JP5761968B2 - Composite container for hydrogen storage and hydrogen filling method - Google Patents

Description

  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.

  Currently, in consideration of the environment, development of a fuel cell vehicle (FCV) that uses hydrogen as energy and generates and runs on a fuel cell 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, there are several problems to be solved in order to store in a container. 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.

  As the FCV hydrogen fuel container, a composite container (CFRP container) using an aluminum liner or a resin liner is used for weight reduction. However, since the thermal conductivity of the resin liner layer and the CFRP layer is low, the hydrogen temperature exceeds the allowable temperature of the CFRP container when hydrogen is rapidly filled into 70 MPaFCV.

  For example, it takes 50 minutes or more to fill a 150 L CFRP container made of a 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.

  For this reason, at the hydrogen station, a precooling device is used immediately before filling with hydrogen, and a method of cooling hydrogen is adopted. However, in order to fill in 3 minutes, it is said that a cooling capacity at -50 ° C is required, and the equipment cost and running cost increase, the hydrogen supply cost also increases, and environmentally friendly fuel. 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.

JP 2001-287905 A

  Under the circumstances as described above, there is a demand for a hydrogen storage composite container 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.

  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.

  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.

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.

  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 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.

  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.

It is a general | schematic fragmentary sectional view of the composite container for hydrogen storage which concerns on one Embodiment of this invention.

  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.

(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.

  The liner 2 is a cylindrical body having both end portions formed in a dome shape (hemisphere), the inside is hollow, and has a structure for filling at least one end portion 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.

  In the present invention, the liner 2 is reinforced with fibers and a 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.

  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.

  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.

  The 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 a plant material formed through two or more activation steps is activated by activating two or more times after carbonizing plant materials such as coconut shells, rice straw, bamboo, and wood chips. The activated carbon thus obtained is an activated carbon having a large surface area and capable of storing hydrogen, and having developed micropores, and is an activated carbon having a high level of hydrogen storage capacity when a plant-derived component other than carbon acts favorably.

  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.

  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.

  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.

The plant material-derived activated carbon thus produced has a specific surface area of 800 to 3000 m ² / g and a micropore volume of 0.5 to ² cc / g measured by the BET method.

  Plants contain components other than carbon even when carbonized, and have better hydrogen storage capacity than simple 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. 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.

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).

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).

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).

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).

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).

  As shown in the 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.

  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.

  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.

  As the activated carbon supporting Li, activated carbon derived from a plant material activated two or more times as described above may be used.

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 material activation product thus produced also has a specific surface area of 800 to 3000 m ² / g and a micropore volume of 0.5 to ² cc / g as measured by the BET method.

  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.

  Thereafter, the liner 2 is reinforced with the fibers and the resin 4 to form the hydrogen storage composite container 1 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.

  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.

  That is, when hydrogen is charged at a high pressure, heat is generated and the maximum use reference 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.

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 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 the 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, assuming that 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, and 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.

  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 insulating 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.

  In this example, it was examined so that it could 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 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.

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).

  4 kg (17.7% by volume) of 4 kg (17.7% by volume) was introduced into the container in which the porous carbon material was produced, and high-temperature filling with hydrogen at an initial temperature of 25 ° C. to 70 MPa was performed 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.

(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).

  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.

(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).

  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 rapidly filled 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.

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).

  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.

(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).

  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.

(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).

(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.

(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).

  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.

(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.

(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.

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.

  The composite container for hydrogen storage of 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 is provided in a hydrogen vehicle. Further, it can be used as a conventional propane gas cylinder for a domestic hydrogen 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.

  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 (7)

  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. The composite container for hydrogen storage according to claim 1, wherein the porous carbon material is present on a surface inside the liner. A hydrogen supply pipe is provided at at least one end of the liner, the hydrogen supply pipe extends into the liner, and a portion of the hydrogen supply pipe that extends into the liner has a filter-like pipe having innumerable holes. The composite container for hydrogen storage according to claim 1 or 2. Said porous carbon material, the specific surface area measured by the BET method is intended 800~3000m ² / g, micropore volume is 0.5~2cc / g, any one of claims 1 to 3 A composite container for hydrogen storage as described in 1. The composite container for hydrogen storage according to any one of claims 1 to 4, wherein the porous carbon material is activated carbon derived from a plant material formed through two or more activation steps. The composite container for hydrogen storage according to any one of claims 1 to 5 , wherein the porous carbon material is activated carbon containing Li atoms. The hydrogen storage composite container according to any one of claims 1 to 6 , wherein the heat capacity of the porous carbon material absorbs the adsorption heat of hydrogen and the compression heat of hydrogen that is not adsorbed, thereby filling the container. A hydrogen filling method in which hydrogen is compressed and filled so that the temperature of the produced hydrogen is lower than the heat resistant temperature of the resin.

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