WO2012070573A1 - Composite container for storage of hydrogen, and hydrogen-filling method - Google Patents

Composite container for storage of hydrogen, and hydrogen-filling method Download PDF

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Publication number
WO2012070573A1
WO2012070573A1 PCT/JP2011/076910 JP2011076910W WO2012070573A1 WO 2012070573 A1 WO2012070573 A1 WO 2012070573A1 JP 2011076910 W JP2011076910 W JP 2011076910W WO 2012070573 A1 WO2012070573 A1 WO 2012070573A1
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Prior art keywords
hydrogen
carbon material
porous carbon
container
temperature
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PCT/JP2011/076910
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French (fr)
Japanese (ja)
Inventor
順二 岡崎
大島　伸司
幸次郎 中川
愛 蓑田
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Ｊｘ日鉱日石エネルギー株式会社
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Publication of WO2012070573A1 publication Critical patent/WO2012070573A1/en

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • 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
    • 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
    • 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
    • Y02E60/32—Hydrogen storage
    • 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 composite container for hydrogen storage and a hydrogen filling method. More specifically, by using a material excellent in hydrogen storage capacity, a hydrogen storage composite container having excellent durability, and a simple hydrogen filling method that does not require precooling or requires less precooling. It is about.
  • FCV fuel cell vehicle
  • FCV hydrogen fuel container uses a composite container (CFRP container) using an aluminum liner or a resin liner for weight reduction.
  • CFRP container composite container
  • the thermal conductivity of the resin liner layer or the CFRP layer is low, the hydrogen temperature exceeds the allowable temperature of the CFRP (carbon fiber reinforced resin) container when hydrogen is rapidly filled up to 70 MPa in FCV.
  • Patent Document 1 describes that hydrogen is stored in activated carbon and used in a fuel cell. However, these are general activated carbons, and there is no mention of an effective method for introducing the activated carbon into the container.
  • the present invention is capable of storing as much hydrogen as possible and does not require precooling at the time of hydrogen filling, or requires less precooling, and a hydrogen storage composite container that can be charged with hydrogen more easily than before, and the composite It aims at providing the hydrogen filling method to a container.
  • the present invention is a composite container in which a liner is reinforced with fibers and a resin, and has a hydrogen storage capacity of 0.5 mass% when the temperature is 303 K and the hydrogen equilibrium pressure is 35 MPa.
  • a hydrogen storage composite container in which 5 to 25% by volume of the above porous carbon material is present. Any material may be used for the liner.
  • the hydrogen storage amount can be increased by allowing the porous carbon material to exist inside, and the porous carbon material absorbs heat, so that the hydrogen temperature can be increased. Can be suppressed. Therefore, in addition to being able to store a large amount of hydrogen, the composite container for hydrogen storage according to the present invention can eliminate the need for precool equipment or reduce the precool capacity.
  • the composite container for hydrogen storage of the present invention is suitable as a container for hydrogen fuel for FCV.
  • a simple endothermic material may be used. In that case, it is necessary to increase the capacity of the container in order to maintain the hydrogen storage amount.
  • the endothermic material can be provided with a hydrogen storage capability, so that the object can be achieved without changing the container capacity.
  • the porous carbon material preferably has a specific surface area measured by the BET method of 800 to 3000 m 2 / g and a micropore volume of 0.5 to 2 cc / g.
  • the porous carbon material is preferably an activated carbon derived from a plant raw material formed through two or more activation steps or an activated carbon containing Li atoms.
  • the present invention is also a composite container in which a liner is reinforced with fibers and a resin, and has a hydrogen storage capacity of 0.5% by mass or more when the temperature is 303 K and the hydrogen equilibrium pressure is 35 MPa.
  • the heat capacity of the porous carbon material absorbs the adsorption heat of hydrogen and the compression heat of hydrogen that is not adsorbed.
  • a hydrogen filling method in which hydrogen is compressed and filled so that the temperature is equal to or lower than the heat resistant temperature of the resin.
  • a hydrogen storage composite container that can store a large amount of hydrogen, does not require precooling when filling with hydrogen, or requires less precooling, and can be charged with hydrogen more easily than before. it can.
  • a hydrogen filling method that uses the above composite container for hydrogen storage, does not require precooling, or requires less precooling, and can easily fill a larger amount of hydrogen than before. it can.
  • FIG. 1 is a schematic partial cross-sectional view of a hydrogen storage composite container according to an embodiment of the present invention.
  • the hydrogen storage composite container 1 includes a container portion 6 in which a liner 2 is reinforced with fibers and a resin 4.
  • the liner 2 is a cylindrical body having both ends formed in a dome shape (hemispherical shape), the inside is hollow, and has a structure for filling at least one end with hydrogen.
  • the cylindrical portions other than the both end portions may be formed with a constant diameter, but may have a structure in which the diameter of the central portion is somewhat larger.
  • the material constituting the liner 2 may be any material as long as a certain strength can be obtained, such as a metal such as stainless steel or aluminum, or a plastic such as polyethylene.
  • the structure filled with hydrogen provided at at least one end of the liner 2 is generally composed of a base 12 and a hydrogen supply pipe 14 extending in a nozzle shape outside the liner 2.
  • the hydrogen supply pipe 14 may also extend inside the liner 2 as shown in FIG. In that case, the portion (inner nozzle) extending into the liner 2 of the hydrogen supply pipe 14 is, for example, a filter-like pipe having numerous holes, and hydrogen is blown uniformly by the inner nozzle. May be.
  • the liner 2 is reinforced with fibers and resin 4.
  • the container part 6 is manufactured by winding the carbon fiber impregnated with resin around the liner 2, for example.
  • the winding method is arbitrary.
  • a tow prepreg in which a carbon fiber or the like is impregnated with a resin in advance is used, or a liquid resin is impregnated in a liquid resin at the time of winding.
  • the resin used is generally a thermosetting resin, and a typical one is an epoxy resin.
  • Examples of the winding method include a method of winding continuously and densely by hoop winding, helical winding or the like. Such a resin is wound around the liner 2 and then heated and cured.
  • the thickness of the reinforcing layer including the fibers and the resin 4 varies depending on the hydrogen filling pressure, but is generally 5 mm to 10 cm and is about 3% to 20% of the diameter of the liner 2.
  • the hydrogen storage capacity is 0.5 mass% or more
  • the porous carbon material 8 of 0.6 to 3% by mass is present in an amount of 5 to 25% by volume.
  • Such a porous carbon material 8 may be a general one, but particularly preferred is an activated carbon derived from a plant raw material having a high hydrogen storage capacity and formed through two or more activation steps. Furthermore, the porous carbon material 8 is preferably activated carbon containing Li atoms.
  • the activated carbon derived from plant raw materials formed through two or more activation steps is obtained by activating two or more times after carbonizing plant raw materials such as coconut shells, rice straw, bamboo, and wood chips.
  • the activated carbon thus obtained is activated carbon having a large surface area and easy to occlude hydrogen and having developed micropores, and is an activated carbon having a high level of hydrogen occlusion ability by the action of plant-derived components other than carbon.
  • the plant raw material as it is or carbonized at a temperature of 300 to 1,000 ° C. is subjected to the first stage activation treatment. If necessary, the plant material may be pulverized before activation.
  • the activation method includes steam activation, alkali activation and the like, and any activation method may be used, but an activation method using an alkali metal or alkaline earth metal hydroxide is particularly preferable.
  • an alkali metal hydroxide For example, 0.2 to 5 parts by mass of an alkali metal hydroxide is added to 1 part by mass of a carbide obtained by carbonizing a plant raw material, and the treatment is performed at a temperature of about 500 to 800 ° C. for about 0.1 to 5 hours. Do. At this time, potassium hydroxide is particularly preferable as the alkali metal hydroxide. Thereafter, unreacted alkali metal hydroxide is removed by washing. In washing, it is possible to remove alkali using hydrochloric acid or the like as necessary. Then, after making it dry, it activates again. At this time, steam activation may be performed, or an alkali metal hydroxide may be reacted in the same manner.
  • potassium hydroxide may be used, and since it is easy to form micropores, lithium hydroxide may be used, or some alkali metal hydroxides may be used in combination. Thereafter, similarly, it is washed if necessary and dried. Further, activation may be repeated.
  • the activated carbon derived from plant raw materials thus produced has a specific surface area measured by the BET method of 800 to 3000 m 2 / g and a micropore volume of 0.5 to 2 cc / g.
  • Plants contain components other than carbon even when carbonized, and have better hydrogen storage capacity than mere activated carbon due to interaction with hydrogen. On the other hand, components other than carbon may hinder activation, and by activating twice or more, preferable activation and pore formation are possible.
  • the activated carbon containing Li atoms is a general activated carbon in which Li ions are bonded (supported) to oxygen functional groups on the surface.
  • the oxygen-containing functional group is preferably at least one selected from the group consisting of a phenolic hydroxyl group, a quinone group, a lactone carboxyl group, and a carboxyl group.
  • the following chemical formula (5) shows a state in which Li is not bonded to a part of the surface of the porous carbon material in which carboxyl groups and hydroxyl groups are formed as oxygen-containing functional groups.
  • the following chemical formula (6) shows a state where Li is bonded to a part of the surface of the porous carbon material shown in the following chemical formula (5).
  • Li is bonded to oxygen contained in the oxygen-containing functional group to form a LiO group.
  • the LiO group has a property of strongly adsorbing hydrogen molecules. Therefore, when the LiO group is formed on the surface of the porous carbon material, the adsorption density of hydrogen molecules in the hydrogen storage material is increased, and the hydrogen storage capacity is significantly improved as compared with the conventional case.
  • the oxygen-containing functional group is particularly preferably a phenolic hydroxyl group among the functional groups described above.
  • Li bonded to a phenolic hydroxyl group is more preferable than Li bonded to other oxygen-containing functional groups.
  • the amount of Li contained in the hydrogen storage material may be about 0.1 to 3 mmol / g. However, the amount of Li contained in the hydrogen storage material is not limited to this range. The larger the amount of Li introduced into the hydrogen storage material, the better the hydrogen storage capacity.
  • Such activated carbon carrying Li may be activated carbon derived from plant materials activated two or more times as described above.
  • an activated product of a fibrous raw material may be used.
  • the activated material of the fibrous raw material is preferably activated PAN (polyacrylonitrile).
  • the activated material of the fibrous raw material is manufactured by a manufacturing method including two steps of “carbonization” and “activation” in the same manner as the activated carbon derived from the plant raw material described above. It is preferable that the activated fiber material is also activated two or more times. Moreover, it is preferable that the activated material of a fibrous raw material is what carried Li as mentioned above.
  • the fibrous raw material activation product thus produced also has a specific surface area measured by the BET method of 800 to 3000 m 2 / g and a micropore volume of 0.5 to 2 cc / g.
  • such a porous carbon material 8 is present inside the liner 2.
  • the powder of the porous carbon material 8 is dispersed in an evaporable organic solvent, it is cast into a flexible sheet such as paper, and the end dome member is used.
  • the end dome member is used.
  • the liner 2 is reinforced with fibers and resin 4 to form the composite container 1 for hydrogen storage of the present invention.
  • the amount of the porous carbon material 8 inside the composite container 1 is preferably 5 to 25% by volume of the volume of the place where hydrogen is stored in the space where the hydrogen inside the liner 2 exists.
  • the amount of the porous carbon material 8 depends on the relationship between the amount of heat generated when hydrogen is charged, the amount of heat absorbed by the porous carbon material 8, and the amount of heat generated when hydrogen is occluded. It is desirable to adjust so that the temperature of the hydrogen charged in the inside is lower than the heat resistant temperature of the resin or lower than the temperature stipulated by laws and regulations.
  • the porous carbon material 8 is present so that the temperature raised by the heat generated from the amount of heat is less than the heat resistant temperature (safe temperature) of the resin. At this time, if the temperature that can be used is determined according to a standard, the amount of the porous carbon material 8 is preferably determined in accordance with the temperature.
  • the amount of the porous carbon material 8 required at this time is, for example, 5 to 25% by volume, preferably 8 to 15% of the volume of the storage place when 70 MPa is filled for 3 minutes according to the current standards of the automobile industry association.
  • the required hydrogen storage capacity is 0.5% by mass or more, preferably in the range of 0.6 to 3% by mass. If the temperature is out of this range, the temperature is not lowered sufficiently.
  • the porous carbon material 8 is present in a certain amount on the inner surface of the liner 2 because a heat insulation effect is produced in addition to the effect of suppressing the temperature rise due to the heat capacity.
  • This manufacturing method is arbitrary.
  • the porous carbon material 8 may be attached to the inner surface of the liner 2 using a binder such as a resin, and the powder of the porous carbon material 8 is dispersed in an evaporable organic solvent as before. Then, after being cast on the surface inside the liner 2, it may be held by pressing with a breathable net-like material.
  • the temperature of hydrogen was examined so as to be kept at 85 ° C. or less which is the safety standard of the automobile industry association. At this temperature, it was confirmed that there was no influence on the resin used (heat resistant temperature of 120 ° C. or higher).
  • Example 1 A CFRP container made of an aluminum liner provided with a filter-like hydrogen supply pipe having innumerable holes of 1 ⁇ m or less was produced.
  • the specifications of the produced container were an internal volume of 10 L, an inner diameter of 160 mm, a length of 520 mm, and a minimum burst pressure of 180 MPa.
  • the PAN-based fibrous carbon material was baked at 600 ° C., 0.08 mol of KOH was added per 1 g of the baked fibrous carbon material, and activation treatment was performed at 600 ° C. for 2 hours in an inert gas atmosphere. Thereafter, the activation treatment was again performed at 750 ° C. in an inert gas atmosphere with 0.1 mol of KOH per 1 g of the fibrous carbon material after activation.
  • the obtained porous carbon material had a specific surface area measured by BET method of 2281 m 2 / g and a micropore volume of 1.276 cc / g.
  • the hydrogen storage capacity of the obtained porous carbon material was 0.6 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
  • Example 2 The PAN-based fibrous carbon material was baked at 600 ° C., 0.08 mol of KOH was added per 1 g of the baked fibrous carbon material, and activation treatment was performed at 600 ° C. for 2 hours in an inert gas atmosphere. Then, activation treatment was again performed at 750 ° C. in an inert gas atmosphere with 0.1 mol of LiOH per 1 g of the fibrous carbon material after activation, and Li was introduced into the material. The amount of introduced Li was 0.3% by mass.
  • the obtained porous carbon material had a specific surface area measured by the BET method of 2128 m 2 / g and a micropore volume of 1.316 cc / g.
  • the hydrogen storage capacity of the obtained porous carbon material was 1.2 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
  • Example 3 The rice husk was baked at 500 ° C., 0.05 mol of KOH was added per 1 g of the baked rice husk, and activated at 750 ° C. for 1 hour in an inert gas atmosphere. Thereafter, activation treatment was performed again at 750 ° C. in an inert gas atmosphere with 0.1 mol of LiOH per 1 g of chaff after activation, and Li was introduced into the material. The amount of introduced Li was 0.2% by mass.
  • the obtained porous carbon material had a specific surface area measured by BET method of 2348 m 2 / g and a micropore volume of 1.158 cc / g.
  • the hydrogen storage capacity of the obtained porous carbon material was 1.0 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
  • Example 4 Coke was baked at 700 ° C., 0.07 mol of KOH was added per 1 g of the baked coke, and activation treatment was performed at 750 ° C. for 2 hours in an inert gas atmosphere. Thereafter, the activation treatment was performed again at 750 ° C. in an inert gas atmosphere with 0.1 mol of NaOH per 1 g of coke after activation.
  • the obtained porous carbon material had a specific surface area measured by the BET method of 2048 m 2 / g and a micropore volume of 1.208 cc / g.
  • the hydrogen storage capacity of the obtained porous carbon material was 0.5 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
  • Example 5 The coconut palm was baked at 700 ° C., 0.05 mol of KOH was added per 1 g of the baked coconut palm, and activation treatment was performed at 750 ° C. for 2 hours in an inert gas atmosphere. Then, activation treatment was performed again at 750 ° C. in an inert gas atmosphere with 0.1 mol of LiOH per gram of activated palm, and Li was introduced into the material. The amount of introduced Li was 0.3% by mass.
  • the obtained porous carbon material had a specific surface area measured by the BET method of 2118 m 2 / g and a micropore volume of 1.402 cc / g.
  • the hydrogen storage capacity of the obtained porous carbon material was 1.3 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
  • Example 1 4 kg (18.2% by volume) of commercially available activated carbon for deodorization was introduced into a container having the same specifications as in Example 1, and hydrogen at an initial temperature of 25 ° C. was charged at a high speed to 70 MPa in 3 minutes.
  • the hydrogen temperature in the container immediately after filling was 98 ° C., and the amount of filled hydrogen was 0.26 kg.
  • the hydrogen storage capacity of the activated carbon was 0.0 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
  • Example 6 The coconut palm was baked at 700 ° C., 0.05 mol of KOH was added per 1 g of the baked coconut palm, and activation treatment was performed at 750 ° C. for 2 hours in an inert gas atmosphere. Then, after cleaning, when the temperature reached 450 ° C., the second stage oxygen activation treatment was performed with a mixed gas (flow rate: 3 Nm 3 / h) with nitrogen having an oxygen concentration of 5% by volume.
  • the obtained porous carbon material had a specific surface area measured by the BET method of 1988 m 2 / g and a micropore volume of 1.305 cc / g.
  • the hydrogen storage capacity of the obtained porous carbon material was 1.4 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
  • Example 7 For a container having the same specifications as in Example 1, 4 kg (16.8% by volume) of the porous carbon material of Example 4 was dissolved in acetone and cast on the inner surface of the container as uniformly as possible, and then acetone was removed. did. Thereafter, the porous carbon material was held by covering with a nonwoven fabric.
  • hydrogen with an initial temperature of 25 ° C. was filled at high speed to 70 MPa in 3 minutes.
  • the hydrogen temperature in the container immediately after filling was 85 ° C., and the amount of filled hydrogen was 0.31 kg, but it was confirmed that the heat conduction to the outside was gentle.
  • Example 8 4 kg (17.5 vol%) of the porous carbon material of Example 5 was dissolved in acetone so as to be as uniform as possible on the inner surface of the container so as to be as uniform as possible on the inner surface of the container having the same specifications as in Example 1. After casting, acetone was removed. Thereafter, the porous carbon material was held by covering with a nonwoven fabric.
  • hydrogen with an initial temperature of 25 ° C. was filled at high speed to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 84 ° C., and the amount of filled hydrogen was 0.31 kg, but it was confirmed that the heat conduction to the outside was gentle.
  • Example 9 In order to be as uniform as possible on the inner surface of the container having the same specifications as in Example 1, 4 kg (17.7% by volume) of the porous carbon material of Example 6 was dissolved in acetone to be as uniform as possible on the inner surface of the container. After casting, acetone was removed. Thereafter, the porous carbon material was held by covering with a nonwoven fabric.
  • hydrogen with an initial temperature of 25 ° C. was filled at high speed to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 84 ° C., and the amount of filled hydrogen was 0.31 kg, but it was confirmed that the heat conduction to the outside was gentle.
  • the composite container for hydrogen storage according to the present invention can be used as a fuel tank for an engine in a hydrogen society where hydrogen is used for transportation infrastructure or in a hydrogen vehicle.
  • it can be used as a propane gas cylinder as a hydrogen storage container for a household fuel cell.
  • it can be used in a hydrogen supply place that does not have complicated and expensive equipment, and greatly contributes to the spread of hydrogen as energy. It is clear that the implementation of the present invention can contribute to the environment and contribute to the realization of a continuity society.
  • SYMBOLS 1 Composite container for hydrogen storage, 2 ... Liner, 4 ... Fiber and resin, 6 ... Container part, 8 ... Porous carbon material, 12 ... Base, 14 ... Hydrogen supply pipe

Abstract

The present invention provides a composite container for storing hydrogen, which can store a large amount of hydrogen, does not require pre-cooling or requires slight pre-cooling in the filling of hydrogen, and can fill hydrogen more readily compared with conventional containers. One aspect of the present invention is a composite container, wherein a liner (2) is reinforced by fibers and a resin (4), and wherein 5-25 vol% of a porous carbon material (8) having a hydrogen storage capacity of 0.5 mass% or more at a temperature of 303 K and under a hydrogen equilibrium pressure of 35 MPa is present in the inside of the container.

Description

水素貯蔵用複合容器及び水素充填方法Composite container for hydrogen storage and hydrogen filling method
　本発明は、水素貯蔵用複合容器及び水素充填方法に関する。より詳しくは、水素吸蔵能に優れた材料を使用することにより、耐久性に優れた水素貯蔵用の複合容器、及び、プレクールを必要としない、もしくは、プレクールが少なくてすむ簡便な水素の充填方法に関するものである。 The present invention relates to a composite container for hydrogen storage and a hydrogen filling method. More specifically, by using a material excellent in hydrogen storage capacity, a hydrogen storage composite container having excellent durability, and a simple hydrogen filling method that does not require precooling or requires less precooling. It is about.
　現在、環境に配慮し、水素をエネルギーとし、燃料電池で発電し走行する燃料電池車（ＦＣＶ）の開発が進められている。一般にＦＣＶは、水素を何らかの形で自動車に貯蔵するものである。例えば、ボンベのような容器に水素を気体や液体として貯蔵したり、あるいは、水素吸蔵合金で固形化し貯蔵する。自動車においては、軽量化が必要であり、水素吸蔵合金のような重量があるものは敬遠される傾向にある。しかし、容器で水素を保存するには、いくつかの解決しなければならない課題がある。一つは、限られた容器のスペースでできるだけ多量の水素を貯蔵する必要があること、もう一つは貯蔵する速度を早くすることである。例えば、ＦＣＶへの水素充填時間は３分以内であることが求められている。 Currently, in consideration of the environment, the development of a fuel cell vehicle (FCV) that uses hydrogen as energy and generates electricity with a fuel cell and runs is underway. In general, FCV stores hydrogen in an automobile in some form. For example, hydrogen is stored in a container such as a cylinder as a gas or liquid, or is solidified and stored with a hydrogen storage alloy. In automobiles, it is necessary to reduce the weight, and those having a weight such as a hydrogen storage alloy tend to be avoided. However, in order to store hydrogen in a container, there are some problems that must be solved. One is to store as much hydrogen as possible in a limited container space, and the other is to increase the storage speed. For example, the hydrogen filling time for FCV is required to be within 3 minutes.
　ＦＣＶ用水素燃料容器は、軽量化のためにアルミライナーや樹脂ライナーを用いた複合容器（ＣＦＲＰ容器）が使用されている。しかし、樹脂ライナー層やＣＦＲＰ層の熱伝導率が低いため、ＦＣＶへ水素を７０ＭＰａまで高速充填した場合に水素の温度がＣＦＲＰ（炭素繊維強化樹脂）容器の許容温度を超えてしまう。 The FCV hydrogen fuel container uses a composite container (CFRP container) using an aluminum liner or a resin liner for weight reduction. However, since the thermal conductivity of the resin liner layer or the CFRP layer is low, the hydrogen temperature exceeds the allowable temperature of the CFRP (carbon fiber reinforced resin) container when hydrogen is rapidly filled up to 70 MPa in FCV.
　例えば、１５０Ｌの樹脂ライナー製ＣＦＲＰ容器に水素を７０ＭＰａまで８５℃を超えないように充填しようとすれば５０分以上の時間がかかる。また、同容器に３分充填を目指した高速充填を行うと、１０ＭＰａで８５℃に到達してしまい、フル充填時の４０％も水素を充填することができない。 For example, it takes 50 minutes or more to fill a 150 L CFRP container made of resin liner with hydrogen up to 70 MPa so as not to exceed 85 ° C. Moreover, if high-speed filling aiming at 3 minutes filling to the same container is performed, it will reach 85 degreeC at 10 MPa, and 40% at the time of full filling cannot be filled with hydrogen.
　このため、水素ステーションでは水素の充填直前にプレクール装置を使用し、水素を冷却する手法を取り入れている。しかし、３分で充填するためには、－５０℃での冷却能力が必要であると言われており、設備コスト、ランニングコストが上昇し、水素供給コストも上昇し、せっかく環境に配慮した燃料だとしても、普及に足かせがかかってしまう。例えば、特許文献１では、水素を活性炭で貯蔵し燃料電池に使用することが記載されている。しかしながら、これらは一般的な活性炭であり、また、活性炭を容器に導入する効果的な方法については言及されていない。 For this reason, the hydrogen station uses a pre-cooling device just before filling with hydrogen to introduce a method of cooling the hydrogen. However, in order to fill in 3 minutes, it is said that a cooling capacity at -50 ° C is required, which increases the equipment cost and running cost, and also increases the hydrogen supply cost. Even so, the spread will be hampered. For example, Patent Document 1 describes that hydrogen is stored in activated carbon and used in a fuel cell. However, these are general activated carbons, and there is no mention of an effective method for introducing the activated carbon into the container.
特開２００１－２８７９０５号公報JP 2001-287905 A
　上記のような状況下、できるだけ多くの水素を貯蔵でき、水素充填時においては、従来の充填よりも簡便な充填ができる水素貯蔵用複合容器が求められている。よって本発明は、できるだけ多くの水素を貯蔵でき、水素充填時においてプレクールを必要としない、もしくは、プレクールが少なくてすみ、従来よりも簡便に水素を充填できる水素貯蔵用複合容器、及び、その複合容器への水素充填方法を提供することを目的とする。 Under such circumstances, there is a demand for a composite container for storing hydrogen that can store as much hydrogen as possible, and that can be filled more easily than conventional filling when filling with hydrogen. Therefore, the present invention is capable of storing as much hydrogen as possible and does not require precooling at the time of hydrogen filling, or requires less precooling, and a hydrogen storage composite container that can be charged with hydrogen more easily than before, and the composite It aims at providing the hydrogen filling method to a container.
　上記目的を達成するために、本発明は、ライナーを繊維および樹脂で補強した複合容器であって、内部に、温度３０３Ｋ、水素の平衡圧３５ＭＰａであるときの水素吸蔵能が０．５質量％以上である多孔性炭素材料を５～２５体積％存在させた、水素貯蔵用複合容器を提供する。上記ライナーの材質はいかなるものであっても良い。 In order to achieve the above object, the present invention is a composite container in which a liner is reinforced with fibers and a resin, and has a hydrogen storage capacity of 0.5 mass% when the temperature is 303 K and the hydrogen equilibrium pressure is 35 MPa. Provided is a hydrogen storage composite container in which 5 to 25% by volume of the above porous carbon material is present. Any material may be used for the liner.
　本発明の水素貯蔵用複合容器によれば、内部に上記多孔性炭素材料を存在させることで、水素貯蔵量を増大させることができるとともに、多孔性炭素材料が熱を吸収することで、水素温度の上昇を抑えることができる。そのため、本発明の水素貯蔵用複合容器は、多くの水素を貯蔵できることに加え、プレクール設備を不要とする、あるいはプレクール能力を削減することが可能となる。本発明の水素貯蔵用複合容器は、ＦＣＶ用水素燃料用容器として好適である。なお、温度上昇を抑える目的であれば、単純な吸熱材を用いてもよいが、その場合は水素貯蔵量を維持するために容器の容量を増やす必要がある。これを避けるために、本発明においては吸熱材に水素吸蔵能を持たせることで、容器容量を変えることなく目的を果たすことができる。 According to the composite container for hydrogen storage of the present invention, the hydrogen storage amount can be increased by allowing the porous carbon material to exist inside, and the porous carbon material absorbs heat, so that the hydrogen temperature can be increased. Can be suppressed. Therefore, in addition to being able to store a large amount of hydrogen, the composite container for hydrogen storage according to the present invention can eliminate the need for precool equipment or reduce the precool capacity. The composite container for hydrogen storage of the present invention is suitable as a container for hydrogen fuel for FCV. For the purpose of suppressing the temperature rise, a simple endothermic material may be used. In that case, it is necessary to increase the capacity of the container in order to maintain the hydrogen storage amount. In order to avoid this, in the present invention, the endothermic material can be provided with a hydrogen storage capability, so that the object can be achieved without changing the container capacity.
　ここで、上記多孔性炭素材料は、ＢＥＴ法により測定される比表面積が８００～３０００ｍ２／ｇ、ミクロ孔容積が０．５～２ｃｃ／ｇであるものであることが好ましい。上記多孔性炭素材料は、２回以上の賦活工程を経て形成された植物原料由来の活性炭、または、Ｌｉ原子を含む活性炭であることが好ましい。 Here, the porous carbon material preferably has a specific surface area measured by the BET method of 800 to 3000 m 2 / g and a micropore volume of 0.5 to 2 cc / g. The porous carbon material is preferably an activated carbon derived from a plant raw material formed through two or more activation steps or an activated carbon containing Li atoms.
　本発明はまた、ライナーを繊維および樹脂で補強した複合容器であって、内部に、温度３０３Ｋ、水素の平衡圧３５ＭＰａであるときの水素吸蔵能が０．５質量％以上である多孔性炭素材料を５～２５体積％存在させた水素貯蔵用複合容器に、上記多孔性炭素材料の熱容量が水素の吸着熱と吸着されない水素の圧縮熱とを吸収することで、容器内に充填された水素の温度が上記樹脂の耐熱温度以下となるように、水素を圧縮し充填する水素充填方法を提供する。 The present invention is also a composite container in which a liner is reinforced with fibers and a resin, and has a hydrogen storage capacity of 0.5% by mass or more when the temperature is 303 K and the hydrogen equilibrium pressure is 35 MPa. In the composite container for hydrogen storage in which 5 to 25% by volume of hydrogen is present, the heat capacity of the porous carbon material absorbs the adsorption heat of hydrogen and the compression heat of hydrogen that is not adsorbed. Provided is a hydrogen filling method in which hydrogen is compressed and filled so that the temperature is equal to or lower than the heat resistant temperature of the resin.
　本発明によれば、多量に水素を貯蔵でき、水素充填時においてプレクールを必要としない、もしくは、プレクールが少なくてすみ、従来よりも簡便に水素を充填できる水素貯蔵用複合容器を提供することができる。また、本発明によれば、上記水素貯蔵用複合容器を用い、プレクールを必要としない、もしくは、プレクールが少なくてすみ、従来よりも簡便に多量の水素を充填できる水素充填方法を提供することができる。 According to the present invention, it is possible to provide a hydrogen storage composite container that can store a large amount of hydrogen, does not require precooling when filling with hydrogen, or requires less precooling, and can be charged with hydrogen more easily than before. it can. In addition, according to the present invention, it is possible to provide a hydrogen filling method that uses the above composite container for hydrogen storage, does not require precooling, or requires less precooling, and can easily fill a larger amount of hydrogen than before. it can.
本発明の一実施形態に係る水素貯蔵用複合容器の概略部分断面図である。It is a general | schematic fragmentary sectional view of the composite container for hydrogen storage which concerns on one Embodiment of this invention.
　以下、図面を参照しながら本発明の好適な実施形態について詳細に説明する。なお、図面の寸法比率は図示の比率に限られるものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In addition, the dimensional ratio of drawing is not restricted to the ratio of illustration.
　（水素貯蔵用複合容器）
　図１は、本発明の一実施形態に係る水素貯蔵用複合容器の概略部分断面図である。図１に示すように、水素貯蔵用複合容器１は、ライナー２を繊維および樹脂４で補強した容器部６を備える。 (Composite container for hydrogen storage)
FIG. 1 is a schematic partial cross-sectional view of a hydrogen storage composite container according to an embodiment of the present invention. As shown in FIG. 1, the hydrogen storage composite container 1 includes a container portion 6 in which a liner 2 is reinforced with fibers and a resin 4.
　ライナー２は、両端部をドーム状（半球状）に形成した円柱体であり、内部は中空をなし、少なくとも一方の端部に、水素を充填するための構造を有するものである。両端部以外の円柱状の部位は、一定の直径で形成されていてもよいが、中央部の直径が多少大きい構造であってもよい。ライナー２を構成する材料としては、ステンレス、アルミニウム等の金属、あるいはポリエチレン等のプラスチックなど一定の強度が得られるものであればいかなるものであっても良い。 The liner 2 is a cylindrical body having both ends formed in a dome shape (hemispherical shape), the inside is hollow, and has a structure for filling at least one end with hydrogen. The cylindrical portions other than the both end portions may be formed with a constant diameter, but may have a structure in which the diameter of the central portion is somewhat larger. The material constituting the liner 2 may be any material as long as a certain strength can be obtained, such as a metal such as stainless steel or aluminum, or a plastic such as polyethylene.
　ライナー２の少なくとも一端に設けられた水素を充填する構造は、一般的に口金１２と、ライナー２の外部にノズル状に伸びた水素供給管１４とで構成される。水素供給管１４は、必要に応じ、図１に示すようにライナー２の内部にも伸びていてもよい。その場合、水素供給管１４のライナー２内部に伸びた部分（内部ノズル）は、例えば、無数の穴が開いたフィルター状の管となっており、この内部ノズルによって均一に水素が吹き込まれるようにしてあってもよい。 The structure filled with hydrogen provided at at least one end of the liner 2 is generally composed of a base 12 and a hydrogen supply pipe 14 extending in a nozzle shape outside the liner 2. The hydrogen supply pipe 14 may also extend inside the liner 2 as shown in FIG. In that case, the portion (inner nozzle) extending into the liner 2 of the hydrogen supply pipe 14 is, for example, a filter-like pipe having numerous holes, and hydrogen is blown uniformly by the inner nozzle. May be.
　本発明においてライナー２は、繊維および樹脂４で補強される。補強の方法は任意であるが、容器部６は、例えば、樹脂で含浸した炭素繊維をライナー２に巻装することによって、製造される。巻装の方法は任意であり、例えば、あらかじめ樹脂を炭素繊維等に含浸してあるトウプリプレグを使用したり、炭素繊維を巻装時に液体状の樹脂に含浸し使用するなどの用法がある。使用する樹脂は一般的に熱硬化性の樹脂であり、典型的なものはエポキシ樹脂である。巻装の方法は、フープ巻き、ヘリカル巻き等により連続的に密に巻回する方法が挙げられる。こうした樹脂は、ライナー２に巻装した後、加熱され硬化される。 In the present invention, the liner 2 is reinforced with fibers and resin 4. Although the method of reinforcement is arbitrary, the container part 6 is manufactured by winding the carbon fiber impregnated with resin around the liner 2, for example. The winding method is arbitrary. For example, a tow prepreg in which a carbon fiber or the like is impregnated with a resin in advance is used, or a liquid resin is impregnated in a liquid resin at the time of winding. The resin used is generally a thermosetting resin, and a typical one is an epoxy resin. Examples of the winding method include a method of winding continuously and densely by hoop winding, helical winding or the like. Such a resin is wound around the liner 2 and then heated and cured.
　繊維および樹脂４を含む補強層の厚みは、水素充填圧力によって異なるが、一般的には５ｍｍ～１０ｃｍであり、ライナー２の直径の３％～２０％程度である。 The thickness of the reinforcing layer including the fibers and the resin 4 varies depending on the hydrogen filling pressure, but is generally 5 mm to 10 cm and is about 3% to 20% of the diameter of the liner 2.
　本発明においては、こうしたライナー２を繊維および樹脂４で補強した容器部６内に、温度が３０３Ｋであり、水素の平衡圧が３５ＭＰａであるときに、水素吸蔵能が０．５質量％以上、好ましくは、０．６～３質量％である多孔性炭素材料８を、５～２５体積％存在させるものである。 In the present invention, when the temperature is 303 K and the hydrogen equilibrium pressure is 35 MPa in the container portion 6 in which such a liner 2 is reinforced with fibers and the resin 4, the hydrogen storage capacity is 0.5 mass% or more, Preferably, the porous carbon material 8 of 0.6 to 3% by mass is present in an amount of 5 to 25% by volume.
　かかる多孔性炭素材料８は、一般的なものでも良いが、特に好ましいものは、水素の吸蔵能が高い、２回以上の賦活工程を経て形成された植物原料由来の活性炭である。さらに、多孔性炭素材料８は、Ｌｉ原子を含む活性炭であることが好ましい。 Such a porous carbon material 8 may be a general one, but particularly preferred is an activated carbon derived from a plant raw material having a high hydrogen storage capacity and formed through two or more activation steps. Furthermore, the porous carbon material 8 is preferably activated carbon containing Li atoms.
　２回以上の賦活工程を経て形成された植物原料由来の活性炭とは、ヤシガラ、モミガラ、竹、木材チップ等の植物原料を炭化させた後に２回以上賦活させたものである。こうして得られる活性炭は、表面積が大きく水素を吸蔵しやすいミクロ孔の発達した活性炭であり、炭素以外の植物由来の成分が好ましく作用することによって、高度な水素吸蔵能を有する活性炭である。 The activated carbon derived from plant raw materials formed through two or more activation steps is obtained by activating two or more times after carbonizing plant raw materials such as coconut shells, rice straw, bamboo, and wood chips. The activated carbon thus obtained is activated carbon having a large surface area and easy to occlude hydrogen and having developed micropores, and is an activated carbon having a high level of hydrogen occlusion ability by the action of plant-derived components other than carbon.
　本発明においては、植物原料をそのまま、あるいは３００～１，０００℃の温度で炭化処理したものを第一段の賦活処理に供する。必要に応じ、賦活の前に植物原料の粉砕を行っても良い。 In the present invention, the plant raw material as it is or carbonized at a temperature of 300 to 1,000 ° C. is subjected to the first stage activation treatment. If necessary, the plant material may be pulverized before activation.
　賦活方法は、水蒸気賦活、アルカリ賦活等があり、どのような賦活方法でもよいが、特に好ましいのは、アルカリ金属、アルカリ土類金属の水酸化物を使用した賦活方法である。 The activation method includes steam activation, alkali activation and the like, and any activation method may be used, but an activation method using an alkali metal or alkaline earth metal hydroxide is particularly preferable.
　例えば、植物原料を炭化して得られた炭化物１質量部に対して、アルカリ金属水酸化物を０．２～５質量部加え、温度５００～８００℃程度で０．１～５時間程度処理を行う。この際、アルカリ金属水酸化物として特に好ましいのは、水酸化カリウムである。この後、未反応のアルカリ金属水酸化物を洗浄によって除去する。洗浄では、必要に応じ塩酸等を使用してアルカリを除去することも可能である。その後、乾燥させた後、再度賦活する。この際は、水蒸気賦活をすることも良いし、同じようにアルカリ金属水酸化物を反応させても良い。この際は、水酸化カリウムを使用しても良いし、ミクロ孔の形成がしやすいことから、水酸化リチウムを使用してもよく、いくつかのアルカリ金属水酸化物を併用しても良い。この後、同様に、必要に応じて洗浄して、乾燥させる。さらに賦活を繰り返しても良い。 For example, 0.2 to 5 parts by mass of an alkali metal hydroxide is added to 1 part by mass of a carbide obtained by carbonizing a plant raw material, and the treatment is performed at a temperature of about 500 to 800 ° C. for about 0.1 to 5 hours. Do. At this time, potassium hydroxide is particularly preferable as the alkali metal hydroxide. Thereafter, unreacted alkali metal hydroxide is removed by washing. In washing, it is possible to remove alkali using hydrochloric acid or the like as necessary. Then, after making it dry, it activates again. At this time, steam activation may be performed, or an alkali metal hydroxide may be reacted in the same manner. In this case, potassium hydroxide may be used, and since it is easy to form micropores, lithium hydroxide may be used, or some alkali metal hydroxides may be used in combination. Thereafter, similarly, it is washed if necessary and dried. Further, activation may be repeated.
　こうして製造された植物原料由来の活性炭は、ＢＥＴ法により測定される比表面積が８００～３０００ｍ２／ｇ、ミクロ孔容積が０．５～２ｃｃ／ｇである。 The activated carbon derived from plant raw materials thus produced has a specific surface area measured by the BET method of 800 to 3000 m 2 / g and a micropore volume of 0.5 to 2 cc / g.
　植物には、炭化しても炭素以外の成分が含まれており、水素との相互作用により、単なる活性炭よりも水素吸蔵能が優れるものである。一方で、炭素以外の成分は、賦活を妨げることがあり、二回以上賦活することにより、好ましい賦活と、細孔の形成が可能となるものである。 Plants contain components other than carbon even when carbonized, and have better hydrogen storage capacity than mere activated carbon due to interaction with hydrogen. On the other hand, components other than carbon may hinder activation, and by activating twice or more, preferable activation and pore formation are possible.
　Ｌｉ原子を含む活性炭とは、一般の活性炭において、表面の含酸素官能基にＬｉイオンを結合（担持）させたものである。ここで、含酸素官能基は、フェノール性水酸基、キノン基、ラクトン性カルボキシル基及びカルボキシル基からなる群より選択される少なくとも一種であることが好ましい。 The activated carbon containing Li atoms is a general activated carbon in which Li ions are bonded (supported) to oxygen functional groups on the surface. Here, the oxygen-containing functional group is preferably at least one selected from the group consisting of a phenolic hydroxyl group, a quinone group, a lactone carboxyl group, and a carboxyl group.
　多孔性炭素材の表面の一部と、その表面に形成されたフェノール性水酸基の構造の一例を、下記化学式（１）に示す。
Figure JPOXMLDOC01-appb-C000001
 An example of the structure of a part of the surface of the porous carbon material and the phenolic hydroxyl group formed on the surface is shown in the following chemical formula (1).
Figure JPOXMLDOC01-appb-C000001
　多孔性炭素材の表面の一部と、その表面に形成されたキノン基の構造の一例を、下記化学式（２）に示す。
Figure JPOXMLDOC01-appb-C000002
 An example of the structure of a part of the surface of the porous carbon material and the quinone group formed on the surface is shown in the following chemical formula (2).
Figure JPOXMLDOC01-appb-C000002
　多孔性炭素材の表面の一部と、その表面に形成されたラクトン性カルボキシル基の構造の一例を、下記化学式（３）に示す。
Figure JPOXMLDOC01-appb-C000003
 An example of the structure of a part of the surface of the porous carbon material and the lactone carboxyl group formed on the surface is shown in the following chemical formula (3).
Figure JPOXMLDOC01-appb-C000003
　多孔性炭素材の表面の一部と、その表面に形成されたカルボキシル基の構造の一例を、下記化学式（４）に示す。
Figure JPOXMLDOC01-appb-C000004
 An example of the structure of a part of the surface of the porous carbon material and the carboxyl group formed on the surface is shown in the following chemical formula (4).
Figure JPOXMLDOC01-appb-C000004
　下記化学式（５）は、含酸素官能基としてカルボキシル基と水酸基が形成された多孔性炭素材の表面の一部にＬｉが結合していない状態を示す。下記化学式（６）は、下記化学式（５）に示す多孔性炭素材の表面の一部にＬｉが結合している状態を示す。
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
 The following chemical formula (5) shows a state in which Li is not bonded to a part of the surface of the porous carbon material in which carboxyl groups and hydroxyl groups are formed as oxygen-containing functional groups. The following chemical formula (6) shows a state where Li is bonded to a part of the surface of the porous carbon material shown in the following chemical formula (5).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
　上記化学式（５）及び（６）に示すように、Ｌｉが、含酸素官能基に含まれる酸素に結合し、ＬｉＯ基が形成されていることが好ましい。ＬｉＯ基は、水素分子を強く吸着する性質を有する。したがって、ＬｉＯ基が多孔性炭素材の表面に形成されることによって、水素吸蔵材における水素分子の吸着密度が増加して、水素吸蔵能が従来に比べて著しく向上する。 As shown in the above chemical formulas (5) and (6), it is preferable that Li is bonded to oxygen contained in the oxygen-containing functional group to form a LiO group. The LiO group has a property of strongly adsorbing hydrogen molecules. Therefore, when the LiO group is formed on the surface of the porous carbon material, the adsorption density of hydrogen molecules in the hydrogen storage material is increased, and the hydrogen storage capacity is significantly improved as compared with the conventional case.
　含酸素官能基は、上述した官能基の中でも、フェノール性水酸基であることが特に好ましい。水素吸蔵能を向上させるためには、フェノール性水酸基に結合したＬｉのほうが他の含酸素官能基に結合したＬｉよりも好ましい。 The oxygen-containing functional group is particularly preferably a phenolic hydroxyl group among the functional groups described above. In order to improve the hydrogen storage capacity, Li bonded to a phenolic hydroxyl group is more preferable than Li bonded to other oxygen-containing functional groups.
　水素吸蔵材に含まれるＬｉの量は、０．１～３ｍｍｏｌ／ｇ程度であればよい。ただし、水素吸蔵材に含まれるＬｉの量はこの範囲に限定されない。水素吸蔵材へのＬｉの導入量が大きいほど水素吸蔵能が向上する。 The amount of Li contained in the hydrogen storage material may be about 0.1 to 3 mmol / g. However, the amount of Li contained in the hydrogen storage material is not limited to this range. The larger the amount of Li introduced into the hydrogen storage material, the better the hydrogen storage capacity.
　こうしたＬｉを担持した活性炭は、上述の２回以上賦活をした植物原料由来の活性炭を使用しても良い。 Such activated carbon carrying Li may be activated carbon derived from plant materials activated two or more times as described above.
　また、多孔性炭素材料８としては、繊維状原料の賦活物を用いてもよい。繊維状原料の賦活物は、賦活されたＰＡＮ（ポリアクリロニトリル）であることが好ましい。繊維状原料の賦活物は、上述した植物原料由来の活性炭と同様に、「炭化」及び「賦活」の２工程を含む製造方法により製造される。繊維状原料の賦活物も、２回以上賦活させたものであることが好ましい。また、繊維状原料の賦活物も、上述したようにＬｉを担持させたものであることが好ましい。こうして製造される繊維状原料の賦活物も、ＢＥＴ法により測定される比表面積が８００～３０００ｍ２／ｇ、ミクロ孔容積が０．５～２ｃｃ／ｇである。 Further, as the porous carbon material 8, an activated product of a fibrous raw material may be used. The activated material of the fibrous raw material is preferably activated PAN (polyacrylonitrile). The activated material of the fibrous raw material is manufactured by a manufacturing method including two steps of “carbonization” and “activation” in the same manner as the activated carbon derived from the plant raw material described above. It is preferable that the activated fiber material is also activated two or more times. Moreover, it is preferable that the activated material of a fibrous raw material is what carried Li as mentioned above. The fibrous raw material activation product thus produced also has a specific surface area measured by the BET method of 800 to 3000 m 2 / g and a micropore volume of 0.5 to 2 cc / g.
　本発明においては、こうした多孔性炭素材料８をライナー２の内部に存在させる。存在させ方は任意であるが、例えば、多孔性炭素材料８の粉末を蒸発の可能な有機溶媒に分散させた後、紙などの柔軟性のあるシートにキャストし、それを端部ドーム部材と一体成形された気体が表面から噴出自在な内部ノズルに巻きつけた後、円柱の側面ともう一方の端部ドーム部材を成形するなどの方法がある。また、多孔性炭素材料８の粉末をキャストしたシートを、ライナー２の円柱部分や端部ドーム部材の内面に貼り付けてもよい。 In the present invention, such a porous carbon material 8 is present inside the liner 2. For example, after the powder of the porous carbon material 8 is dispersed in an evaporable organic solvent, it is cast into a flexible sheet such as paper, and the end dome member is used. There is a method of forming a side surface of the cylinder and the other end dome member after the integrally formed gas is wound around an internal nozzle that can be ejected from the surface. Moreover, you may affix the sheet | seat which cast the powder of the porous carbon material 8 on the cylindrical part of the liner 2, or the inner surface of an edge dome member.
　この後、ライナー２は、繊維および樹脂４で補強され、本発明の水素貯蔵用複合容器１となる。 Thereafter, the liner 2 is reinforced with fibers and resin 4 to form the composite container 1 for hydrogen storage of the present invention.
　複合容器１内部の多孔性炭素材料８の量は、ライナー２内部の水素が存在する空間で実質的に水素を貯蔵する場所の容積の５～２５体積％であることがよい。 The amount of the porous carbon material 8 inside the composite container 1 is preferably 5 to 25% by volume of the volume of the place where hydrogen is stored in the space where the hydrogen inside the liner 2 exists.
　ただし、多孔性炭素材料８の量は、水素を充填するときに発熱する熱量と、多孔性炭素材料８の吸収する熱量と、水素を吸蔵する際に発熱する熱量との関係において、複合容器１内に充填された水素の温度が樹脂の耐熱温度以下、または法令等に定められた温度以下となるように、調節することが望ましい。 However, the amount of the porous carbon material 8 depends on the relationship between the amount of heat generated when hydrogen is charged, the amount of heat absorbed by the porous carbon material 8, and the amount of heat generated when hydrogen is occluded. It is desirable to adjust so that the temperature of the hydrogen charged in the inside is lower than the heat resistant temperature of the resin or lower than the temperature stipulated by laws and regulations.
　すなわち、水素を高圧で充填すると発熱し、容器の最高使用基準温度を超えてしまうことがある。本発明においては、多孔性炭素材料８の熱容量によってそれを防ぐことができる。 That is, when hydrogen is charged at a high pressure, heat is generated and the maximum use temperature of the container may be exceeded. In the present invention, this can be prevented by the heat capacity of the porous carbon material 8.
　また、多孔性炭素材料８に一定の量の水素が吸着すると吸着熱が生じ、吸着された分、圧縮熱が減少する。すなわち、
　（水素の圧縮による熱放出量）＋（水素の多孔性炭素材料８への吸着による熱放出量）
　　－（水素の多孔性炭素材料８への吸着による体積減少による熱放出量の減少）
　　－（多孔性炭素材料８の熱吸収による熱放出量の減少）
　　－（自然冷却による大気への熱の放出）
の熱量からの発熱により、上昇した温度が、樹脂の耐熱温度（安全温度）以下となるように、多孔性炭素材料８を存在させるのが良い。この際、別途規格によって、使用できる温度が決まっていれば、それに合わせて多孔性炭素材料８の量を決定することがよい。 Further, when a certain amount of hydrogen is adsorbed on the porous carbon material 8, heat of adsorption is generated, and the heat of compression is reduced by the amount adsorbed. That is,
(Heat release amount due to hydrogen compression) + (Heat release amount due to adsorption of hydrogen to porous carbon material 8)
-(Reduction in heat release due to volume reduction due to adsorption of hydrogen to porous carbon material 8)
-(Reduction in heat release due to heat absorption of porous carbon material 8)
-(Release of heat to the atmosphere by natural cooling)
It is preferable that the porous carbon material 8 is present so that the temperature raised by the heat generated from the amount of heat is less than the heat resistant temperature (safe temperature) of the resin. At this time, if the temperature that can be used is determined according to a standard, the amount of the porous carbon material 8 is preferably determined in accordance with the temperature.
　この際に必要な多孔性炭素材料８の量は、例えば、現在の自動車工業会の基準で、７０ＭＰａを３分充填とすると、貯蔵する場所の容積の５～２５体積％、好ましくは８～１５体積％であり、かつ、必要な水素吸蔵能が０．５質量％以上、好ましくは０．６～３質量％の範囲である。この範囲を外れると、十分な温度低下がなされない。 The amount of the porous carbon material 8 required at this time is, for example, 5 to 25% by volume, preferably 8 to 15% of the volume of the storage place when 70 MPa is filled for 3 minutes according to the current standards of the automobile industry association. The required hydrogen storage capacity is 0.5% by mass or more, preferably in the range of 0.6 to 3% by mass. If the temperature is out of this range, the temperature is not lowered sufficiently.
　また、図１に示すように、ライナー２の内部の表面に一定の量で多孔性炭素材料８を存在させれば、その熱容量による温度上昇の抑制効果に加え、断熱効果も生じるため好ましい。この製造方法は任意である。例えば、ライナー２内部の表面に樹脂等のバインダーを用いて多孔性炭素材料８を付着させてもよいし、先と同じように、多孔性炭素材料８の粉末を蒸発の可能な有機溶媒に分散させた後、ライナー２内部の表面にキャストしたのち、通気性のある網状の材料で押さえることで保持しても良い。 Further, as shown in FIG. 1, it is preferable that the porous carbon material 8 is present in a certain amount on the inner surface of the liner 2 because a heat insulation effect is produced in addition to the effect of suppressing the temperature rise due to the heat capacity. This manufacturing method is arbitrary. For example, the porous carbon material 8 may be attached to the inner surface of the liner 2 using a binder such as a resin, and the powder of the porous carbon material 8 is dispersed in an evaporable organic solvent as before. Then, after being cast on the surface inside the liner 2, it may be held by pressing with a breathable net-like material.
　本実施例では、水素の温度を、自動車工業会の安全基準の８５℃以下に保てるように検討した。なお、この温度では使用された樹脂（耐熱温度１２０度以上）になんらの影響もないことを確認した。 In this example, the temperature of hydrogen was examined so as to be kept at 85 ° C. or less which is the safety standard of the automobile industry association. At this temperature, it was confirmed that there was no influence on the resin used (heat resistant temperature of 120 ° C. or higher).
（実施例１）
　１μｍ以下の無数の穴が開いたフィルター状の水素供給管を備えたアルミライナー製ＣＦＲＰ容器を作製した。作製した容器の仕様は、内容量１０Ｌ、内径１６０ｍｍ、長さ５２０ｍｍ、最小破裂圧力１８０ＭＰａであった。 Example 1
A CFRP container made of an aluminum liner provided with a filter-like hydrogen supply pipe having innumerable holes of 1 μm or less was produced. The specifications of the produced container were an internal volume of 10 L, an inner diameter of 160 mm, a length of 520 mm, and a minimum burst pressure of 180 MPa.
　ＰＡＮ系繊維状炭素材料を６００℃で焼成し、焼成後の繊維状炭素材料１ｇあたり０．０８ｍｏｌのＫＯＨを加え、不活性ガス雰囲気下、６００℃で２時間賦活処理した。その後再度、賦活後の繊維状炭素材料１ｇあたり０．１ｍｏｌのＫＯＨにより、不活性ガス雰囲気下、７５０℃で再度賦活処理を行なった。得られた多孔性炭素材料は、ＢＥＴ法により測定される比表面積が２２８１ｍ２／ｇ、ミクロ孔容積が１．２７６ｃｃ／ｇであった。得られた多孔性炭素材料の水素吸蔵能は、水素の平衡圧３５ＭＰａ、温度３０℃（３０３Ｋ）で０．６質量％であった。 The PAN-based fibrous carbon material was baked at 600 ° C., 0.08 mol of KOH was added per 1 g of the baked fibrous carbon material, and activation treatment was performed at 600 ° C. for 2 hours in an inert gas atmosphere. Thereafter, the activation treatment was again performed at 750 ° C. in an inert gas atmosphere with 0.1 mol of KOH per 1 g of the fibrous carbon material after activation. The obtained porous carbon material had a specific surface area measured by BET method of 2281 m 2 / g and a micropore volume of 1.276 cc / g. The hydrogen storage capacity of the obtained porous carbon material was 0.6 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
　この多孔性炭素材料を作製した容器に４ｋｇ（１７．７体積％）導入し、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素の温度は８５℃、充填された水素量は０．２８ｋｇであった。 4 kg (17.7% by volume) was introduced into the container in which the porous carbon material was produced, and hydrogen at an initial temperature of 25 ° C. was rapidly filled to 70 MPa in 3 minutes. The temperature of the hydrogen in the container immediately after filling was 85 ° C., and the amount of filled hydrogen was 0.28 kg.
（実施例２）
　ＰＡＮ系繊維状炭素材料を６００℃で焼成し、焼成後の繊維状炭素材料１ｇあたり０．０８ｍｏｌのＫＯＨを加え、不活性ガス雰囲気下、６００℃で２時間賦活処理した。その後、賦活後の繊維状炭素材料１ｇあたり０．１ｍｏｌのＬｉＯＨにより、不活性ガス雰囲気下、７５０℃で再度賦活処理を行い、材料にＬｉを導入した。導入されたＬｉ量は０．３質量％であった。得られた多孔性炭素材料は、ＢＥＴ法により測定される比表面積が２１２８ｍ２／ｇ、ミクロ孔容積が１．３１６ｃｃ／ｇであった。得られた多孔性炭素材料の水素吸蔵能は、水素の平衡圧３５ＭＰａ、温度３０℃（３０３Ｋ）で１．２質量％であった。 (Example 2)
The PAN-based fibrous carbon material was baked at 600 ° C., 0.08 mol of KOH was added per 1 g of the baked fibrous carbon material, and activation treatment was performed at 600 ° C. for 2 hours in an inert gas atmosphere. Then, activation treatment was again performed at 750 ° C. in an inert gas atmosphere with 0.1 mol of LiOH per 1 g of the fibrous carbon material after activation, and Li was introduced into the material. The amount of introduced Li was 0.3% by mass. The obtained porous carbon material had a specific surface area measured by the BET method of 2128 m 2 / g and a micropore volume of 1.316 cc / g. The hydrogen storage capacity of the obtained porous carbon material was 1.2 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
　この多孔性炭素材料を実施例１と同じ仕様の容器に４ｋｇ（１６．５体積％）導入し、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素の温度は８４℃、充填された水素量は０．３０ｋｇであった。 4 kg (16.5% by volume) of this porous carbon material was introduced into a container having the same specifications as in Example 1, and hydrogen at an initial temperature of 25 ° C. was rapidly filled to 70 MPa in 3 minutes. The temperature of the hydrogen in the container immediately after filling was 84 ° C., and the amount of filled hydrogen was 0.30 kg.
（実施例３）
　もみがらを５００℃で焼成し、焼成後のもみがら１ｇあたり０．０５ｍｏｌのＫＯＨを加え、不活性ガス雰囲気下、７５０℃で１時間賦活処理した。その後、賦活後のもみがら１ｇあたり０．１ｍｏｌのＬｉＯＨにより、不活性ガス雰囲気下、７５０℃で再度賦活処理を行い、材料にＬｉを導入した。導入されたＬｉ量は０．２質量％であった。得られた多孔性炭素材料は、ＢＥＴ法により測定される比表面積が２３４８ｍ２／ｇ、ミクロ孔容積が１．１５８ｃｃ／ｇであった。得られた多孔性炭素材料の水素吸蔵能は、水素の平衡圧３５ＭＰａ、温度３０℃（３０３Ｋ）で１．０質量％であった。 (Example 3)
The rice husk was baked at 500 ° C., 0.05 mol of KOH was added per 1 g of the baked rice husk, and activated at 750 ° C. for 1 hour in an inert gas atmosphere. Thereafter, activation treatment was performed again at 750 ° C. in an inert gas atmosphere with 0.1 mol of LiOH per 1 g of chaff after activation, and Li was introduced into the material. The amount of introduced Li was 0.2% by mass. The obtained porous carbon material had a specific surface area measured by BET method of 2348 m 2 / g and a micropore volume of 1.158 cc / g. The hydrogen storage capacity of the obtained porous carbon material was 1.0 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
　この多孔性炭素材料を実施例１と同じ仕様の容器に４ｋｇ（１８．０体積％）導入し、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素温度は８３℃、充填された水素量は０．２９ｋｇであった。 4 kg (18.0% by volume) of this porous carbon material was introduced into a container having the same specifications as in Example 1, and hydrogen at an initial temperature of 25 ° C. was charged at a high speed to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 83 ° C., and the amount of filled hydrogen was 0.29 kg.
（実施例４）
　コークスを７００℃で焼成し、焼成後のコークス１ｇあたり０．０７ｍｏｌのＫＯＨを加え、不活性ガス雰囲気下、７５０℃で２時間賦活処理した。その後、賦活後のコークス１ｇあたり０．１ｍｏｌのＮａＯＨにより、不活性ガス雰囲気下、７５０℃で再度賦活処理を行った。得られた多孔性炭素材料は、ＢＥＴ法により測定される比表面積が２０４８ｍ２／ｇ、ミクロ孔容積が１．２０８ｃｃ／ｇであった。得られた多孔性炭素材料の水素吸蔵能は、水素の平衡圧３５ＭＰａ、温度３０℃（３０３Ｋ）で０．５質量％であった。 Example 4
Coke was baked at 700 ° C., 0.07 mol of KOH was added per 1 g of the baked coke, and activation treatment was performed at 750 ° C. for 2 hours in an inert gas atmosphere. Thereafter, the activation treatment was performed again at 750 ° C. in an inert gas atmosphere with 0.1 mol of NaOH per 1 g of coke after activation. The obtained porous carbon material had a specific surface area measured by the BET method of 2048 m 2 / g and a micropore volume of 1.208 cc / g. The hydrogen storage capacity of the obtained porous carbon material was 0.5 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
　この多孔性炭素材料を実施例１と同じ仕様の容器に４ｋｇ（１６．８体積％）導入し、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素温度は８５℃、充填された水素量は０．２８ｋｇであった。 4 kg (16.8% by volume) of this porous carbon material was introduced into a container having the same specifications as in Example 1, and hydrogen at an initial temperature of 25 ° C. was rapidly filled to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 85 ° C., and the amount of filled hydrogen was 0.28 kg.
（実施例５）
　やしがらを７００℃で焼成し、焼成後のやしがら１ｇあたり０．０５ｍｏｌのＫＯＨを加え、不活性ガス雰囲気下、７５０℃で２時間賦活処理した。その後、賦活後のやしがら１ｇあたり０．１ｍｏｌのＬｉＯＨにより、不活性ガス雰囲気下、７５０℃で再度賦活処理を行い、材料にＬｉを導入した。導入されたＬｉ量は０．３質量％であった。得られた多孔性炭素材料は、ＢＥＴ法により測定される比表面積が２１１８ｍ２／ｇ、ミクロ孔容積が１．４０２ｃｃ／ｇであった。得られた多孔性炭素材料の水素吸蔵能は、水素の平衡圧３５ＭＰａ、温度３０℃（３０３Ｋ）で１．３質量％であった。 (Example 5)
The coconut palm was baked at 700 ° C., 0.05 mol of KOH was added per 1 g of the baked coconut palm, and activation treatment was performed at 750 ° C. for 2 hours in an inert gas atmosphere. Then, activation treatment was performed again at 750 ° C. in an inert gas atmosphere with 0.1 mol of LiOH per gram of activated palm, and Li was introduced into the material. The amount of introduced Li was 0.3% by mass. The obtained porous carbon material had a specific surface area measured by the BET method of 2118 m 2 / g and a micropore volume of 1.402 cc / g. The hydrogen storage capacity of the obtained porous carbon material was 1.3 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
　この多孔性炭素材料を実施例１と同じ仕様の容器に４ｋｇ（１７．５体積％）導入し、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素温度は８５℃、充填された水素量は０．３１ｋｇであった。 4 kg (17.5% by volume) of this porous carbon material was introduced into a container having the same specifications as in Example 1, and hydrogen at an initial temperature of 25 ° C. was rapidly filled to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 85 ° C., and the amount of filled hydrogen was 0.31 kg.
（比較例１）
　市販の脱臭用粉末活性炭を実施例１と同じ仕様の容器に４ｋｇ（１８．２体積％）導入し、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素温度は９８℃、充填された水素量は０．２６ｋｇであった。この活性炭の水素吸蔵能は、水素の平衡圧３５ＭＰａ、温度３０℃（３０３Ｋ）で０．０質量％であった。 (Comparative Example 1)
4 kg (18.2% by volume) of commercially available activated carbon for deodorization was introduced into a container having the same specifications as in Example 1, and hydrogen at an initial temperature of 25 ° C. was charged at a high speed to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 98 ° C., and the amount of filled hydrogen was 0.26 kg. The hydrogen storage capacity of the activated carbon was 0.0 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
（比較例２）
　実施例１と同じ仕様の容器に多孔性炭素材料を入れずに、初期温度２５℃の水素を上記実施例１と同じ速度（１．６ｇ／秒）で高速充填したところ、圧力が３ＭＰａに達した時点で水素温度が８５℃となったため、充填を中止した。再度充填速度を落とし（０．５ｇ／秒）水素を充填したところ、２分、１０ＭＰａで８５℃となった。このときの水素充填量は０．０６ｋｇであった。 (Comparative Example 2)
When a porous carbon material was not put in a container having the same specifications as in Example 1 and hydrogen at an initial temperature of 25 ° C. was charged at a high speed at the same rate (1.6 g / sec) as in Example 1, the pressure reached 3 MPa. At that time, the hydrogen temperature reached 85 ° C., so the filling was stopped. When the filling rate was reduced again (0.5 g / sec) and hydrogen was charged, the temperature reached 85 ° C. at 10 MPa for 2 minutes. The hydrogen filling amount at this time was 0.06 kg.
（実施例６）
　やしがらを７００℃で焼成し、焼成後のやしがら１ｇあたり０．０５ｍｏｌのＫＯＨを加え、不活性ガス雰囲気下、７５０℃で２時間賦活処理した。その後、洗浄の後、４５０℃になった時点で、第二段の酸素賦活処理を、酸素濃度５体積％の窒素との混合ガス（流速３Ｎｍ３／ｈ）により行った。得られた多孔性炭素材料は、ＢＥＴ法により測定される比表面積が１９８８ｍ２／ｇ、ミクロ孔容積が１．３０５ｃｃ／ｇであった。得られた多孔性炭素材料の水素吸蔵能は、水素の平衡圧３５ＭＰａ、温度３０℃（３０３Ｋ）で１．４質量％であった。 (Example 6)
The coconut palm was baked at 700 ° C., 0.05 mol of KOH was added per 1 g of the baked coconut palm, and activation treatment was performed at 750 ° C. for 2 hours in an inert gas atmosphere. Then, after cleaning, when the temperature reached 450 ° C., the second stage oxygen activation treatment was performed with a mixed gas (flow rate: 3 Nm 3 / h) with nitrogen having an oxygen concentration of 5% by volume. The obtained porous carbon material had a specific surface area measured by the BET method of 1988 m 2 / g and a micropore volume of 1.305 cc / g. The hydrogen storage capacity of the obtained porous carbon material was 1.4 mass% at an equilibrium pressure of hydrogen of 35 MPa and a temperature of 30 ° C. (303 K).
　この多孔性炭素材料を実施例１と同じ仕様の容器に４ｋｇ（１７．７体積％）導入し、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素温度は８４℃、充填された水素量は０．３１ｋｇであった。 4 kg (17.7% by volume) of this porous carbon material was introduced into a container having the same specifications as in Example 1, and hydrogen at an initial temperature of 25 ° C. was rapidly filled to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 84 ° C., and the amount of filled hydrogen was 0.31 kg.
（実施例７）
　実施例１と同じ仕様の容器に対し、実施例４の多孔性炭素材料４ｋｇ（１６．８体積％）をアセトンに溶解して容器の内表面にできるだけ均一になるようキャストした後、アセトンを除去した。その後、不織布で覆い多孔性炭素材料を保持した。この容器内に、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素温度は８５℃、充填された水素量は０．３１ｋｇであったが、外部への熱伝導が緩やかであることを確認した。 (Example 7)
For a container having the same specifications as in Example 1, 4 kg (16.8% by volume) of the porous carbon material of Example 4 was dissolved in acetone and cast on the inner surface of the container as uniformly as possible, and then acetone was removed. did. Thereafter, the porous carbon material was held by covering with a nonwoven fabric. In this container, hydrogen with an initial temperature of 25 ° C. was filled at high speed to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 85 ° C., and the amount of filled hydrogen was 0.31 kg, but it was confirmed that the heat conduction to the outside was gentle.
（実施例８）
　実施例１と同じ仕様の容器の内表面にできるだけ均一になるように、実施例５の多孔性炭素材料４ｋｇ（１７．５体積％）をアセトンに溶解して容器の内表面にできるだけ均一になるようキャストした後、アセトンを除去した。その後、不織布で覆い多孔性炭素材料を保持した。この容器内に、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素温度は８４℃、充填された水素量は０．３１ｋｇであったが、外部への熱伝導が緩やかであることを確認した。 (Example 8)
4 kg (17.5 vol%) of the porous carbon material of Example 5 was dissolved in acetone so as to be as uniform as possible on the inner surface of the container so as to be as uniform as possible on the inner surface of the container having the same specifications as in Example 1. After casting, acetone was removed. Thereafter, the porous carbon material was held by covering with a nonwoven fabric. In this container, hydrogen with an initial temperature of 25 ° C. was filled at high speed to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 84 ° C., and the amount of filled hydrogen was 0.31 kg, but it was confirmed that the heat conduction to the outside was gentle.
（実施例９）
　実施例１と同じ仕様の容器の内表面にできるだけ均一になるように、実施例６の多孔性炭素材料４ｋｇ（１７．７体積％）をアセトンに溶解して容器の内表面にできるだけ均一になるようキャストした後、アセトンを除去した。その後、不織布で覆い多孔性炭素材料を保持した。この容器内に、初期温度２５℃の水素を３分間で７０ＭＰａまで高速充填した。充填直後の容器内水素温度は８４℃、充填された水素量は０．３１ｋｇであったが、外部への熱伝導が緩やかであることを確認した。 Example 9
In order to be as uniform as possible on the inner surface of the container having the same specifications as in Example 1, 4 kg (17.7% by volume) of the porous carbon material of Example 6 was dissolved in acetone to be as uniform as possible on the inner surface of the container. After casting, acetone was removed. Thereafter, the porous carbon material was held by covering with a nonwoven fabric. In this container, hydrogen with an initial temperature of 25 ° C. was filled at high speed to 70 MPa in 3 minutes. The hydrogen temperature in the container immediately after filling was 84 ° C., and the amount of filled hydrogen was 0.31 kg, but it was confirmed that the heat conduction to the outside was gentle.
　本発明の水素貯蔵用複合容器は、来る水素社会において、水素を輸送のインフラに使用し、あるいは水素自動車に備え、エンジンの燃料のタンクとして使用できる。また、家庭用燃料電池に用いる水素の貯蔵容器として、かつてのプロパンガスボンベのような使用も可能である。すなわち複雑で経費のかかる設備を持たない水素供給場所でも使用することができ、水素のエネルギーとしての普及に大きく貢献するものである。本発明を実施することで、環境に貢献でき、継続性社会の実現の一助となることは明らかである。 The composite container for hydrogen storage according to the present invention can be used as a fuel tank for an engine in a hydrogen society where hydrogen is used for transportation infrastructure or in a hydrogen vehicle. In addition, it can be used as a propane gas cylinder as a hydrogen storage container for a household fuel cell. In other words, it can be used in a hydrogen supply place that does not have complicated and expensive equipment, and greatly contributes to the spread of hydrogen as energy. It is clear that the implementation of the present invention can contribute to the environment and contribute to the realization of a continuity society.
　１…水素貯蔵用複合容器、２…ライナー、４…繊維および樹脂、６…容器部、８…多孔性炭素材料、１２…口金、１４…水素供給管。 DESCRIPTION OF SYMBOLS 1 ... Composite container for hydrogen storage, 2 ... Liner, 4 ... Fiber and resin, 6 ... Container part, 8 ... Porous carbon material, 12 ... Base, 14 ... Hydrogen supply pipe | tube.

Claims (5)

  1. 　ライナーを繊維および樹脂で補強した複合容器であって、内部に、温度３０３Ｋ、水素の平衡圧３５ＭＰａであるときの水素吸蔵能が０．５質量％以上である多孔性炭素材料を５～２５体積％存在させた、水素貯蔵用複合容器。 A composite container in which a liner is reinforced with fibers and a resin, and 5 to 25 volumes of a porous carbon material having a hydrogen storage capacity of 0.5 mass% or more when the temperature is 303 K and the hydrogen equilibrium pressure is 35 MPa. % Hydrogen storage composite container.
  2. 　前記多孔性炭素材料が、ＢＥＴ法により測定される比表面積が８００～３０００ｍ２／ｇ、ミクロ孔容積が０．５～２ｃｃ／ｇであるものである、請求項１記載の水素貯蔵用複合容器。 The composite container for hydrogen storage according to claim 1, wherein the porous carbon material has a specific surface area measured by the BET method of 800 to 3000 m 2 / g and a micropore volume of 0.5 to 2 cc / g. .
  3. 　前記多孔性炭素材料が、２回以上の賦活工程を経て形成された植物原料由来の活性炭である、請求項１又は２記載の水素貯蔵用複合容器。 The hydrogen storage composite container according to claim 1 or 2, wherein the porous carbon material is activated carbon derived from a plant raw material formed through two or more activation steps.
  4. 　前記多孔性炭素材料が、Ｌｉ原子を含む活性炭である、請求項１～３のいずれか一項に記載の水素貯蔵用複合容器。 The composite container for hydrogen storage according to any one of claims 1 to 3, wherein the porous carbon material is activated carbon containing Li atoms.
  5. 　ライナーを繊維および樹脂で補強した複合容器であって、内部に、温度３０３Ｋ、水素の平衡圧３５ＭＰａであるときの水素吸蔵能が０．５質量％以上である多孔性炭素材料を５～２５体積％存在させた水素貯蔵用複合容器に、前記多孔性炭素材料の熱容量が水素の吸着熱と吸着されない水素の圧縮熱とを吸収することで、容器内に充填された水素の温度が前記樹脂の耐熱温度以下となるように、水素を圧縮し充填する水素充填方法。 A composite container in which a liner is reinforced with fibers and a resin, and 5 to 25 volumes of a porous carbon material having a hydrogen storage capacity of 0.5 mass% or more when the temperature is 303 K and the hydrogen equilibrium pressure is 35 MPa. %, The heat capacity of the porous carbon material absorbs the heat of adsorption of hydrogen and the heat of compression of hydrogen that is not adsorbed, so that the temperature of the hydrogen filled in the container can be reduced. A hydrogen filling method in which hydrogen is compressed and filled so as to be equal to or lower than the heat resistant temperature.
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