydride powder.
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball.
  • a ball containing magnesium hydride powder was produced.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • a coating agent of a cyclic olefin polymer (ZEONEX T62R, manufactured by Zeon Corporation) dissolved in toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was prepared, and the above-mentioned magnesium hydride powder-containing balls were added to the coating agent. After drying at 120° C.
  • the ball was impregnated with the coating agent again and dried at 120° C. for 10 minutes to form a cyclic olefin polymer layer with a dry thickness of 10 ⁇ m over the entire surface of the ball.
  • the nonvolatile content of the coating agent was 10% by weight.
  • Example 7 Using an injection molding machine equipped with a spherical mold with a diameter of 14 mm, commercially available low-density polyethylene (Novatec LD LJ803, manufactured by Nippon Polyethylene Co., Ltd.) melted at 190°C was made into a molten state, and the spherical metal was heated to 80°C. After feeding it into a mold, it was cooled and formed into a ball shape to produce a polyethylene ball. The surface area of this ball was approximately 6.2 cm2 .
  • Novatec LD LJ803 manufactured by Nippon Polyethylene Co., Ltd.
  • the polyethylene ball was immersed in the first coating agent and dried at 120°C for 10 minutes, then the ball was immersed again in the first coating agent and dried at 120°C for 10 minutes, and a hydrogen film with a dry film thickness of 10 ⁇ m was added.
  • a polyethylene layer containing magnesium chloride powder was formed on the entire surface of the ball.
  • a second coating agent of a cyclic olefin copolymer (APEL6509T, manufactured by Mitsui Chemicals, Inc.) dissolved in toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was prepared.
  • the ball is immersed in the second coating agent and dried at 120°C for 10 minutes, and then the ball is immersed in the second coating agent again and dried at 120°C for 10 minutes to form a cyclic olefin copolymer layer with a dry thickness of 10 ⁇ m.
  • the polyethylene layer containing magnesium hydride powder was formed on the entire surface of the ball.
  • the nonvolatile content of the coating agents was 10% by weight, and the amount of magnesium hydride powder in the first coating agent was 3% by weight of the nonvolatile content.
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball. This was molded to produce a ball containing magnesium hydride powder.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball. This was molded to produce a ball containing magnesium hydride powder.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball. This was molded to produce a ball containing magnesium hydride powder.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball. This was molded to produce a ball containing magnesium hydride powder.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • the magnesium hydride-containing compound was molten, fed into the spherical mold heated to 80°C, and then cooled to form a ball.
  • a ball containing magnesium hydride powder was produced.
  • the surface area of this magnesium hydride powder-containing ball was approximately 6.2 cm 2 .
  • a coating agent of a cyclic olefin copolymer (APEL6509T, manufactured by Mitsui Chemicals, Inc.) dissolved in toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was prepared, and the above magnesium hydride powder-containing balls were added to the coating agent.
  • the ball was again dipped in the coating agent and dried at 120° C. for 10 minutes to form a cyclic olefin copolymer layer with a dry thickness of 10 ⁇ m over the entire surface of the ball.
  • Constant temperature and humidity test As a method to simulate long-term storage of a hydrogen generator, a constant temperature and humidity test was conducted as an accelerated test in a constant temperature and humidity environment. The constant temperature and humidity test was carried out for 20 hours under conditions of a temperature of 85° C. and a humidity of 85 RH%, in which the hydrogen generators obtained in the respective examples and comparative examples were housed in IC400 manufactured by Espec.
  • the experimental device was stored for 2 days in a water bath adjusted to 40°C.
  • the hydrogen gas generated in chamber 1 moves to chamber 2, and the ion-exchanged water that filled chamber 2 is pushed up to chamber 3. Since the volume of the ion-exchanged water pushed up into the chamber 3 was equivalent to that of the hydrogen gas generated in the chamber 1, the volume of the hydrogen gas was determined by measuring the volume of the ion-exchanged water using a syringe. Pass/fail judgment was made based on whether or not an amount of hydrogen generation of 1.8 mL or more in 100 mL could be obtained even after the constant temperature and humidity test.
  • the hydrogen generators of Examples 1 to 7 produced 2.8 to 5.0 mL of hydrogen for two days both before and after the constant temperature and humidity test. It can be seen that the amount is 1.8 mL or more, which is the standard for practical use. That is, even after long-term storage, the required amount of hydrogen generation was obtained when desired.

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Abstract

Le problème décrit par la présente invention est de fournir un générateur d'hydrogène permettant d'obtenir la quantité d'hydrogène requise au moment voulu, même si l'hydrogène a été stocké pendant une période relativement longue. La solution consiste en un générateur d'hydrogène comprenant : un corps façonné dans lequel des particules de génération d'hydrogène qui génèrent de l'hydrogène lors de la mise en contact de l'eau sont dispersées dans une matrice ; et une couche de protection qui est formée sur la surface du corps façonné. Le générateur d'hydrogène est caractérisé en ce que : (1) la matrice contient un composant de résine et ne contient substantiellement aucun copolymère d'oléfine cyclique et aucun polymère d'oléfine cyclique ; (2) la couche de protection contient au moins un type parmi le copolymère d'oléfine cyclique et le polymère d'oléfine cyclique ; et (3) la teneur des particules génératrices d'hydrogène dans le corps façonné est de 0,1 à 0,45 % en poids.
PCT/JP2023/029910 2022-08-22 2023-08-19 Générateur d'hydrogène WO2024043197A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100150824A1 (en) * 2008-11-21 2010-06-17 Lynntech, Inc. Hydrogen generator with reactant dilution scheme
JP2017165704A (ja) * 2015-09-09 2017-09-21 メロディアン株式会社 水素を有効成分とする疲労回復用水素水及び疲労回復方法
JP2019182699A (ja) * 2018-04-06 2019-10-24 東洋アルミニウム株式会社 水素発生材料及びその製造方法
JP3238228U (ja) * 2022-04-28 2022-07-11 東洋アルミニウム株式会社 水素発生容器

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100150824A1 (en) * 2008-11-21 2010-06-17 Lynntech, Inc. Hydrogen generator with reactant dilution scheme
JP2017165704A (ja) * 2015-09-09 2017-09-21 メロディアン株式会社 水素を有効成分とする疲労回復用水素水及び疲労回復方法
JP2019182699A (ja) * 2018-04-06 2019-10-24 東洋アルミニウム株式会社 水素発生材料及びその製造方法
JP3238228U (ja) * 2022-04-28 2022-07-11 東洋アルミニウム株式会社 水素発生容器

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