JPS58195768A - Metallic hydride device - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to metal hydrides and devices.

Certain metals and alloys2. It absorbs hydrogen exothermically to form a metal hydride, and this metal hydride h<-q□,
□Yo8. , You 7. . 6. In recent years, various metal hydride devices such as heat pumps that utilize the characteristics of metal hydrides have been proposed.

Figure 1 shows a combination of a first metal hydride (hereinafter referred to as MHI) with a low equilibrium decomposition pressure and a second metal hydride (hereinafter referred to as MB2) with a high equilibrium decomposition pressure in the operating temperature range. 1 is a cycle diagram showing the operation of a device that obtains cold output or thermal output through so-called right-handed recycling, in which the horizontal axis represents the reciprocal of the absolute temperature T, and the vertical axis represents the equilibrium decomposition pressure P of metal hydrides. indicates the logarithm of

Initially, the above cycle will be explained assuming that MHI is in a state in which it has sufficiently absorbed hydrogen (point D) and MB2 is in a state in which it has sufficiently released hydrogen (point C).

In principle, first, MHI is heated by a high-temperature heat medium at a temperature TH, and MB2 is connected to a medium-temperature heat medium at a temperature TM.
HI emits hydrogen endothermically at point A), and this hydrogen is
H2 is exothermically occluded (point B). After hydrogen transfer is completed, when MHI is switched to a medium temperature heating medium with temperature TM and connected, and MB2 is switched to and connected to a low temperature heating medium with temperature TL, MB2 endothermically releases hydrogen (point C). , MHI absorbs this hydrogen exothermically (point D). Again, MH
A new cycle is started by connecting I to the high temperature heat medium and MB2 to the medium temperature heat medium.

Here, if the high-temperature heat medium is used as the driving heat source, the cold output can be obtained by using the low-temperature heat medium as the cooling load (point C), and
Thermal output can be obtained by using the intermediate temperature heating medium as the heating load (points B and/or D). Therefore, if another working pair is made to perform the same cycle as above with a half-cycle delay, cooling output or heating output can be obtained alternately from each working pair, and the cooling output can be used for cooling. Additionally, the thermal output can be used for space heating and hot water supply.

The device using one working pair as described above is known as a so-called four-cylinder device, in which the metal hydride is filled in closed containers that form a heat exchanger, and each closed container receives heat supplied by a pipe line. They are alternately heated and cooled in a medium to perform a hydrogen storage and release reaction between the working pair. That is, MHI and MB2 are filled into first and second closed containers, respectively, and the containers are communicated with each other through a communication pipe equipped with a control valve such as a solenoid valve that can be opened and closed so that hydrogen can move between the containers. Similarly, MHI and MB2 are filled in third and fourth closed containers, respectively, and communicated so that hydrogen can be transferred to form a second working pair.

However, in such a device, for example, when obtaining cold output, as is clear from the operation explained above,
After hydrogen transfer from MHI to MB2 is completed in the first working pair, when MHI is connected to a medium-temperature heating medium at temperature TM' (point D), hydrogen transfer from MB2 to MHI starts, and MB2 becomes hydrogen. Outputs cold energy by endothermic release of MB2 and its closed container itself (points B-C), so the above cold energy output is consumed to cool down MB2 and its closed container itself to temperature TL (points B-C).
The available cooling output will be reduced. Similarly, in the second working pair, after hydrogen transfer from MB2 to MHI is completed, MHI is connected to a high temperature heating medium and MB2 is connected to a medium temperature heating medium to heat them to a predetermined temperature. But especially M
It takes a lot of thermal energy input to heat HI to temperature TH (point DA). As described above, the above-mentioned apparatus requires a large amount of thermal energy, and a part of the cooling output is consumed for cooling the apparatus itself, so there is a problem that the coefficient of performance of the apparatus becomes small.

The high temperature heat medium is used as the driving heat source, and the medium temperature heat medium is used as the heating load.
In particular, when obtaining thermal output from MH2, it requires a lot of thermal energy and human power to heat MHI from temperature TM' to temperature TI (temperature TI), and when MH2 absorbs hydrogen and outputs thermal heat, the output also decreases. A part of it is consumed in heating MH2 from temperature TL to temperature TM (point C-B), so
Similarly, the coefficient of performance of the device becomes smaller.

The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide a metal/heater oxide device which requires less thermal energy input and has a high coefficient of performance.

The metal hydride device of the present invention has a first reactor filled with a metal hydride having a small equilibrium decomposition pressure of
The closed container and the second closed container filled with a second metal hydride having a high equilibrium decomposition pressure are connected so that hydrogen can move, forming a first working pair, and the second sealed container is filled with the first metal hydride. a third sealed container filled with the second metal hydride and a fourth sealed container filled with the second metal hydride.
The closed containers are connected to each other so that hydrogen can move therethrough to form a second working pair, and the first and third closed containers are capable of exchanging heat with a high-temperature heat medium and a medium-temperature heat medium through heat medium pipes, respectively. and the second and fourth closed containers are connected in a heat exchangeable and switchable manner to a medium-temperature heat medium and a low-temperature heat medium, respectively, by means of heat medium conduits, and in the first working pair, the first Hydrogen is endothermically released from the first metal hydride in the closed container and exothermically occluded in the second metal hydride in the second closed container, and at the same time, a fourth metal hydride is released in the second working pair. Hydrogen is endothermically released from the second metal hydride in the sealed container, and hydrogen is exothermically absorbed into the first metal hydride in the third sealed container, and then hydrogen is absorbed into the first metal hydride in the third sealed container. In the working pair of 11111, hydrogen is endothermically released from the second metal hydride in the second sealed container, and hydrogen is exothermically occluded in the first metal hydride in the first sealed container. At the same time, in the second working pair, hydrogen is endothermically released from the first metal hydride in the third closed container, and hydrogen is exothermically occluded in the second metal hydride in the fourth closed container. In a metal hydride apparatus having a cycle, the first and third
A bypass pipe is provided in the heat medium pipe that circulates and supplies a high temperature or medium temperature heat medium to the sealed container, and a connecting pipe is provided between the first and third sealed containers to enable heat exchange. A first heat exchange pipe of a closed loop is formed between the first and third sealed containers by being cut off from the medium temperature heating medium, and the medium temperature or low temperature heating medium is circulated through the second and fourth sealed containers. A bypass pipe line is provided in the heat medium pipe line to be supplied, and a connecting pipe line is provided between the second and fourth sealed containers to enable heat exchange, so that the second and fourth closed containers are isolated from the medium temperature and low temperature heat medium. forming a second heat exchange conduit in a closed loop between the four sealed containers, and the hydrogen release or occlusion of the first metal hydride in the first sealed container is completed;
After the first metal hydride in the third closed container has finished absorbing or desorbing hydrogen, heat is exchanged between the first and third closed containers through the first heat exchange pipe of the closed loop. At the same time, after the second metal hydride in the second sealed container has finished releasing or storing hydrogen, and the second metal hydride in the fourth sealed container has finished storing or releasing hydrogen, the closed container is closed. It is characterized in that heat is exchanged between the second and fourth closed containers using the second heat exchange pipe line of the loop.

FIG. 2 is a device circuit diagram showing a preferred embodiment of the metal hydride device of the present invention.

First, the case of obtaining cold heat will be explained. Closed containers 1 and 3 forming heat exchangers are filled with MHI, and control valves 11 and 1 are connected to a high temperature heat medium 5 having a temperature TH forming a driving heat source.
The heat medium pipes 21 are connected to each other in a switchable and heat exchangeable manner by heat medium pipes 21 having heat medium pipes 2, and are provided with the control valve to a medium temperature heat medium 6 having a temperature TM' using water as a heat medium, for example. They are each connected in a switchable and heat exchangeable manner by means of channels 22. The high-temperature heat medium conduit and the medium-temperature heat medium conduit each have heat medium pumps 31 and 32, and the conduits are selected by a control valve to alternately circulate and supply heat medium 0 to a predetermined closed container. On the other hand, the closed containers 2 and 4 are each filled with MH2, and are connected to the intermediate temperature heat medium 7 of the temperature TM through a pipe line 23 equipped with control valves 13 and 14, respectively, in a switchable and heat exchangeable manner, and, for example, , are connected to a low-temperature heat medium 8 having a temperature TL, which constitutes a low-temperature load using cold water as a heat medium, through a heat medium pipe 24 equipped with the control valve, respectively, in a switchable and heat exchangeable manner. The medium temperature heat medium pipe and the low temperature heat medium pipe are also each provided with a heat medium pump 33.
and 34 are provided, and the control valves 13 and 14 select a pipe line to alternately circulate and supply the heating medium to a predetermined closed container.

Further, the closed containers 1 and 2 are communicated with each other through a communication pipe 41 equipped with a control valve 15 such as a solenoid valve that can be opened and closed.
Similarly, the closed containers 3 and 4 are connected to each other through a communication pipe 42 equipped with a control valve 16 so that opening and closing can be controlled.
□ Forms the second working pair.

In the present invention, between the rain j・□1 and the third sealed container there is a connecting pipe 2 equipped with a control capable of opening/closing...Qj%17.
5 is provided, and a bypass pipe 27 is provided in the heat medium pipe that circulates and supplies high-temperature or medium-temperature heat medium 1 to the first and third closed containers, and a bypass pipe 27 is provided to connect the connecting pipe 25 and the bypass pipe. 27 form a first heat exchange line forming a closed loop between the first and third closed containers. In the illustrated device circuit, a bypass pipe 27 is provided between the inlet of the heat medium pipe to the first closed container and the outlet of the heat medium pipe to the third closed container. is not limited to this, but shares a part of the heat medium pipe, and
What is necessary is just to form a closed loop-shaped conduit between the first and third closed containers together with a connecting conduit that connects the first and third closed containers.

Similarly, a connecting pipe 26 equipped with a control valve 1'8 capable of opening and closing is provided between the second and fourth sealed containers, and a medium- or low-temperature heat source is provided between the second and fourth sealed containers. A bypass 1 pipe 28 is provided in the heat medium pipe that circulates and supplies the medium, and a second heat exchange pipe that forms a closed loop is also formed between the second and fourth closed containers. Ru. .

Two inter-vessel heat exchange pumps 35 and 36 are disposed in each of the closed loop heat exchange pipes, and are driven synchronously based on a cycle to be described later, between the first and third closed vessels. In addition, heat exchange is performed by circulating a heat medium between the second and fourth closed containers. Note that check valves 51 to 56 are provided in each heat medium pipe and heat exchange pipe as necessary.

In addition, the drawing shows two types of medium-temperature heating medium 6 at temperatures TM' and TM.
and 7 are shown, but there is no problem even if these temperatures are the same.

Next, the operation of the above-mentioned apparatus will be explained with reference to the cycle diagram shown in FIG. 3 for obtaining a cold output.

The closed vessels 1, 2.3 and 4 are turned on and are at C8A and B, respectively, and the cycle starts when the hydrogen transfer is completed. Therefore, the closed container 3 is heated by the high-temperature heating medium to a temperature TH, and the closed container 1 is heated to a temperature TM by the medium-temperature heating medium.
' is maintained. Further, the closed container 4 is maintained at a temperature TM by a medium-temperature heating medium, and the closed container 2 is connected to a low-temperature heating medium and is at a temperature TL.

Here, the operation of all the heat medium pumps 31 to 34 is stopped to stop the supply of heat medium to each closed container, and the control valves 17 and 18 are opened to open the connecting pipes 25 and 26. Inter-vessel heat exchange pump 35 for each of the first and second heat exchange pipes
When 36 and 36 are driven, a hot wire is circulated between the first and third closed containers by the first heat exchange pipe line, thereby performing heat exchange.

As a result, the closed container 1 is heated to the temperature TF, and
The closed container 3 is cooled to a temperature TE. That is, on the cycle diagram, the MHI in the closed container l is preheated and moves from point F to point F.
The MHI in the sealed container 3 is precooled and moves from point A to point E. At the same time, a heat medium is circulated through the second heat exchange pipe between the closed container 2 at temperature TL and the closed container 4 at temperature TM to perform heat exchange, and the closed container 2 is heated to a temperature TK, and the closed container 4 is sealed. Container 4 is cooled to temperature TG. That is, the MH2 in the closed containers 2 and 4 are precooled or preheated, respectively, from points C and B to points K and G.

In this way, heat exchange is performed between the first and third closed containers, and heat exchange is also performed between the second and fourth closed containers, so that each of them is preheated or precooled. , the inter-vessel heat exchange pumps 35 and 36 are stopped, the control valves 17 and 18 are closed, and heat exchange between the closed vessels is stopped.

Next, the heat medium pumps 31 and 32 are driven again to supply the high temperature heat medium 5 to the closed container l and heat it to the temperature TH.
I is brought from point F to point A, while the closed container 3 is cooled from the temperature TE to TM' by supplying the medium temperature heat medium 6 again.

Next, by opening the control valve 15 while keeping the closed container 1 at the temperature TH and the closed container 3 at the temperature TM, the hydrogen released endothermically by the MHI in the closed container 1 is transferred to the closed container at the temperature TK through the communication pipe 41. On the other hand, the hydrogen released by MH2 in the closed container 4 at the temperature TG flows into the closed container 3 at the temperature TM' through the communication pipe 42. As a result, in the closed container 2, hydrogen storage of MH2 is prevented. The refrigerant temperature rises from TK to TM, while the closed vessel 1 emits hydrogen endothermically and reaches the temperature TL.Here, the heat medium pumps 353 and 34 are driven to bring the temperature to TM. Heat medium 7 is placed in container 2
At the same time, the low temperature heat medium 8 is supplied to the closed container 4 to cause the low temperature heat medium to output cold heat.

This completes the half cycle, but the same operation is repeated between different closed containers in the latter half cycle.

As described above, according to the device of the present invention, hydrogen is transferred between the first and second closed containers forming the first working pair and between the third and fourth closed containers forming the second working pair. After the transfer is completed, heat is exchanged between the first and third sealed containers and between the second and fourth sealed containers to prepare each sealed container for the next hydrogen storage or release. to pre-cool or pre-heat the
The thermal energy required to heat the sealed container itself is reduced, and the amount of cold energy consumed for cooling the metal hydride itself and the sealed container filled with it is also reduced. , the coefficient of performance of the device is improved. Further, since the heat exchange pipes between the closed containers share a part of the heat medium pipe, the arrangement of the six pipes is simple.

It will be easily understood that the same applies to the case where thermal output is obtained by a clockwise cycle.

The present invention is also applicable to the device shown in FIG. 4 which operates by so-called left-handed recycling.

In Figure 4, as is clear from comparison with Figure 3,
Hydrogen transfer of A-H is performed on the low temperature side and hydrogen transfer of C-D is performed on the high temperature side, forming an A-B-C-D cycle. The closed containers 3 of the second working pair are connected to the high temperature heat medium and the medium temperature heat medium in a switchable and heat exchangeable manner, respectively, and the closed containers 2 of the first working pair and the closed containers 4 of the second working pair are connected to the medium temperature heat medium. and a low-temperature heating medium, respectively, in a switchable and heat exchangeable manner.

In such a device, for example, if a medium-temperature heat medium is used as the drive heat source and a cooler is used that uses a heat medium such as water or air as the low-temperature heat medium, thermal output can be obtained from the high-temperature heat medium. Therefore, in this device as well, after hydrogen transfer is completed between each working pair, heat exchange is performed between the first and third closed containers and between the second and fourth closed containers, respectively. , especially M.H.
Less input thermal energy is required when heating I from temperature TM to temperature TH.

Furthermore, in the present invention, as shown in FIG. 2, control valves 61 to 64 are provided in each heat medium pipe, and a second bypass connects the outlet and inlet of each heat medium pipe through the control valve. Conduits 71 to 74 can be provided. In this device, when the heat exchange is performed between the predetermined closed containers as described above after the hydrogen transfer is completed between each working pair, even if the heat medium pump continues to operate, the heat medium is not supplied to the closed containers. Then, the heat medium is circulated through the second bypass pipe, and the inter-vessel heat exchange pump is driven to circulate the heat medium between the closed vessels. Pumps generally consume a large amount of electricity when they start operating, but in metal hydride equipment, heat exchange between containers is usually performed several times an hour, so the heat medium pump must be stopped and restarted each time. For example, electricity consumption will be higher for the less wealthy. However, according to the present invention, as described above, the heat medium control valve and the second bypass line form a circulation line that does not supply the heat medium to the closed container even if the heat medium pump continues to operate. , unnecessary consumption of power can be avoided.

[Brief explanation of the drawing]

FIG. 1 is a cycle diagram for explaining the operation of the conventional device, FIG. 2 is a circuit diagram of the device of the present invention, and FIG. 3 is a cycle diagram for explaining the operation of the device of the present invention.
FIG. 4 is another cycle diagram. 1.2.3.4... Sealed container, 5... High temperature heat medium, 6
．． 7...Medium temperature heating medium, 8...Low temperature heating medium, 11.12,
]3.14.15.16.17.18...Control valve, 2
1.22.23.24...heat medium pipe, 25.26...
・Connection pipe line, 27.28... Bypass pipe line, 41.4
2...Communication pipe. Patent Applicant: Sekisui Chemical Co., Ltd. 1 Representative Mototoshi Fujinuma 9 Figure 3 1 Figure 4 1/7 - Supplementary Procedures (Method) 1.・J) F+'s large and small 157th year patent i No. 797! il issue 2,
Akira's name: Person who operates metal aqueous compound device 3, supplement 11 Personal relationship: Patent applicant

Claims (1)

[Claims] (Hydrogen moves between the first closed container filled with a first metal hydride with a low equilibrium decomposition pressure and the second closed container filled with a second metal hydride with a high equilibrium decomposition pressure in the 11 operating temperature range. in communication with the first actuating pair so as to obtain;
A third sealed container filled with the first metal hydride and a fourth sealed container filled with the second metal hydride are communicated so that hydrogen can move therethrough to form a second working pair; and third
The sealed containers are respectively connected to a high temperature heat medium and a medium temperature heat medium by heat medium pipes in a heat exchangeable and switchable manner, and
The second and fourth sealed containers are connected to a medium-temperature heating medium and a low-temperature heating medium, respectively, by heating medium pipes in a heat exchangeable and switchable manner, and in the first working pair, the first metal of the first sealed container is Hydrogen is endothermically released from the hydride and exothermically stored in the second metal hydride in the second closed container 1, while the second metal hydride in the fourth closed container 1 is simultaneously released in the second working pair. Hydrogen is released endothermically from the metal hydride of
exothermically occluded in a first metal hydride in a sealed container;
Next, in the first working pair, hydrogen is endothermically released from the second metal hydride in the second sealed container, and hydrogen is exothermically occluded in the first metal hydride in the first sealed container. At the same time, hydrogen is endothermically released from the first metal hydride in the third sealed container in the second working pair, and is exothermically transferred to the second metal hydride in the fourth sealed container. In a metal hydride apparatus having an occlusion cycle, a bypass pipe is provided in the heat medium pipe that circulates and supplies a high temperature or medium temperature heat medium to the first and third closed containers;
A connecting pipe is provided between the closed containers to enable heat exchange, and a first heat exchange pipe of a closed loop is formed between the first and third closed containers by being isolated from the high-temperature and medium-temperature heating medium. At the same time, a bypass pipe is provided in the heat medium pipe that circulates and supplies medium-temperature or low-temperature heat medium to the second and fourth closed containers, and the second and fourth closed containers are connected for heat exchange. A conduit is provided to form a second heat exchange conduit in a closed loop between the second and fourth closed vessels in isolation from the medium and low temperature heat transfer medium, and After the hydrogen storage or desorption of the metal hydride is completed and the hydrogen storage or desorption of the first metal hydride in the third closed container is completed, the first heat exchange pipe of the closed loop At the same time, heat is exchanged between the first and third sealed containers, the release or storage of hydrogen in the second metal hydride in the second sealed container is completed, and the second metal hydride in the fourth sealed container finishes. A metal hydride device characterized in that after hydrogen storage or release is completed, heat is exchanged between the second and fourth closed containers through the closed loop second heat exchange pipe.