JPH09242995A - Square heat transfer vessel filled with hydrogen storage alloy for storing hydrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat transfer vessel for hydrogen storage alloy which provides large hydrogen storage alloy storage amount per unit volume and has excellent heat transfer performance. SOLUTION: End casings are arranged at both ends of a unit vessel casing which is made flat by knotching at least one corner among four corners and is essentially in square column shaped cylindrical shape in the unit vessel casing so that a hydrogen storage alloy filled part is formed. A large square column- shaped cylindrical body constituted by arranging many unit cell vessels 12 provided with a hydrogen gas flow tube 3 which passes through the end casing at one end of the unit vessel casing lengthwise and crosswise adheres into an external casing 4 in the end casing at one end thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage alloy filled prismatic heat transfer container for hydrogen storage.

[0002]

2. Description of the Related Art In recent years, a high-purity hydrogen gas purifying device or a heat recovery device (heat pump) utilizing the characteristics of a hydrogen storage alloy has been developed. Most of the containers that store the hydrogen storage alloy used in these devices are cylindrical containers, for example, a small diameter heat transfer tube is placed inside a cylindrical container and the hydrogen storage alloy is stored outside the heat transfer tube. A method of doing so has been proposed (JP-A-6-42699). These conventional techniques focus on increasing the heat transfer characteristics, that is, the reaction rate, for use in hydrogen purification or heat pumps.

[0003]

As described above, in order to utilize hydrogen purification or heat pump, etc., conventionally,
Development has been made with a focus on heat transfer characteristics, that is, to increase the reaction rate. However, in recent years, there has been a demand for the development of hydrogen storage containers such as hydrogen storage tanks for hydrogen automobiles or hydrogen storage tanks for power generation systems using a solid polymer electrolyte membrane in the field of utilizing hydrogen gas as a fuel. These storage facilities need to store as much hydrogen gas as possible in a limited space. This means how much hydrogen storage alloy can be stored in a unit volume, but naturally it requires some heat transfer means for releasing and supplying hydrogen from the hydrogen storage alloy. is there.

Since most conventional hydrogen storage alloy containers are cylindrical containers, considering the installation space in terms of the projected volume ratio, there are many waste spaces in which hydrogen storage alloy is not stored. In addition, since heat transfer performance is prioritized in the container as well, a large number or a large volume of heat medium passages are provided. This also leads to a decrease in the storage capacity of the hydrogen storage alloy.

In view of the above-mentioned state of the art, the present invention is different from the object of the prior art and solves the problem of how much hydrogen can be stored. Is to provide.

[0006]

According to the present invention, (1) a hydrogen storage alloy is filled in an essentially prismatic cylindrical unit container casing in which at least one of the four corners is cut to be flat. The end casings are arranged at both ends so as to form a section, and the end casing at one end thereof is provided with a unit cell container provided with a hydrogen gas flow tube penetrating the casing,
A hydrogen-storing alloy-filled rectangular transmission for hydrogen storage, characterized in that a large number of prismatic cylindrical bodies, which are constructed by arranging many hydrogen gas flow tubes in the same direction vertically and horizontally, are closely packed in an outer casing. Heat container, (2) An essentially prismatic cylindrical unit container casing having at least one side of four sides formed with a small recessed portion which is semi-circular in a cross section and continuous in the container longitudinal direction in a cross section. A hydrogen storage alloy-filled prismatic heat transfer container for hydrogen storage according to the above (1),
(3) The hydrogen storage alloy-filled rectangular heat transfer container for hydrogen storage according to the above (1) or (2), wherein the material of the prismatic cylindrical unit container casing is essentially clad steel.

(Operation) Essentially, a prismatic cylindrical unit container casing (at least one of the four corners is flattened by removing at least one of the four corners or at least one of the four sides has a side in a cross section). A heat transfer container in which a plurality of unit cell containers configured by accommodating a hydrogen storage alloy in a semi-circular shape with small depressions continuous in the longitudinal direction of the container are vertically and horizontally integrated Thereby, the storage amount of the hydrogen storage alloy can be improved as compared with the unit cell container configured by the cylindrical unit container casing, and as a result, a large amount of hydrogen can be stored.

In addition, when a large number of unit cell containers are stacked, the prismatic cylindrical unit container casings are provided with a prismatic shape between the adjoining casings due to the broken and flat corners or small semicircular recesses formed in the casings. A small space communicating with the longitudinal direction of the cylindrical unit container casing is formed. By using this small space as a flow path for the cooling / heating medium, the function of the heat transfer fin can be provided to the prismatic cylindrical unit container casing.

In addition, the prismatic cylindrical unit container casing member is made of clad steel as shown in Table 1 below, and the surface in contact with the stored hydrogen storage alloy is made of a material having a high thermal conductivity, whereby the cooling / heating medium is cooled. More heat can be transferred and received efficiently.

[0010]

[Table 1]

When a hydrogen gas is occluded in the small space of the heat transfer container having the above functions, a refrigerant is passed through the space.
The reaction heat generated by the storage of hydrogen gas is first transferred to the unit cell container, and then cooled and discharged by the refrigerant flowing in the small space through the unit cell container. Also, when releasing hydrogen gas from the hydrogen storage alloy, if a heat medium is passed through a small space,
The heat is transferred to the unit cell container and then to the hydrogen storage alloy contained therein to release hydrogen gas.

[0012]

EXAMPLES Hereinafter, the effects of the present invention will be clarified by giving specific examples of the hydrogen storage alloy-filled prismatic heat transfer container for hydrogen storage of the present invention.

(Embodiment 1) FIG. 1 shows an example of a unit cell container 12 of a heat transfer container in Embodiment 1 of the present invention. In FIG. 1, a prismatic tubular unit container casing 1 having a flattened flat corner portion 2 in which two corner portions out of four angles are flattened, and a hydrogen flow tube 3 through which hydrogen gas flows Are placed. The hydrogen flow tube 3 has a filter function that allows hydrogen gas to pass therethrough but does not allow hydrogen storage alloy to pass therethrough, and is made of, for example, a sintered metal or a resin fiber material. The hydrogen storage alloy is filled in the hydrogen storage alloy filling section 6 (see FIG. 3 for details) between the unit container casing 1 and the hydrogen flow tube 3. Hydrogen storage alloys are, for example, LaMmNi ₅ (lanthanum misch metal,
Nickel), etc., and is appropriately selected depending on the cooling / heating medium temperature conditions and the absorbed / desorbed hydrogen pressure conditions in the application.

FIG. 2 shows an example (perspective view) of a heat transfer container in which the unit cell containers 12 are integrated. In this example, the unit cell containers 12 are integrated in three stages vertically and five stages horizontally. However, the number of these accumulations is appropriately set according to the application.

In the embodiment 1 of the present invention, the unit cell container having two missing flat corners 2 of the unit cell container 12 shown in FIG. 1 is formed in a large size so that the missing flat corners 2 of the adjoining containers 12 are joined together. The case where a prismatic cylindrical body is formed is shown. That is, the unit cell container A: 7, the unit cell container B: 8, the unit cell container C: 9, and the unit cell container D: 10 are unit cell containers having the same shape, but each container is rotated by 90 °. As a result, the defective flat corners 2 form a space serving as the cooling / heating medium flow path 5 outside each unit cell container 12, as shown in FIG.

As in the first embodiment, the outer casing of the heat-transfer container is made of, for example, SUS316L on the outermost surface of the large prismatic cylindrical body composed of the unit cell containers 12 stacked in three rows vertically and five rows horizontally. 4 are arranged to fix the unit cell container 12 and form the outer peripheral cooling / heating medium passage 11.

FIG. 3 shows an assembled sectional view of the heat transfer container. The hydrogen storage alloy filled in the unit cell container 12 is housed by the end casings 18 and 18 'at both ends thereof. A hydrogen flow tube 3 is sealed and penetrated at one end thereof by means such as welding, and further reaches an outer cooling / heating medium chamber-hydrogen chamber partition plate 19, which is also sealed and penetrated by means such as welding and is attached. To be

The hydrogen flow tube 3 has a porous portion made of sintered metal or polymer fiber, etc., at the portion in contact with the hydrogen storage alloy, but other portions requiring hydrogen gas confidentiality are made of a steel pipe such as stainless steel. Are joined together.

As described above, heat is transferred from the hydrogen storage alloy to the refrigerant in the cold / heat medium passage 5 through the unit container casing 1, or hydrogen is passed from the heat medium in the cold / heat medium passage 5 through the unit container casing 1. In heat transfer for heating and raising the temperature of the storage alloy, the unit container casing 1 functions as a heat transfer fin. Therefore, the unit container casing 1 also functions as a heat transfer fin, whereby a more compact heat transfer container is formed.

A cold / heat medium chamber 13 is formed between the end casing 18 and the cold / heat medium chamber-hydrogen chamber partition plate 19. The cooling / heating medium flow path 5 and the outer peripheral cooling / heating medium flow path 11 formed by the flat portions 2 between the unit cell vessels 12 are connected to the cooling / heating medium flow inlet 14. The cold / heat medium to be cooled is the cold / heat medium chamber 13, the cold / heat medium flow path 5 and the outer peripheral portion
It flows through the heat medium passage 11. At the other end, the end casing 18 'and the outer casing 4 of the heat transfer container similarly form a cooling / heating medium chamber 13'. This cold / heat medium chamber 13 ′ is also connected to the cold / heat medium flow path 5, and the cold / heat medium flowing in from the cold / heat medium inlet 14 is cooled / heat medium flow path 5 and the outer periphery cold / heat. A cooling / heating medium outlet 15 is connected to the cooling / heating medium chamber 13 'through the medium flow path 11 so as to reach the cooling / heating medium chamber 13'.
Is more exhausted. A hydrogen chamber 16 is formed between the cooling / heating medium chamber-hydrogen chamber partition plate 19 and the heat transfer container outer casing 4. A hydrogen gas inlet / outlet 17 is arranged so as to communicate with the hydrogen chamber 16.

The operation of this structure is as follows. When hydrogen is stored in the hydrogen storage alloy, hydrogen gas is supplied from the hydrogen gas outlet / inlet 17 at a predetermined pressure to flow therein. The hydrogen gas flows through the hydrogen chamber 16 and further into the hydrogen flow tube 3, reaches the hydrogen storage alloy filling section 6 through the porous portion forming the hydrogen flow tube 3, and is stored in the hydrogen storage alloy. At this time, the cooling medium is supplied from the cooling / heating medium inlet 14, and each cooling / cooling medium is supplied from the cooling / heating medium chamber 13.
It is dispersed in the heat medium flow path 5 and the outer peripheral cold / heat medium flow path 11, flows to reach the other cold / heat medium chamber 13 ′, and is discharged from the cold / heat medium outlet 15. Reaction heat generated when hydrogen is stored in the hydrogen storage alloy by flowing a refrigerant through each of the cooling / heating medium flow paths 5 and the outer peripheral cooling / heating medium flow path 11 is passed through the hydrogen storage alloy and the unit container casing 1. While reaching and discharging the refrigerant, the hydrogen storage alloy is cooled and the hydrogen storage reaction is promoted.

When releasing hydrogen from the hydrogen storage alloy, the heat medium is supplied from the cold / heat medium inflow port 14. The heat medium is distributed from the cold / heat medium chamber 13 to the respective cold / heat medium flow paths 5 and the outer peripheral cold / heat medium flow path 11, and reaches the other cold / heat medium room 13 ′ where It is discharged from the heat medium outlet 15. By flowing the heat medium through each of the cold / heat medium flow paths 5 and the outer peripheral cold / heat medium flow path 11, heat is transferred from the heat medium to the hydrogen storage alloy through the unit container casing 1, and the hydrogen storage alloy is heated and heated. It is heated to generate and release hydrogen gas. The released hydrogen gas flows from the porous portion of the hydrogen flow tube 3 into the hydrogen flow tube 3 to reach the hydrogen chamber 16, and is then discharged from the hydrogen gas inflow / outlet port 17.

As shown in FIG. 2, the unit cell container 12 of the heat transfer container according to the first embodiment is arranged in the upper, lower, left and right unit cell containers 12.
Although the description has been given by taking as an example the case in which the defect flat corners 2 are arranged adjacent to each other, as shown in FIG.
As shown in FIG. 4 (cross-sectional view), it is preferable not to collect the flat defect portions 2 because the cooling / heating medium flow passages are arranged in their entirety.

(Embodiment 2) FIG. 5 shows another example of the unit cell container 12 of the heat transfer container in Embodiment 2 of the present invention. FIG.
The symbols in have the same meanings as in FIG. In FIG. 5, the unit cell container 12 is essentially the same as that of FIG. 1 except that the unit cell container 12 is a prismatic cylindrical unit container casing 1 in which all four corners are flat flat corners 2.

FIG. 6 shows an example of a heat transfer container formed by accumulating the unit cell containers 12 of FIG. The reference numerals in FIG. 6 have the same meanings as in FIG. This example shows an example in which the unit cell containers 12 are vertically stacked in three stages and horizontally in five stages to form a large prismatic cylindrical body, but the number of these stacks is appropriately set according to the application. As in Example 2, the unit cell container 12 having four flat corners 2 at all four corners is stacked and stacked when the flat flat corners 2 of adjacent containers are stacked together. A space serving as the cooling / heating medium flow path 5 is formed outside the unit cell container 12 by the defective flat corner portion 2. A heat transfer container outer casing 4 is arranged on the outermost surface of the unit cell containers 12 in which three vertical units and five horizontal units are integrated. The unit cell container 12 is fixed and the outer peripheral cooling / heating medium flow passage 11 is formed. Forming is the same as in the first embodiment. The entire structure and operation are the same as those of the first embodiment except that the contact area with the cooling / heating medium is increased and the cooling / heating efficiency is improved.

(Embodiment 3) FIG. 7 shows another structural example of the unit cell container 12 of the heat transfer container in Embodiment 3 of the present invention.
In the third embodiment, one of the prismatic cylindrical unit container casings 1 is used.
The configuration is the same as that of the first embodiment except that the unit cell container 12 has a semi-arcuate small depression 2'that is continuous in the longitudinal direction of the container in a cross section at one side. Therefore, the small depression 2 in FIG. Reference numerals other than 'have the same meanings as in FIG.

FIG. 8 shows an example of a heat transfer container in which the unit cell container 12 of FIG. 7 is integrated. In this example, the unit cell container 1
An example is shown in which 2 is vertically stacked in 3 stages and 5 in a horizontal direction to form a large prismatic cylindrical body, and the number of these is appropriately set according to the application. The reference numerals have the same meanings as in FIG.

The unit cell container 12 having one small depression 2'on the side surface of the unit cell as in the third embodiment has a small depression 2'of the unit cell and an adjacent container when accumulating them. The sides are aligned and stacked. A space serving as the cooling / heating medium flow path 5 is formed outside the unit cell container 12 by the side surface of the unit cell container 12 adjacent to the small depression 2 ′ of one unit cell container 12. An outer casing 4 of the heat transfer container is arranged on the outermost surface of the unit cell containers 12 in which the unit cell containers 12 are arranged in three rows vertically and five rows horizontally, and the unit cell vessels 12 are fixed and the outer peripheral cooling / heating medium passages 11 are formed. The whole structure of the heat transfer container of this embodiment and the operation when the position of the semi-arc shaped small depression 2'is near the center of the side are the same as those of the first embodiment, and therefore the description thereof is omitted.

When the unit container casing 1 is filled with a hydrogen storage alloy, as shown in FIG.
If 1 is sufficiently filled in the container and is in contact with the side of the container, heat is transferred from the entire surface of the container. Therefore, the small depression 2'is preferably provided near the center of the side. However, FIG.
As shown in (b), a space 22 may be formed in the upper side portion due to consolidation of the hydrogen storage alloy 21 or the like, and in that case, the cooling / heating medium passage has the length of the heat transfer portion (t in FIG. 9B). (Corresponding to the above), and it is effective to dispose the small depression 2 ′ at a position offset from the center of the side as shown in FIGS. 7, 8 and 9 (b). Is. Note that the same arrangement is used in FIGS. 10 and 11 described later.

(Embodiment 4) FIG. 10 shows another structural example of the unit cell container 12 of the heat transfer container in Embodiment 4 of the present invention. The reference numerals in FIG. 10 have the same meanings as in FIG. Unit container casing 1 in FIG.
Is essentially the same as that of FIG. 7 except that it is a prismatic cylindrical unit container casing 1 having two small depressions 2'on its two side surfaces.

FIG. 11 shows an example of a heat transfer container formed by accumulating the unit cell containers 12 of FIG. The reference numerals in FIG. 11 have the same meanings as in FIG. In this example, the unit cell containers 12 are vertically stacked in three stages and horizontally in five stages, but the number of these units is appropriately set according to the application. As shown in FIG. 10, the unit cell container 12 having the two small depressions 2'on its side surface as in the fourth embodiment is integrated with the adjacent small depressions 2'of the adjacent containers as shown in FIG. As a result, a space serving as the cooling / heating medium channel 5 is formed outside the unit cell container 12. An outer casing 4 of the heat transfer container is arranged on the outermost surface of the unit cell containers 12 in which the unit cell containers 12 are arranged in three rows vertically and five rows horizontally, and the unit cell vessels 12 are fixed and the outer peripheral cooling / heating medium passages 11 are formed. Below is the overall structure and operation
The description is omitted because it is the same as the third embodiment except that the contact area with the heating medium is increased and the cooling / heating efficiency is improved.

(Fifth Embodiment) FIGS. 12 and 13 show another structural example of the unit cell container 12 of the heat transfer container in the fifth embodiment of the present invention. The reference numerals in FIGS. 12 and 13 have the same meanings as in FIG. The unit container casing 1 shown in FIGS. 12 and 13 is essentially the unit container casing 1 in the shape of a prismatic cylinder having three or four small depressions 2 ′ on all three or four side faces thereof, except that the unit container casing 1 shown in FIG. Is the same as

FIG. 14 shows an example of a heat transfer container in which the unit cell containers 12 of FIG. 12 or 13 are integrated. Since the reference numerals in FIG. 14 have the same meanings as in FIG. 6, description thereof will be omitted. In this example, the unit cell containers 12 are vertically stacked in three stages and horizontally in five stages, but the number of these units is appropriately set according to the application. As shown in FIG. 13, unit cell containers 12 each having three or four small depressions 2 ′ on the side surface thereof are integrated as shown in FIG. A space is created. The heat transfer container outer casing 4 is arranged on the outermost surface of the unit cell container 12 in which the unit cell container 12 has three columns vertically and five columns horizontally, and fixes the unit cell container 12 and forms the outer peripheral cooling / heating medium passage 11. To do. The entire structure and operation are the same as those of the third embodiment except that the contact area with the cooling / heating medium is increased and the cooling and heating efficiency is improved.

(Embodiment 6) FIG. 15 shows an example of a heat transfer container in which the unit cell containers 12 shown in FIG. 13 are integrated. The reference numerals in FIG. 15 have the same meanings as in FIG. In this example, the unit cell containers 12 are vertically stacked in three stages and horizontally in five stages, but the number of these units is appropriately set according to the application. As shown in FIG. 15, the unit cell container 12 having four small recesses 2'on four sides of the unit container casing as in this embodiment is assembled by stacking the adjacent small recesses 2'of adjacent containers as shown in FIG. It As a result, a space serving as the cooling / heating medium channel 5 is formed outside the unit cell container 12. Further, the heat transfer container outer casing 4 is arranged on the outermost surface of the unit cell container 12 thus integrated, and fixes the unit cell container 12 and forms the outer peripheral cooling / heating medium passage 11.
The entire structure and operation are the same as in Example 3 except that the contact area with the cooling / heating medium is increased and the cooling and heating efficiency is improved.

In the heat transfer container of the present invention as shown in Embodiments 1 to 6 above, the member of the unit container casing may be arbitrarily selected according to the properties of the cooling / heating medium and the hydrogen storage alloy. However, it is preferable to use the clad steel as shown in Table 1 above from the viewpoint of improving the container strength and heat transfer performance. When clad steel is used as the material of the unit container casing, the clad steel inner member 20 that is in contact with the hydrogen storage alloy is made of a material with high thermal conductivity and the clad steel outer member 19 is heated as shown in FIG. By using a material having a low conductivity, it is possible to efficiently transfer heat from the cold / heat medium. The unit container casing member is made of SUS3 with water or hot water as a cooling / heating medium.
Table 2 shows the results of examining the difference in fin efficiency between the case of using 16 L and the case of using various clad steels.

[0036]

[Table 2] From Table 2, it is understood that when clad steel is used as the unit container casing member, the fin efficiency is improved 1.43 to 1.68 times as compared with the case where SUS316L is 1.

[0037]

According to the rectangular heat transfer container for hydrogen storage alloy of the present invention, since the container shape is rectangular, a larger amount of hydrogen storage alloy can be stored, and unit cell containers are integrated. By adopting the method of forming a set of heat transfer containers, the flow path is inevitably secured without providing the cooling / heating medium flow path. Further, the hydrogen storage alloy amount storage amount can be arbitrarily and easily set by the number of combinations of unit cell containers. Also, regarding the heat transfer property, the unit container casing is made to function as a heat transfer fin, so that the heat transfer container can be made more compact.

Further, by using clad steel for the unit container casing member, the strength of the container is improved, the thermal conductivity of the member is increased, and the efficiency of the heat transfer fin is improved. The release reaction rate is improved. As a result, the heat storage container for hydrogen storage alloy has a large amount of hydrogen storage alloy stored per unit volume and excellent heat transfer performance.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional perspective view of a unit cell container according to a first embodiment.

FIG. 2 is a cross-sectional perspective view of the heat transfer container according to the first embodiment.

FIG. 3 is a vertical sectional view of the heat transfer container according to the first embodiment.

FIG. 4 is a vertical cross-sectional view showing a modified example of the heat transfer container according to the first embodiment.

FIG. 5 is a partial cross-sectional perspective view of a unit cell container according to the second embodiment.

FIG. 6 is a cross-sectional view of the heat transfer container according to the second embodiment.

FIG. 7 is a partial cross-sectional perspective view of a unit cell container according to a third embodiment.

FIG. 8 is a cross-sectional view of the heat transfer container according to the third embodiment.

FIG. 9 is an explanatory diagram showing a state of filling a hydrogen storage alloy into a unit container casing.

FIG. 10 is a partial cross-sectional perspective view of the unit cell container according to the fourth embodiment.

FIG. 11 is a cross-sectional view of the heat transfer container according to the fourth embodiment.

FIG. 12 is a partial cross-sectional perspective view of a unit cell container according to a fifth embodiment.

FIG. 13 is a partial cross-sectional perspective view of a unit cell container according to Examples 5 and 6.

FIG. 14 is a cross-sectional view of the heat transfer container according to the fifth embodiment.

FIG. 15 is a cross-sectional view of the heat transfer container according to the sixth embodiment.

FIG. 16 is a cross-sectional view showing another aspect of the heat transfer container according to the present invention.

Front page continuation (72) Inventor Tatsushi Kashiwagi 4-33 Komachi, Naka-ku, Hiroshima City, Hiroshima Prefecture Chugoku Electric Power Co., Inc. 72) Inventor Akio Dewa 1-1, Kotobuki-cho, Mihara-shi, Hiroshima Mihara Rishige Engineering Co., Ltd.

Claims (3)

[Claims] 1. An essentially prismatic cylindrical unit container casing in which at least one of the four corners is cut and made flat so as to form a hydrogen storage alloy filled portion at both ends. A unit cell container having a casing arranged and a hydrogen gas flow tube penetrating the casing in an end casing at one end is arranged in a large number in a vertical and horizontal direction so that the hydrogen gas flow tubes are in the same direction. A prismatic heat transfer container filled with a hydrogen storage alloy for hydrogen storage, characterized in that a prismatic cylindrical body is closely packed in an outer casing. 2. An essentially prismatic tubular unit container casing, wherein at least one of the four sides has a semi-circular arc-shaped cross-section in the cross-section and small depressions continuous in the longitudinal direction of the container. The hydrogen-storing alloy-filled prismatic heat transfer container for hydrogen storage according to claim 1, wherein 3. The hydrogen storage alloy-filled rectangular heat transfer container for hydrogen storage according to claim 1, wherein the material of the prismatic cylindrical unit container casing is essentially clad steel.