JP2008133834A - Hydrogen storage device and hydrogen storage method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen storage device and a hydrogen storage method capable of using a practicable and a lightweight hydrogen storage cartridge, even if using a hydrogen storage material requiring high pressure when storing hydrogen. <P>SOLUTION: This hydrogen storage device stores the hydrogen in the hydrogen storage cartridge 1 filled with the hydrogen storage material capable of storing the hydrogen by pressure, and has a pressure vessel 2 endurable against hydrogen filling pressure, the hydrogen storage cartridge stored in its pressure vessel, a pipe 3 introducing the hydrogen into its hydrogen storage cartridge, and a pipe 14 introducing gas into a clearance between the pressure vessel and the hydrogen storage cartridge, and has a mechanism for controlling a pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrogen storage device and a hydrogen storage method for a hydrogen storage material that stores hydrogen under high pressure.

  As a hydrogen storage material, hydrogen storage alloys have been studied and developed for a long time, but the hydrogen storage rate per unit weight is low, and it has not yet been put into practical use. Various hydrogen storage tanks using hydrogen storage alloys have been studied in Japanese Patent Application Laid-Open Nos. 2000-120996, 2002-122294, 2002-221297, 2002-340430, and the like. Yes.

  In general, hydrogen storage tanks filled with hydrogen storage materials centered on hydrogen storage alloys, which are generally considered, are mostly on-vehicle tanks. In this case, the hydrogen storage tank is fixed to the vehicle, The tank is filled directly. Since the chemical reaction when storing hydrogen is an exothermic reaction, even in the case of a hydrogen storage alloy, a system for cooling the hydrogen storage material is required when storing hydrogen. In consideration of practicality, the hydrogen filling rate is regarded as important. However, as the hydrogen filling rate is increased, the amount of heat generated per unit time increases, and an efficient cooling system becomes important.

  On the other hand, there is a possibility of refilling the entire tank as a form of the hydrogen storage tank. In this case, since the entire tank is replaced, when handling in and out is considered, the size of the hydrogen storage tank including the hydrogen storage material is small and preferably light. In addition, since the hydrogen filling can be performed in another place in advance, there is no strict restriction on the hydrogen filling time compared to the case of the on-vehicle fixed tank.

Recently, several new high-capacity hydrogen storage materials have been proposed, and Patent Document 1 has found a material that exhibits a high storage capacity under a high pressure.
JP 2004-196634 A

  However, when using a material as shown in Patent Document 1, the thickness of the hydrogen storage tank must be designed to be thick enough to withstand the hydrogen filling pressure, resulting in a heavy hydrogen storage tank. I don't get it. For this reason, even if the capacity of the hydrogen storage material is high, there is a problem that an effective hydrogen storage density cannot be obtained as a tank system.

  In view of this point, the present invention provides a hydrogen storage device that can use a practical and lightweight hydrogen storage tank (hereinafter referred to as a hydrogen storage cartridge) even when using a hydrogen storage material that requires a high pressure during storage. It aims at providing the hydrogen storage method.

  As a result of diligent research to solve the above problems, the present inventors have found that even when using a hydrogen storage cartridge with low pressure resistance that can be reduced in weight, the hydrogen can be stored in a pressure resistant container that can withstand the hydrogen filling pressure when storing hydrogen. It is possible to store a hydrogen storage cartridge and apply a hydrogen pressure in the hydrogen storage cartridge, and control the pressure so that the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge does not exceed the design pressure of the hydrogen storage cartridge. The present invention is completed by obtaining knowledge that a hydrogen storage material filled in a hydrogen storage cartridge and requiring a high pressure when storing hydrogen can be used to store hydrogen. It came to.

That is, the present invention provides the following (1) to (6).
(1) A hydrogen storage device for storing hydrogen in a hydrogen storage cartridge filled with a hydrogen storage material capable of storing hydrogen by pressure,
A pressure vessel that can withstand the hydrogen filling pressure, the hydrogen storage cartridge housed in the pressure vessel, a pipe for introducing hydrogen into the hydrogen storage cartridge, and a gas in a gap between the pressure vessel and the hydrogen storage cartridge A hydrogen storage device, comprising: a pipe to be introduced; and a mechanism for controlling a pressure difference between an internal pressure and an external pressure of the hydrogen storage cartridge.
(2) A hydrogen storage device for storing hydrogen in a hydrogen storage cartridge filled with a hydrogen storage material capable of storing hydrogen by pressure and heating,
A pressure- and heat-resistant container that can withstand the hydrogen filling pressure and has an external heating device; the hydrogen storage cartridge housed in the pressure- and heat-resistant container; a pipe for introducing hydrogen into the hydrogen storage cartridge; A hydrogen storage device comprising: a container and a pipe for introducing a gas into a gap between the hydrogen storage cartridge; and a mechanism for controlling a pressure difference between an internal pressure and an external pressure of the hydrogen storage cartridge.
(3) A hydrogen storage method for storing hydrogen in a hydrogen storage cartridge filled with a hydrogen storage material capable of storing hydrogen by pressure,
The hydrogen storage cartridge is housed in a pressure-resistant container that can withstand the hydrogen filling pressure, and hydrogen is introduced into the hydrogen storage cartridge to apply pressure, and the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge is A hydrogen storage method, wherein hydrogen is stored in a hydrogen storage material in a hydrogen storage cartridge while controlling the pressure so as not to exceed a design pressure of the cartridge.
(4) A hydrogen storage method for storing hydrogen in a hydrogen storage cartridge filled with a hydrogen storage material capable of storing hydrogen by pressure and heating,
The hydrogen storage cartridge is housed in a pressure and heat-resistant container that can withstand the hydrogen filling pressure and has a heating device outside, and while introducing the hydrogen into the hydrogen storage cartridge while heating the hydrogen storage cartridge, pressure is applied. The hydrogen storage material stores the hydrogen in the hydrogen storage material in the hydrogen storage cartridge while controlling the pressure so that the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge does not exceed the design pressure of the hydrogen storage cartridge. Method.
(5) In the above (3) and (4), the hydrogen storage cartridge while controlling the pressure so that the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge is within 80% of the design pressure of the hydrogen storage cartridge. A hydrogen storage method comprising storing hydrogen in a hydrogen storage material therein.
(6) In the above (3) and (4), the hydrogen storage method is characterized in that the design pressure of the hydrogen storage cartridge is 0.1 MPa or more and less than 1 MPa.

  According to the present invention, since the weight of the hydrogen storage cartridge filled with the hydrogen storage material can be significantly reduced, the hydrogen weight density per tank weight can be maintained high. In addition, the weight reduction of the tank facilitates the transportation, and the transportation energy and cost per unit weight can be greatly reduced.

  Examples of embodiments according to the present invention are shown in FIG. 1 and FIG. 1 and 2 both show an example in which a heating device is provided outside a pressure-resistant (heat-resistant) container.

  The main structure of the hydrogen storage device according to the present invention shown in FIG. 1 includes a hydrogen storage cartridge 1, a pressure and heat resistant container 2, a hydrogen introduction pipe 3, a pressure controller 4, a heating device 5, and a temperature controller 6. It is a simple system.

  First, the hydrogen storage cartridge 1 may be a cartridge with a low design pressure, and can be reduced in weight by thinning the material. A hydrogen introduction side connector 8 and a hydrogen discharge side connector 9 are incorporated in the lid portion 7. These connectors have a structure in which hydrogen flows only in one direction, and do not open unless a pressure of 80% or more of the design pressure of the hydrogen storage cartridge 1 is applied. When filling the hydrogen storage material, the lid portion 7 is opened for filling. The hydrogen storage cartridge 1 filled with the hydrogen storage material is housed in the pressure and heat resistant container 2 and is firmly fixed by a screw method or the like.

  The pressure and heat resistant container 2 has a structure that can withstand the pressure and temperature during hydrogen storage. Further, an external pressure gas introduction connector 10 is provided. This connector does not have directionality for gas in and out. A thermometer 11 for measuring the temperature of the hydrogen storage cartridge 1 is attached.

  After the hydrogen storage cartridge 1 and the pressure-resistant and heat-resistant container 2 are connected, a hydrogen introduction pipe 3 is connected to each connector. Hydrogen is gradually introduced through the introduction connector 8 while being adjusted to a predetermined pressure by the pressure control valve 12. The pressure is measured with a pressure gauge 13. A pipe for introducing hydrogen into the inside of the hydrogen storage cartridge 1 and a pipe for introducing hydrogen into the gap between the hydrogen storage cartridge 1 and the pressure and heat resistant container 2 are connected to each other, and the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge 1 Does not occur.

  A heating device 5 such as a heater is installed outside the pressure and heat resistant container 2. The measured value at the thermometer 11 is transmitted to the temperature controller 6 and controlled to reach a predetermined temperature. Accordingly, the hydrogen storage material can be smoothly filled by controlling the internal hydrogen storage material at a suitable temperature.

  After the occlusion of hydrogen in the hydrogen storage material inside the hydrogen storage cartridge 1 is completed at a predetermined temperature and pressure, the pressure is gradually relaxed by the pressure control valve 12, and the temperature is lowered to normal pressure and normal temperature. In this case, excessive pressure hydrogen in the hydrogen storage cartridge 1 is released from the discharge-side connector 9.

  The main structure of the hydrogen storage device according to the present invention shown in FIG. 2 is as follows: a hydrogen storage cartridge 1, a pressure and heat resistant container 2, a hydrogen introduction pipe 3, an external pressure gas introduction pipe 14, a pressure controller 4, a heating device 5, When the system comprising the temperature controller 6 and the piping for introducing hydrogen into the inside of the hydrogen storage cartridge 1 and the piping for introducing gas into the gap between the hydrogen storage cartridge 1 and the pressure and heat resistant container 2 are separated. is there.

  The hydrogen storage cartridge 1 may be a cartridge having a low design pressure, and can be reduced in weight by thinning the material. A connector 19 including a valve for opening and closing is installed on the lid portion 7. The valve is normally closed and is opened when hydrogen is stored or released. In addition, this connector does not have directionality. In addition, an internal pressure gauge 15 for measuring the pressure inside the hydrogen storage cartridge 1 is installed. A safety valve 20 is installed in the pipe connected to the internal pressure gauge 15. The safety valve 20 is not opened unless a pressure of 80% or more of the design pressure of the hydrogen storage cartridge 1 is applied. When the pressure is increased, the outer valve is completely closed. When filling the hydrogen storage material, the lid portion 7 is opened for filling. The hydrogen storage cartridge 1 filled with the hydrogen storage material is housed in the pressure and heat resistant container 2 and is firmly fixed by a screw method or the like.

  The pressure and heat resistant container 2 has a structure that can withstand the pressure and temperature during hydrogen storage. Further, an external pressure gas introduction connector 10 and an external pressure gauge 16 for measuring the external pressure of the hydrogen storage cartridge 1 are installed. This connector does not have directionality for gas in and out. A thermometer 11 for measuring the temperature of the hydrogen storage cartridge 1 is attached.

  After the hydrogen storage cartridge 1 and the pressure and heat resistant container 2 are connected, the hydrogen introduction pipe 3 having the internal pressure control valve 17 is connected to the valve connector 19. On the other hand, the external pressure gas introduction pipe 14 provided with the external pressure control valve 18 is connected to the external pressure gas introduction connector 10. Occlusion hydrogen is introduced from the valve connector 19 and gas is introduced from the external pressure gas introduction pipe 14. At this time, the internal pressure and the external pressure are detected by the internal pressure gauge 15 and the external pressure gauge 16, The pressure difference is controlled so as not to become larger than the design pressure of the hydrogen storage cartridge 1. The gas for introducing the external pressure is not particularly limited, but nitrogen, argon, air or the like is used.

  A heating device 5 such as a heater is installed outside the pressure and heat resistant container 2. The measured value at the thermometer 11 is transmitted to the temperature controller 6 and controlled to reach a predetermined temperature. Accordingly, the hydrogen storage material can be smoothly filled by controlling the internal hydrogen storage material at a suitable temperature.

  After the storage of hydrogen in the hydrogen storage material inside the hydrogen storage cartridge 1 is completed at a predetermined temperature and pressure, the temperature is decreased and the pressure is gradually decreased so as not to cause a pressure difference between the internal pressure and the external pressure. .

  Note that the heating device must be installed when the hydrogen storage material inside the hydrogen storage cartridge requires heating when storing hydrogen, or when the hydrogen storage performance is improved by heating. This is not particularly necessary for hydrogen storage materials that can sufficiently store hydrogen. As a result, the pressure-resistant and heat-resistant container that houses the hydrogen storage cartridge also has a particularly large heat-resistant performance in consideration of the heat of reaction generated during hydrogen storage in the case of hydrogen storage materials that can sufficiently store hydrogen only by pressure. In many cases, this is not necessary.

  The hydrogen storage method according to the present invention can be realized by using a hydrogen storage device having the mechanism exemplified above. That is, the hydrogen storage cartridge is housed in a pressure-resistant container that can withstand the hydrogen filling pressure, and hydrogen is introduced into the hydrogen storage cartridge to apply pressure, and the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge is This is a method for storing hydrogen while controlling the pressure so as not to exceed the design pressure of the storage cartridge.

  In addition, when it is necessary to heat not only the hydrogen pressure but also the hydrogen storage material in order to occlude hydrogen, or when the hydrogen occlusion performance is improved by heating, a pressure-resistant and heat-resistant container having an external heating device is further provided. The hydrogen storage cartridge housed therein is heated to introduce hydrogen into the hydrogen storage cartridge to apply pressure, and the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge The hydrogen is occluded while controlling the pressure so as not to exceed the design pressure.

  By using these hydrogen storage methods, the weight of the hydrogen storage cartridge filled with the hydrogen storage material can be significantly reduced, and the weight reduction of the hydrogen storage cartridge makes it easier to transport, the transport energy per unit weight, Cost can be greatly reduced.

  In the above hydrogen storage method, it is essential that the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge be controlled within a range not exceeding 100% of the design pressure of the hydrogen storage cartridge, and within 80% thereof. It is preferable to be controlled. If it exceeds 100%, the hydrogen storage cartridge may be damaged, and if it exceeds 80% of the design pressure, hydrogen will be discharged from a safety valve or the like, which is not preferable for safety.

  In the above hydrogen storage method, the design pressure of the hydrogen storage cartridge to be used is preferably 0.1 MPa or more and less than 1 MPa. If the design pressure is less than 1 MPa, the choices of materials that can be used as the material of the hydrogen storage cartridge are widened, the degree of weight reduction is increased, and the effect of the hydrogen storage method of the present invention can be sufficiently obtained. The lower limit of the design pressure is 0.1 MPa, which is atmospheric pressure.

  In order to verify the hydrogen storage device of the present invention, a small-scale test device was produced and examined. As a hydrogen storage cartridge, a container having a capacity of 1 L, a weight of 1.8 kg (including a lid), and a design pressure of 0.3 MPa was used. This container was filled with 500 g of an alkali metal aluminum hydride-based hydrogen storage material. And, as a pressure and heat resistant container, use a container with a normal pressure resistance of 10 MPa and a heat resistance of 200 ° C., the conditions at the time of hydrogen storage are 170 ° C., 9 MPa and 2 hours, and the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge is within 0.2 MPa The hydrogen was occluded by controlling so that. Thereafter, the pressure and temperature were lowered to normal temperature and pressure. As a result, the occlusion amount of hydrogen was 24 g (4.8% by mass per storage material).

  On the other hand, when the container is not a double structure as in the present invention, considering the current hydrogen storage conditions, when a pressure-resistant heat-resistant container with a capacity of 1 L is produced, the design pressure is 10 MPa and the heat resistance is 200 ° C. The weight of the storage container is 7.0 kg. The hydrogen storage cartridge (including the lid) according to this example can be reduced in weight by about a quarter compared to the hydrogen storage container.

It is an example (simple system) of the structure of the hydrogen storage apparatus which concerns on this invention. It is another example of a structure of the hydrogen storage apparatus which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Hydrogen storage cartridge 2; Pressure-resistant heat-resistant container 3; Hydrogen introduction piping 4; Pressure control meter 5; Heating device 6; Temperature control meter 7; Lid 8: Inlet side connector 9; Connector 11; Thermometer 12; Pressure control valve 13; Pressure gauge 14; Piping for introducing external pressure gas 15; Internal pressure gauge 16; External pressure gauge 17; Internal pressure control valve 18; External pressure control valve 19; Valve connector 20;

Claims (6)

A hydrogen storage device for storing hydrogen in a hydrogen storage cartridge filled with a hydrogen storage material capable of storing hydrogen by pressure,
A pressure vessel that can withstand the hydrogen filling pressure, the hydrogen storage cartridge housed in the pressure vessel, a pipe for introducing hydrogen into the hydrogen storage cartridge, and a gas in a gap between the pressure vessel and the hydrogen storage cartridge A hydrogen storage device, comprising: a pipe to be introduced; and a mechanism for controlling a pressure difference between an internal pressure and an external pressure of the hydrogen storage cartridge. A hydrogen storage device for storing hydrogen in a hydrogen storage cartridge filled with a hydrogen storage material capable of storing hydrogen by pressure and heating,
A pressure- and heat-resistant container that can withstand the hydrogen filling pressure and has an external heating device; the hydrogen storage cartridge housed in the pressure- and heat-resistant container; a pipe for introducing hydrogen into the hydrogen storage cartridge; A hydrogen storage device comprising: a container and a pipe for introducing a gas into a gap between the hydrogen storage cartridge; and a mechanism for controlling a pressure difference between an internal pressure and an external pressure of the hydrogen storage cartridge. A hydrogen storage method for storing hydrogen in a hydrogen storage cartridge filled with a hydrogen storage material capable of storing hydrogen by pressure,
The hydrogen storage cartridge is housed in a pressure-resistant container that can withstand the hydrogen filling pressure, and hydrogen is introduced into the hydrogen storage cartridge to apply pressure, and the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge is A hydrogen storage method, wherein hydrogen is stored in a hydrogen storage material in a hydrogen storage cartridge while controlling the pressure so as not to exceed a design pressure of the cartridge. A hydrogen storage method for storing hydrogen in a hydrogen storage cartridge filled with a hydrogen storage material capable of storing hydrogen by pressure and heating,
The hydrogen storage cartridge is housed in a pressure and heat-resistant container that can withstand the hydrogen filling pressure and has a heating device outside, and while introducing the hydrogen into the hydrogen storage cartridge while heating the hydrogen storage cartridge, pressure is applied. The hydrogen storage material stores the hydrogen in the hydrogen storage material in the hydrogen storage cartridge while controlling the pressure so that the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge does not exceed the design pressure of the hydrogen storage cartridge. Method.   Storing hydrogen in the hydrogen storage material in the hydrogen storage cartridge while controlling the pressure so that the pressure difference between the internal pressure and the external pressure of the hydrogen storage cartridge is within 80% of the design pressure of the hydrogen storage cartridge. The hydrogen storage method according to claim 3 or 4, wherein:   The hydrogen storage method according to claim 3 or 4, wherein a design pressure of the hydrogen storage cartridge is 0.1 MPa or more and less than 1 MPa.

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