JP2008075697A - Hydrogen storing apparatus, and supplying hydrogen method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen storing apparatus, which can store a sufficient quantity of hydrogen, and also is suitable for carrying and supplying hydrogen. <P>SOLUTION: The hydrogen storing apparatus comprises a hydrogen storing vessel 10 filled with hydrogen adsorptive porous material 12, a heat insulating vacuum vessel 20 surrounding the hydrogen storing vessel 10 so as to form a heat insulating vacuum layer 22 around the hydrogen storing vessel 10, and a cooling pipe 30 which is arranged so as to pass through the inside of the hydrogen storing vessel 10, and makes a refrigerant of 120K or less flow in the case of adsorbing hydrogen into the hydrogen adsorptive porous material 12. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrogen storage device and a hydrogen supply method.

  Hydrogen is widely used in various industrial fields including the oil refining and chemical industries. In particular, since hydrogen is the only substance that is generated after combustion, water has attracted attention as a clean fuel that does not pollute the environment, and research on fuel cells using hydrogen as a fuel has been actively conducted.

  However, hydrogen gas has a problem that it is difficult to store and transport the hydrogen gas as it is because of its large volume per calorie and large energy required for liquefaction (see Non-Patent Document 1). Accordingly, there is a need for a technique for efficiently transporting and storing hydrogen in a mobile object such as a fuel cell vehicle or when a fuel cell is used as a distributed power source. Currently, as a technique for transporting and storing hydrogen, a method of transporting and storing in the state of high-pressure gas or liquid hydrogen, a method of transporting and storing using a hydrogen storage alloy or a hydrogen storage material, and the like have been proposed.

  As a method and apparatus for storing hydrogen, for example, Patent Document 1 below describes a hydrogen storage container using a carbon-based adsorbent that adsorbs and desorbs hydrogen. Patent Document 2 listed below describes a hydrogen gas storage method for cooling hydrogen gas to generate liquefied hydrogen gas. Patent Document 3 listed below describes a gas storage method in which a gas such as hydrogen gas is liquefied and stored in carbon nanotubes or the like by a capillary phenomenon. Furthermore, Patent Document 4 below describes a hydrogen storage device that stores hydrogen as liquefied hydrogen and absorbs boil-off hydrogen gas into a hydrogen storage alloy.

JP 2003-65497 A JP 2001-12663 A JP 2002-128501 A JP 09-264498 A Kobayashi, “Quarterly Energy Comprehensive Engineering”, Vol. 25, No. 4, 2003, p. 73-87

  However, in the methods and apparatuses described in Patent Documents 2 to 4, since hydrogen is stored as liquefied hydrogen, although the amount of hydrogen stored is excellent, the vaporization (boil-off) caused by the low heat of vaporization of hydrogen occurs. There are problems and problems that require containers that can withstand ultra-low temperatures. Moreover, since the liquefaction temperature of hydrogen is an extremely low temperature of −253 ° C., it is difficult to handle, the energy required for liquefaction is enormous, and there is a problem that energy efficiency is low as a whole.

  A method of chemically storing hydrogen using a hydrogen storage alloy is also known as an effective method. However, the hydrogen storage amount of the hydrogen storage alloy is usually about 3%, and there is a problem that the hydrogen storage amount is still insufficient for use in a moving body and the weight increases excessively. Furthermore, since a large amount of heat is required when releasing hydrogen from the hydrogen storage alloy, it has disadvantages such as low energy efficiency and complicated system.

  On the other hand, a method of physically storing hydrogen using a hydrogen storage material as described in Patent Document 1 has been attracting attention because of its easy handling and high energy efficiency. However, although the hydrogen storage container described in Patent Document 1 is suitable for storage in a certain place, there is a problem that it is not necessarily suitable for transporting the container and supplying hydrogen.

  The present invention has been made in view of the above-described problems of the prior art, and provides a hydrogen storage device capable of obtaining a sufficient amount of hydrogen storage without liquefying hydrogen and also suitable for transporting and supplying hydrogen. An object of the present invention is to provide a method of supplying hydrogen using

  In order to achieve the above object, the present invention provides a hydrogen storage container filled with a porous hydrogen storage material and a vacuum surrounding the hydrogen storage container so that a vacuum heat insulating layer is formed around the hydrogen storage container. A heat insulating container; and a cooling pipe that is provided through the inside of the hydrogen storage container and that allows a refrigerant having a temperature of 120 K or less to flow when the porous hydrogen storage material stores hydrogen. A hydrogen storage device is provided.

  The porous hydrogen storage material physically adsorbs hydrogen, and can exhibit a higher hydrogen storage capacity than a hydrogen storage alloy that chemically adsorbs hydrogen depending on the storage and release conditions of hydrogen. In addition, the porous hydrogen storage material has a property that the hydrogen storage amount increases as the temperature is low, and the hydrogen storage material is stored while circulating a coolant having a temperature of 120 K or less in the cooling pipe passing through the hydrogen storage container. By doing so, a sufficient hydrogen storage amount can be obtained.

  In the hydrogen storage device of the present invention, since the hydrogen storage container is surrounded by the vacuum heat insulating container, the temperature in the hydrogen storage container is kept constant by the vacuum heat insulating layer around the hydrogen storage container. . Further, since the cooling pipe is provided through the hydrogen storage container, the cooling effect is enhanced and a good hydrogen storage amount can be obtained. Such a structure of the cooling pipe and the vacuum heat insulating structure facilitate the transportation of the hydrogen storage device, and enables a large amount of hydrogen to be efficiently transported at a constant temperature.

  Furthermore, in the hydrogen storage device of the present invention, the fluid passing therethrough can be easily changed by providing the cooling pipe. Therefore, when supplying hydrogen to a supply destination such as a fuel cell vehicle, it is possible to easily supply hydrogen by circulating a heat medium having a temperature higher than that of the refrigerant used for storing hydrogen in the cooling pipe. It becomes possible. Moreover, when hydrogen is occluded using a porous hydrogen occlusion material, and the supply destination is filled with hydrogen at a high pressure, heat is generated as the hydrogen is compressed. Therefore, for example, when supplying hydrogen to a supplier at room temperature, it is necessary to cool the hydrogen (precool), and it takes time for cooling, so that it is difficult to supply hydrogen in a short time. Had. On the other hand, according to the hydrogen storage device of the present invention, by adjusting the temperature of the heat medium passed through the cooling pipe at the time of hydrogen supply to a sufficiently low temperature, low-temperature hydrogen can be supplied to a filling device such as a compressor, It is possible to efficiently supply hydrogen in a short time without performing the above.

  Further, in the hydrogen storage device of the present invention, the porous hydrogen storage material may be a fibrous carbon material comprising 0.02-0.3 moles of KOH, LiOH and NaOH per gram of the fibrous carbon material. It is preferable that at least one selected base is added and activated at 400 to 1100 ° C. in an inert gas atmosphere. By using such a porous hydrogen storage material, the amount of hydrogen stored can be significantly improved, and a larger amount of hydrogen can be efficiently transported.

  Furthermore, in the hydrogen storage device of the present invention, the refrigerant is preferably liquefied natural gas or liquid nitrogen. Here, the temperature of liquefied natural gas is about 110K, and the temperature of liquid nitrogen is about 77K. These refrigerants are easily available, and a sufficient cooling effect of the hydrogen storage material can be obtained, so that a sufficient hydrogen storage amount can be obtained.

  The present invention also uses the hydrogen storage device of the present invention to store the refrigerant of 120K or less in the cooling pipe to store hydrogen in the porous hydrogen storage material, and 173 to 173 in the cooling pipe. There is provided a hydrogen supply method characterized by comprising a supply step of supplying a hydrogen to a supply destination by allowing a heat medium having a temperature of 373 K to flow and releasing hydrogen from the porous hydrogen storage material.

  According to this hydrogen supply method, by using the hydrogen storage device of the present invention and supplying hydrogen by circulating a heating medium having the above temperature in the cooling pipe, a fuel cell vehicle or the like without performing precooling of hydrogen, etc. It is possible to efficiently supply hydrogen to the supply destination of the battery in a short time.

  Moreover, it is preferable that the hydrogen supply method of this invention further has the transport step which transports the said hydrogen storage apparatus in the state which extracted the said refrigerant | coolant from the inside of the said cooling pipe after the said occlusion step. In this way, by transporting the hydrogen storage device with the refrigerant removed from the cooling pipe, there is no need for a refrigerant that continues to flow into the cooling pipe, and a large amount of hydrogen can be efficiently transported to demand areas in a lighter state. It becomes possible to supply to the supplier. Even in a state where the refrigerant is not circulated in the cooling pipe, the temperature increase in the hydrogen storage container is sufficiently suppressed by the vacuum heat insulating layer.

  According to the present invention, it is possible to provide a hydrogen storage device suitable for transporting and supplying hydrogen and a hydrogen supply method using the same, while a sufficient hydrogen storage amount can be obtained without liquefying hydrogen.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the hydrogen storage device of the present invention. As shown in FIG. 1, the hydrogen storage device 1 includes a hydrogen storage container 10 filled with a porous hydrogen storage material 12 for storing hydrogen, and a vacuum heat insulating layer 22 formed around the hydrogen storage container 10. As shown, the vacuum heat insulating container 20 surrounding the hydrogen storage container 10 and the inside of the hydrogen storage container 10 are provided, and a refrigerant having a temperature of 120K or less is used when the porous hydrogen storage material 12 stores hydrogen. And a cooling pipe 30 through which 32 is circulated. Further, the hydrogen storage device 1 is provided with a hydrogen flow path 14 serving as a hydrogen inlet / outlet with respect to the hydrogen storage container 10. The hydrogen flow path 14 is provided with an open / close valve for controlling the flow of hydrogen, and the cooling pipe 30 is provided with an open / close valve for controlling the flow of refrigerant.

  Although it does not specifically limit as hydrogen stored in the hydrogen storage apparatus 1, For example, hydrocarbon gas fuels, such as natural gas and liquefied petroleum gas (LPG), hydrocarbon liquid fuels, such as kerosene and naphtha, and gasification of coal etc. A hydrogen-containing gas obtained by using a fuel or the like as a raw material and performing only steam reforming, partial oxidation reaction, or subsequent CO shift reaction can be used. Further, hydrogen gas obtained by electrolysis of water, a method using renewable energy such as biomass or sunlight, or the like can also be used. The hydrogen to be stored is preferably purified hydrogen having a purity of preferably 99.9% or more, more preferably 99.99% or more, still more preferably 99.999% or more, and particularly preferably 99.9999% or more.

  The obtained hydrogen is preferably cooled in advance before being introduced into the hydrogen storage container 10. In that case, the obtained hydrogen is cooled to 150 K or less, more preferably 110 K or less, using liquefied natural gas (LNG), liquid nitrogen, or the like. At this time, it is desirable to convert from ortho-type hydrogen to para-type hydrogen that is stable at low temperature stepwise using a catalyst such as iron or chromium.

  The porous hydrogen storage material 12 is not particularly limited as long as it can physically adsorb hydrogen. For example, activated carbon, carbon nanotube, carbon nanofiber, carbon fiber, bamboo charcoal, and activation thereof And the like. These carbon-based materials may support metals such as Pt, Pd, Ni, Al, Mg, Ti, Ta, Ag, Au, Ru, and Rh. Examples of the porous hydrogen storage material 12 other than carbon-based materials include zeolite, molecular sieve, and porous metal complex. Among these porous hydrogen storage materials 12, a porous hydrogen storage material made of a carbon-based material is preferable.

  Further, as the porous hydrogen storage material 12, in particular, the fibrous carbon material is at least one selected from the group consisting of 0.02-0.3 moles of KOH, LiOH and NaOH per gram of the fibrous carbon material. It is preferable to add the base and activate at 400 to 1100 ° C. in an inert gas atmosphere.

  Here, the base used for the activation treatment is preferably KOH. Moreover, it does not specifically limit as an inert gas, For example, nitrogen, argon, etc. can be used.

  The amount of the base to be added needs to be 0.02 to 0.3 mol, preferably 0.03 to 0.2 mol, with respect to 1 g of the fibrous carbon material before the activation treatment. In addition, also when using 2 or more types of bases, it is necessary for the total amount of a base to be 0.02-0.3 mol with respect to 1 g of fibrous carbon materials before an activation process. When the amount of this base is less than 0.02 mol, activation does not proceed sufficiently and the hydrogen storage amount tends to decrease. On the other hand, if the amount of the base exceeds 0.3 mol, the activation yield tends to decrease, which is not practical.

  It is preferable that the temperature of an activation process is 400-1100 degreeC. When this temperature is less than 400 ° C., the reaction does not proceed sufficiently and the hydrogen storage amount tends to decrease. On the other hand, when the temperature exceeds 1100 ° C., the yield of the fibrous carbon material obtained after activation tends to be remarkably lowered, which is not practical. In addition, it is preferable that the temperature of an activation process is 500-1000 degreeC, and it is more preferable that it is 650-900 degreeC.

The porous hydrogen storage material 12 as described above preferably has a specific surface area by the BET method of 500 to 4000 m ² / g, more preferably 1000 to 3800 m ² / g. When the specific surface area is less than 500 m ² / g, it tends to be difficult to sufficiently secure an effective hydrogen storage amount. On the other hand, if the specific surface area exceeds 4000 m ² / g, the yield of the porous hydrogen storage material 12 obtained through the activation treatment or the like tends to be remarkably lowered, which is not practical.

  The porous hydrogen storage material 12 is preferably heat-treated at 150 ° C. or higher and lower than the carbonization temperature in an inert gas atmosphere such as vacuum or argon before storing hydrogen. When heat treatment is not performed or when the temperature of the heat treatment is less than 150 ° C., molecules such as water adsorbed on the porous hydrogen storage material 12 tend to inhibit hydrogen storage, which is not preferable. . On the other hand, when the temperature of the heat treatment is equal to or higher than the temperature at the time of carbonization, the crystal structure of carbon may change, and the hydrogen storage capacity may be reduced. A more desirable heat treatment temperature is 150 to 1500 ° C.

  The hydrogen storage container 10 and the vacuum heat insulation container 20 are constituted by pressure-resistant containers. Examples of the material of these containers include steel, aluminum, and carbon fiber reinforced plastic (CFRP). Among them, CFRP is preferable. Moreover, as a material of the liner of a CFRP container, aluminum, steel, etc. are mentioned, for example.

  The vacuum heat insulating layer 22 is formed by bringing the space defined between the hydrogen storage container 10 and the vacuum heat insulating container 20 into a vacuum state. In addition, it is more preferable that the vacuum heat insulating layer 22 has a structure in which a vacuum heat insulating sheet having a high heat insulating effect is sandwiched.

  The refrigerant 32 is a fluid that circulates in the cooling pipe 30 when at least hydrogen is stored in the porous hydrogen storage material 12. The refrigerant 32 is not particularly limited as long as it is a fluid having a temperature of 120 K or less, and examples thereof include liquefied natural gas (LNG) and liquid nitrogen. Among these, liquefied natural gas (LNG) is preferable from the viewpoint that the cold energy discarded as exhaust heat when vaporizing can be effectively used. Moreover, although the temperature of the refrigerant | coolant 32 needs to be 120K or less, it is more preferable that it is 70-120K.

  The refrigerant 32 can be supplied to the hydrogen storage device 1 from, for example, a refrigerant storage container that stores the refrigerant 32.

  The cooling pipe 30 is provided through the inside of the hydrogen storage container 10, and at least when the hydrogen is stored in the porous hydrogen storage material 12, the refrigerant 32 is circulated in the pipe to cause the porous hydrogen storage material. 12 is for cooling. When releasing the hydrogen stored in the porous hydrogen storage material 12, a desired heat medium having a temperature higher than that of the refrigerant 32 is circulated in the cooling pipe 30 instead of the refrigerant 32.

  The material of the cooling pipe 30 is not particularly limited, and examples thereof include steel and aluminum alloy. In addition, the shape of the cooling pipe 30 is not particularly limited as long as it can sufficiently exchange heat with the porous hydrogen storage material 12. Examples of the shape of the cooling pipe 30 include a shape in which a pipe having a cylindrical cross section is spirally stretched. Moreover, in order to improve the efficiency of heat exchange, you may attach a fin around piping.

  The hydrogen flow path 14 is a hydrogen flow path when hydrogen is introduced into the hydrogen storage container 10 and when hydrogen is released from the hydrogen storage container 10. The material of the hydrogen channel 14 is not particularly limited, and examples thereof include steel and aluminum alloy.

  In the hydrogen storage device 1, the hydrogen storage container 10 is fixed to the vacuum heat insulating container 20 via the cooling pipe 30 and the hydrogen flow path 14. In addition, in order to fix the hydrogen storage container 10 more stably, you may fix the hydrogen storage container 10 to the vacuum heat insulation container 20 using the fixing member which has heat insulation.

  Hydrogen is stored in the hydrogen storage device 1 of the present invention by introducing hydrogen into the hydrogen storage container 10 from the hydrogen flow path 14 while allowing the refrigerant 32 of 120 K or less to flow through the cooling pipe 30. It can be performed by causing the system hydrogen storage material 12 to store.

  Here, the hydrogen pressure during hydrogen storage in the hydrogen storage container is preferably 0.3 to 5.0 MPa, more preferably 0.5 to 3.0 MPa, and 0.7 to 1.0 MPa. It is particularly preferred that If the hydrogen pressure is less than 0.3 MPa, the hydrogen storage amount tends to decrease, and if it exceeds 5.0 MPa, there is a tendency to cause a problem in pressure resistance. Considering the durability of the hydrogen storage container, the hydrogen pressure is desirably 1.0 MPa or less.

  Next, the hydrogen supply method of the present invention will be described. The hydrogen supply method of the present invention uses the hydrogen storage device 1 of the present invention to store the hydrogen in the porous hydrogen storage material 12 by allowing the refrigerant 32 of 120 K or less to flow through the cooling pipe 30 to store the hydrogen. And a supply step of supplying a hydrogen to the supply destination by allowing a heat medium having a temperature of 173 to 373 K to flow through the cooling pipe 30 to release hydrogen from the porous hydrogen storage material 12. It is a characteristic method. Moreover, you may have further the transport step which transports the hydrogen storage apparatus 1 to a desired demand place after the said occlusion step.

  In the storage step, hydrogen is stored in the porous hydrogen storage material 12 as described above using the hydrogen storage device 1 of the present invention described above. Thereby, hydrogen is stored in the hydrogen storage container 10.

  In the transport step, the hydrogen storage device 1 is transported to a demand place such as a hydrogen station by a carrier.

  Although it does not specifically limit as a carrier, A trailer, a railroad, a ship, etc. can be used. At that time, for example, several hydrogen storage devices 1 (about 4 to 16) are bundled into one set (cylinder unit), and in the case of a trailer, several sets (about 1 to 4 sets) are carried by one unit. . In the demand area, only the trailer or the cylinder unit is placed in the demand area to store hydrogen. In addition, you may supply hydrogen from the hydrogen storage apparatus 1 to the storage tank in a demand place.

  Moreover, in the said transport step, it is preferable to transport the hydrogen storage apparatus 1 in the state which extracted the said refrigerant | coolant 32 from the said cooling pipe 30 for weight reduction. When removing the refrigerant 32 from the cooling pipe 30, for example, the opening / closing valve on the other end side is opened while the opening / closing valve on the one end side of the cooling pipe 30 is closed, and the refrigerant 32 is removed. It is preferable that the inside of the cooling pipe 30 is in a reduced pressure state or a vacuum state by removing the refrigerant 32. Although it is preferable that a heat medium such as outside air does not enter the cooling pipe 30 after the refrigerant 32 is removed, even if such a heat medium enters, the heat medium is immediately cooled. The temperature rise within 10 is sufficiently suppressed. In the transport step, the hydrogen storage device 1 may be transported in a state where the cooling pipe 30 is filled with the refrigerant 32. Even in this case, the refrigerant 32 that continues to flow into the cooling pipe 30 is not necessary, so that weight reduction during transportation can be achieved.

  When supplying hydrogen, the hydrogen is released by depressurization by opening the open / close valve of the hydrogen flow path in the hydrogen storage device 1. In the supply step, the heat medium is further circulated in the cooling pipe 30. To release hydrogen efficiently.

  The heating medium used in the supplying step is not particularly limited as long as it is a fluid having a temperature of 173 to 373 K. Examples thereof include dry air and dry gas such as nitrogen and carbon dioxide. Moreover, although the temperature of a heat medium needs to be 173-373K, it is more preferable that it is 200-323K. By using the heat medium in the above temperature range, hydrogen is released at a sufficiently low temperature, and it is possible to omit precooling during hydrogen supply. In addition, from the viewpoint of supplying low-temperature hydrogen more stably, the upper limit value of the temperature of the heat medium is preferably 283K. Further, the introduced heat medium may be circulated and used by adjusting the temperature of the heat medium.

  When supplying hydrogen to a supply destination such as a fuel cell vehicle, for example, when the pressure is increased by a compressor and hydrogen is supplied at a high pressure, the temperature rises due to adiabatic compression. In order to suppress this, a precool system that cools the compressor and precools hydrogen is conventionally effective. In contrast, according to the hydrogen supply method of the present invention, hydrogen is released using the low-temperature heating medium as described above, and the cooled hydrogen is supplied to the compressor as it is and supplied to the supply destination. Because pre-cooling can be omitted.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Example 1)
In a hydrogen storage container (internal volume: 100 L, manufactured by SUS316L) of a hydrogen storage device having a structure similar to that shown in FIG. 1, as a hydrogen storage material, a fibrous carbon material (manufactured by Toho Tenax Co., Ltd., PYROMEX), 0.07 mol of KOH was added per 1 g of fibrous carbon material, and 40 kg of a porous carbon material (specific surface area 2892 m ² / g) obtained by activation at 500 ° C. for 3 hours in an argon gas atmosphere was filled. Next, while flowing liquid nitrogen (temperature: 77 K) as a refrigerant in the cooling pipe, hydrogen gas was introduced from the hydrogen flow path into the hydrogen storage container until the hydrogen pressure in the hydrogen storage container reached 1.0 MPa. . Thereby, hydrogen was stored in the hydrogen storage material, and hydrogen was stored in the hydrogen storage device. At this time, the hydrogen storage amount was 2.42 kg.

(Example 2)
Hydrogen was stored in the hydrogen storage device in the same manner as in Example 1 except that liquefied natural gas (temperature: 110 K) was used instead of liquid nitrogen (temperature: 77 K) as the refrigerant. At this time, the hydrogen storage amount was 2.06 kg.

(Example 3)
Hydrogen was stored in the hydrogen storage device in the same manner as in Example 1 except that hydrogen gas was introduced into the hydrogen storage container until the hydrogen pressure in the hydrogen storage container reached 3.0 MPa. At this time, the hydrogen storage amount was 3.41 kg.

Example 4
Hydrogen was stored in the hydrogen storage apparatus in the same manner as in Example 2 except that hydrogen gas was introduced into the hydrogen storage container until the hydrogen pressure in the hydrogen storage container reached 3.0 MPa. At this time, the hydrogen storage amount was 2.65 kg.

(Example 5)
The hydrogen storage device was the same as in Example 1 except that the hydrogen storage material was activated carbon (manufactured by Kansai Thermal Chemical Co., Ltd., MAXSORB, specific surface area 2800 m ² / g), and this was filled with 35 kg in a hydrogen storage container. Hydrogen was stored. At this time, the hydrogen storage amount was 1.85 kg.

(Example 6)
Hydrogen was stored in the hydrogen storage device in the same manner as in Example 5 except that liquefied natural gas (temperature: 110K) was used instead of liquid nitrogen (temperature: 77K) as the refrigerant. At this time, the hydrogen storage amount was 1.41 kg.

(Comparative Example 1)
Hydrogen was stored in the hydrogen storage device in the same manner as in Example 1 except that the hydrogen storage material was not filled in the hydrogen storage container. At this time, the hydrogen storage amount was 0.32 kg.

(Comparative Example 2)
A hydrogen storage container (internal volume: 100 L) of a hydrogen storage device having the same structure as that shown in FIG. 1 except that it does not have a cooling pipe is filled with 45 kg of the hydrogen storage material used in Example 1 as a hydrogen storage material. did. Next, at room temperature (temperature: 300 K), hydrogen gas was introduced into the hydrogen storage container from the hydrogen flow path until the hydrogen pressure in the hydrogen storage container reached 1.0 MPa. Thereby, hydrogen was stored in the hydrogen storage material, and hydrogen was stored in the hydrogen storage device. The hydrogen storage amount at this time was 0.12 kg.

(Comparative Example 3)
Hydrogen was stored in the hydrogen storage device in the same manner as in Comparative Example 1 except that hydrogen gas was introduced into the hydrogen storage container until the hydrogen pressure in the hydrogen storage container reached 3.0 MPa. At this time, the hydrogen storage amount was 0.99 kg.

(Comparative Example 4)
Hydrogen was stored in the hydrogen storage device in the same manner as in Comparative Example 2 except that hydrogen gas was introduced into the hydrogen storage container until the hydrogen pressure in the hydrogen storage container reached 3.0 MPa. At this time, the hydrogen storage amount was 0.38 kg.

(Comparative Example 5)
A hydrogen storage device having the same structure as that shown in FIG. 1 was prepared except that the cooling pipe was not provided. Next, hydrogen gas was introduced into the hydrogen storage container (internal volume: 100 L) from the hydrogen flow path at room temperature (temperature: 300 K) until the hydrogen pressure in the hydrogen storage container reached 30.0 MPa. Thereby, hydrogen was stored in the hydrogen storage material, and hydrogen was stored in the hydrogen storage device. The amount of hydrogen stored at this time was 2.37 kg.

  As described above, according to the hydrogen storage devices of Examples 1 to 6, it was confirmed that a sufficient hydrogen storage amount was obtained at a lower pressure than the hydrogen storage devices of Comparative Examples 1 to 5. In addition, the hydrogen storage devices of Examples 1 to 6 can be efficiently transported in a state in which the refrigerant is removed from the inside of the cooling pipe at the time of transportation. Further, when supplying hydrogen to a supply destination such as a fuel cell vehicle, By circulating a heat medium of 173 to 373 K in the cooling pipe, it is possible to efficiently supply hydrogen without performing precooling, and therefore, it is very suitable for transporting and supplying hydrogen. On the other hand, in the hydrogen storage devices of Comparative Examples 1 and 2, since no hydrogen storage material was used, a sufficient amount of hydrogen storage could not be obtained. Further, in the hydrogen storage devices of Comparative Examples 3 to 4, since hydrogen is stored at room temperature, precooling is required when supplying hydrogen to a supply destination such as a fuel cell vehicle. Furthermore, in the hydrogen storage device of Comparative Example 5, since the hydrogen pressure was as high as 30.0 MPa, much energy was required for the pressure increase during hydrogen storage.

It is a schematic cross section which shows suitable one Embodiment of the hydrogen storage apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Hydrogen storage apparatus, 10 ... Hydrogen storage container, 12 ... Porous type hydrogen storage material, 20 ... Vacuum heat insulation container, 22 ... Vacuum heat insulation layer, 30 ... Cooling pipe, 32 ... Refrigerant.

Claims (5)

A hydrogen storage container filled with a porous hydrogen storage material;
A vacuum insulation container surrounding the hydrogen storage container such that a vacuum insulation layer is formed around the hydrogen storage container;
A cooling pipe which is provided through the inside of the hydrogen storage container and allows a refrigerant having a temperature of 120 K or less to flow when storing hydrogen in the porous hydrogen storage material;
A hydrogen storage device comprising:   The porous hydrogen storage material adds at least one base selected from the group consisting of 0.02 to 0.3 mol of KOH, LiOH and NaOH to 1 g of the fibrous carbon material. The hydrogen storage device according to claim 1, wherein the hydrogen storage device is activated at 400 to 1100 ° C. in an inert gas atmosphere.   The hydrogen storage device according to claim 1 or 2, wherein the refrigerant is liquefied natural gas or liquid nitrogen. Occlusion step of storing hydrogen in the porous hydrogen storage material by using the hydrogen storage device according to any one of claims 1 to 3 and circulating the refrigerant of 120K or less in the cooling pipe;
A supply step of causing a heating medium at a temperature of 173 to 373 K to flow through the cooling pipe to release hydrogen from the porous hydrogen storage material and supplying the hydrogen to a supply destination;
The hydrogen supply method characterized by having. 5. The hydrogen supply method according to claim 4, further comprising a transporting step of transporting the hydrogen storage device in a state where the refrigerant is removed from the inside of the cooling pipe after the storage step.

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