JP4916367B2 - Device for activating hydrogen storage alloy container - Google Patents

Description

The present invention relates to an active KaSo location of the hydrogen storage alloy container, in particular, by providing a heat removal means comprising a cooling coil in the internally provided with a pressure vessel a hydrogen storage alloy container, realizing shortening of revitalization time It relates to a new improvement.

  Conventionally, as a method for activating a hydrogen storage alloy that has been used, for example, a powdered hydrogen storage alloy is placed in a sealed container provided with a hydrogen introduction tube, and is vacuumed at a temperature of 80 ° C. or more for several hours to several tens of hours. After pulling, a method of introducing hydrogen at several atmospheres or more at a temperature below room temperature is common. Here, evacuation at a high temperature in the first half is called “depressurization activation”, and high-pressure hydrogen introduction at a low temperature in the second half is called “pressurization activation”. Hydrogen-absorbing alloys that are difficult to activate, such as BCC-based hydrogen-absorbing alloys, have higher pressure activation conditions and higher vacuums, and lower pressure activation conditions than AB5- and AB2-based alloys that are easily activated. And high pressure is necessary. In addition, as the activation conditions are increased, the activation time is generally shortened. That is, the time until activation is completed is shorter when the pressure activation step is performed at 150 ° C. than 100 ° C., and when the pressure activation step is performed at 0 ° C. than 20 ° C. or 10 MPa rather than 1 MPa.

  However, when a practical hydrogen storage alloy container is activated, the design conditions and the pressure of the container are naturally limited, and thus the activation conditions cannot be increased without limit. A metal container has a relatively wide allowable temperature range, but exceeding the allowable pressure limit may cause deformation or rupture of the container. Furthermore, since the volume of the hydrogen storage alloy itself changes greatly before and after activation, it is necessary to take into account the expansion pressure of the alloy in addition to the hydrogen gas pressure. That is, the hydrogen pressure introduced during the pressure activation must be lower than the original design pressure of the container. For this reason, in a container containing a hydrogen storage alloy having a slow activation rate, there is a drawback that the time required for activation becomes long.

Further, in order to improve the above-described conventional method, methods described in the following Patent Documents 1 and 2 have been proposed.
That is, in the method of Patent Document 1, a method has been devised in which a hydrogen storage alloy is encapsulated in a plastic container such as a polyethylene bag together with hydrogen and activated by cold isostatic pressing together with the bag. However, considering that the hydrogen storage alloy can absorb nearly 1000 times its own volume of hydrogen, for example, in order to activate a hydrogen storage alloy having a volume of 1 L (approximately 6 to 8 kg), a plastic having a volume of 1 m ³ is required. A container is required. Since the volume of the plastic container increases in proportion to the amount of alloy to be activated, this method is not suitable for mass processing.

  Moreover, in the case of the method of the above-mentioned patent document 2, the hydrogen storage alloy container which opened | released the hydrogen absorption / release hole was put into the vessel provided with the hydrogen gas supply device, the inert gas supply device, and the decompression device, and the inside of the vessel was decompressed. In addition, an apparatus and a method for activating hydrogen by applying hydrogen pressure have been proposed. In this method, since the internal and external pressures of the hydrogen storage alloy container can be made uniform, hydrogen activation can be performed at a high pressure without considering the deformation of the container due to the pressure difference. However, this method has the following drawbacks. (1) Since the entire vessel must be depressurized, it is more difficult to increase the degree of vacuum during the depressurization activation than when depressurizing the hydrogen storage alloy container alone. (2) A large amount of hydrogen is required because not only the alloy container but also the entire vessel must be filled with high-pressure hydrogen. (3) The jacket for heat exchange must be structured to withstand both the internal pressure during decompression and the external pressure during pressurization. (4) When the hydrogen storage alloy container is taken out after activation, the inside of the vessel is replaced with inert gas after releasing hydrogen, and the alloy container must be covered with the inert gas. The equipment and the manufacturing process were complicated.

Japanese Patent No. 2699136 JP 2000-17408 A

Revitalize how the conventional hydrogen occluding alloy container, because it is constructed as described above, the following problems were present.
That is, in order to prevent deformation of the container, the hydrogen pressure during the pressurization activation is kept below a certain level, so that it takes time to activate. Therefore, a method has been devised to reduce the activation time by putting the hydrogen storage alloy before putting into the container together with hydrogen gas into a plastic container and applying hydrostatic pressure, but the container volume before activation becomes very large. Therefore, it is not a realistic method. In addition, a hydrogen storage alloy container with an open lid was placed in a vessel, and hydrogen was introduced into the vessel to devise a method for activation while keeping the pressure inside and outside the alloy container equalized. However, there are problems that the amount of hydrogen required for the process increases, and that it is difficult to take out the alloy container after the activation is completed.

The activation apparatus for a hydrogen storage alloy container according to the present invention can arrange a hydrogen storage alloy container in a pressure resistant container, and a hydrogen pipe communicating with a hydrogen source disposed outside the pressure resistant container is connected to the hydrogen storage alloy container. is, above the pressure vessel is provided an inlet of the fluid to be introduced into the pressure vessel is, in the pressure vessel in a configuration where filling and pressurizing means for filling and pressurization of the fluid is connected, the heat removal means comprising a cooling coil flowed the order refrigerant to remove heat of the fluid is configured to Yes in the pressure vessel.

Activity KaSo location of the hydrogen storage alloy container according to the present invention, since it is constructed as described above, it is possible to obtain the following effects.
In other words, put the hydrogen storage alloy container in a pressure vessel, a heat removal means comprising a cooling coil flowed the refrigerant provided in the pressure vessel, the hydrogen storage alloy container externally on filled with fluid, the hydrogen by the flow body absorption heat Since hydrogen can be removed, the hydrogen activation time can be shortened.

The present invention, by providing a heat removal means comprising cooling coils internally provided with a pressure vessel of the hydrogen absorbing alloy container, activity KaSo location of hydrogen absorbing alloy container so as to achieve a reduction of activity of time The purpose is to provide.

Hereinafter, a preferred embodiment of the active KaSo location of the hydrogen storage alloy container according to the invention will be described with reference to the drawings.
FIG. 1 shows an embodiment of a hydrogen activation apparatus according to the present invention, and a hydrogen pipe 3, a differential pressure gauge 4, and an air vent valve 5 are provided on a lid portion 2 of a pressure vessel indicated by reference numeral 1.

A fluid tank 7 for storing a fluid 6 is connected to the main body 1A of the pressure vessel 1 through a fluid pipe 8, and the fluid pipe 8 is connected to the inlet 9 and the outlet 10 of the main body 1A. Yes.
The fluid pipe 8 is provided with first, second, and third valves 11, 12, and 13, and the fluid 6 is placed between the first and third valves 11 and 13 in the pressure vessel 1. A filling / pressurizing means 14 including a filling / pressurizing pump for filling / pressurizing the inside is provided.

The differential pressure gauge 4 and the filling / pressurizing means 14 are connected to an output control unit 15 and control the feed amount of the fluid 6 of the filling / pressurizing means 14 based on the differential pressure 4 a from the differential pressure gauge 4. It is configured to be able to.
A tank-like hydrogen source 18 composed of a high-pressure hydrogen source is connected to the hydrogen pipe 3 via a pressure gauge 16 and a regulator 17.

Next, the hydrogen activation procedure in the above-described configuration will be described. First, as shown in FIG. 1, fitted with a plurality of hydrogen absorbing alloy container 20 vacuum activation process is completed to the hydrogen pipe 3, as shown in FIG. 2, close the lid section 2. After filling the fluid 6 into the pressure-resistant vessel 1 while evacuating the air in the internal process with the lid 2 closed, hydrogen 18a is introduced. The hydrogen is gradually pressurized while controlling the feed by the filling / pressurizing means 14 so that the differential pressure between the hydrogen 18a and the fluid 6 becomes zero, and when the target pressure is reached, the pressure is kept constant. Wait until the activation is finished. After completion of the hydrogen activation, the pressure of the fluid and the pressure of hydrogen are simultaneously released, and the hydrogen pressure is lowered to the allowable pressure of the hydrogen storage alloy container 20 or less. Finally, the lid 2 of the pressure vessel 1 is opened and the activated hydrogen storage alloy vessel 20 is removed.

  The fluid 6 is preferably water, but oil or antifreeze may be used depending on the activation temperature. As a means for eliminating the differential pressure between the hydrogen pressure and the fluid pressure, in addition to the method of adjusting the feed output according to the output of the differential pressure gauge 4 as shown in FIG. A method of balancing the pressure and the fluid is also possible.

Active KaSo location of the hydrogen storage alloy container described above Thus, it is possible to keep the inner external pressure of the hydrogen storage alloy container 20 in equilibrium, it is minimized while activated at high hydrogen pressures deformation of the hydrogen absorbing alloy vessel 20 Since the hydrogen absorption heat generated by the heat transfer to the surrounding fluid 6 can be removed, the activation time can be shortened. Further, when the cooling coil or Ranaru heat removal means 30 were introduced into the refrigerant as shown in FIG. 3 is arranged in a pressure vessel 1, the removal efficiency of the hydrogen absorption heat is remarkably improved, further shorten the activation time be able to. Here, in addition to the heat removal means 30 for the fluid 6 illustrated in FIG. 3, a cooling coil is wound around the outside of the pressure vessel 1 and the whole pressure vessel 1 is cooled, or a part of the fluid piping is coiled. A method of cooling by immersing in a cooling tank and forcibly circulating a fluid is also possible.

Next, the applicant with the activation device of the hydrogen storage alloy container according to the invention, for comparison with the conventional method, the hydrogen storage alloy tank rated hydrogen capacity 50NL (outer dimensions φ50mm × H132mm, AB5 alloys 330g Internal) An experiment of comparison of activation rates was performed, and the results are described.
The activation procedure according to the conventional method is as follows. (1) Immerse the alloy tank in a water bath at 80 ° C and evacuate for 5 hours. (2) Immerse the alloy tank in a water bath at 15 ° C. and introduce 1 MPa of hydrogen into the interior. The amount of hydrogen absorbed in the alloy tank was measured with a mass flow meter.
Activation procedure according to the present onset illumination device is as follows. (1) Immerse the alloy tank in a water bath at 80 ° C and vacuum for 5 hours. (2) An alloy tank is placed in a pressure vessel in which a coil in which water of 15 ° C. circulates is provided, and a hydrogen pipe is connected to close the pressure vessel. (3) Fill the pressure vessel with water, gradually increase the hydrogen pressure, and equilibrate to increase the water pressure. (4) When both the hydrogen pressure and water pressure reach 5 MPa, stop the pressure increase and measure the hydrogen absorption amount with a mass flow meter. Next, FIG. 4 shows a change in the hydrogen absorption amount of the MH tank when the time when the hydrogen filling is started is set to zero. In the conventional method 3.5 hours took activation, in the onset illuminating device was found to be complete in about 2 hours.

Is a block diagram showing the activity KaSo location of the hydrogen storage alloy container according to the invention. It is a block diagram which shows the state which closed the cover part of FIG. It is a block diagram which shows the other form of FIG. It is a characteristic view which shows the speed comparison of the activation time of this invention apparatus and the conventional method.

DESCRIPTION OF SYMBOLS 1 Pressure-resistant container 1A Main-body part 2 Lid part 3 Hydrogen piping 4 Differential pressure gauge 5 Air vent valve 6 Fluid 7 Fluid tank 8 Fluid piping 9 Inlet 10 Outlet 11-13 First to third valves 14 Filling / pressurizing means 15 Output Control part 16 Pressure gauge 17 Regulator 18 Hydrogen source 18a Hydrogen 20 Hydrogen storage alloy container 30 Heat removal means

Claims (1)

In a pressure vessel (1) can be arranged a plurality of hydrogen absorbing alloy container (20), the hydrogen pipe communicating with the outside disposed hydrogen source (18) of the pressure vessel (1) (3) is the hydrogen Connected to the storage alloy container (20), the pressure vessel (1) is provided with an inlet (9) for the fluid (6) to flow into the pressure vessel (1), and the pressure vessel (1) has the above-mentioned in activity KaSo location of hydrogen absorbing alloy container filling and filling and pressurizing means which can pressure (14) is made of a configuration that is connected in fluid (6),
Said fluid (6) heat consisting cooling coil flowed the order refrigerant removes heat removal means (30) said pressure vessel (1) to closed the hydrogen storage alloy container you characterized in the Activation device.

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