JPS58173358A - Metal 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 hydride devices.

It is known that certain metals and alloys absorb hydrogen exothermically to form metal hydrides, and that these metal hydrides reversibly release hydrogen. Various metal hydride devices have been proposed, such as heat pumps that utilize the properties of metal hydrides. Conventionally, a first metal hydride (MHI) and a second metal hydride (Ml2), which have different equilibrium decomposition pressures, are each filled in a closed container that can exchange heat with a heating medium, and hydrogen is transferred between the containers. In the case of a so-called four-cylinder type metal hydride apparatus, two working pairs are provided to constitute the metal hydride apparatus.

The operation of such a metal hydride device will be explained based on the cycle diagram shown in FIG. 1 in the case where the cold output is obtained by a so-called clockwise cycle.
1'□ In the drawing, the horizontal axis shows the reciprocal of absolute temperature, and the vertical axis shows the logarithm of the equilibrium decomposition pressure of metal hydride.

Initially, it is assumed that MHI is in a state in which it has sufficiently absorbed hydrogen (point D), and Ml2 is in a state in which it has sufficiently released hydrogen (point C). First, MHI, which has a high equilibrium decomposition pressure in the operating temperature range, is heated by a high temperature drive heat source at a temperature TI, and Ml2, which has a low equilibrium decomposition pressure, is heated to a temperature TM, such as the outside air.
When connected to a medium temperature heating medium, Ml-II endothermically releases hydrogen at point A), and Ml2 absorbs this hydrogen exothermically (B). After hydrogen transfer is completed, when MHI is switched to a medium temperature heat medium and connected, and Ml2 is switched to and connected to a low temperature heat medium of temperature TL for cooling load such as chilled water, Ml2
The MHI releases hydrogen endothermically (point c), and MHI absorbs this hydrogen exothermically (point D). Here, a cold output can be obtained in the low-temperature heating medium (point C), and a thermal output can be obtained in the medium-temperature heating medium (points B and D) as required. Again, connect the MHI to a high temperature driven heat source and
2 to a medium temperature heating medium, a new cycle is started.

Therefore, by causing another working pair to perform the same cycle as above with a half-cycle delay, the cooling output associated with the hydrogen release of Ml2 can be obtained alternately from each working pair, and can be used, for example, for cooling. Further, the thermal output can be used for space heating or hot water supply, for example.

However, in conventional metal hydride equipment that uses multiple pairs of the same working pairs made of two types of metal hydrides with different equilibrium decomposition pressures, the temperature of the driving heat source is fixed in advance depending on the types of MHL and Ml2 used. For example, when two or more types of heat sources with different temperatures can be used, such as an expensive heat source such as city gas and a cheap or free heat source such as solar heat or waste heat. In some cases, it is necessary to use only one of the heat sources as the drive heat source depending on the preset operating temperature, especially when a low-cost or free heat source cannot be used as the second heat source, the coefficient of performance of the device may decrease. is low, and its thermoeconomic efficiency is poor.

The present invention has been made to solve these problems, and is capable of efficiently using multiple heat sources at different temperatures as drive heat sources at the same time. Therefore, it is highly economical to use the heat sources and has a high coefficient of performance. The object is to provide a metal hydride device.

The first metal hydride device according to the present invention uses three types of metal hydrides having different equilibrium decomposition pressures in the operating temperature range, and a two-metal hydride device filled with two types of metal hydrides that have different equilibrium decomposition pressures in the operating temperature range.
At least two closed containers are connected to each other so that hydrogen can move to form a working pair, and at least two working pairs are provided, and a first metal hydride having a low equilibrium decomposition pressure is sealed in one of the first working pairs. A second metal hydride having the next lowest equilibrium decomposition pressure is charged into one closed container of the second working pair, and a third metal hydride having the highest equilibrium decomposition pressure is charged into the first and second closed containers. It is characterized in that it is made by filling the remaining airtight container with the working pair of □.

EMBODIMENT OF THE INVENTION The 1st metal hydride apparatus of this invention is demonstrated based on the drawing which shows an Example below.

Figure 2 shows three different equilibrium decomposition pressures in the operating temperature range.
The first using seed metal hydrides MHIMH2 and MH3
An example of a metal hydride apparatus is shown in which MHI with a small equilibrium decomposition pressure and MH2 with the next smallest equilibrium decomposition pressure are filled in closed containers 1 and 3 forming a heat exchanger, respectively, and MB2 with a high equilibrium decomposition pressure is filled with Closed containers 2 and 4 forming a heat exchanger are filled with each other, and the containers 11 and 2 are communicated with each other by a communication pipe 9 so that hydrogen can move, forming a first working pair. 4 are also communicated through the communication pipe 10 to form a second working pair. Each communication pipe is provided with control valves 11 and 12 such as electromagnetic valves, and each communication pipe is opened and closed according to a cycle described later.

Further, the container l is connected to the first driving heat source 5 at a high temperature THI and at a temperature T
The medium temperature heating medium 6 of
It is connected to a second driving heat source 7 of high temperature TH2 (<THI) and a medium temperature heat medium 6 through conduits 15 and 16, respectively, so as to be able to exchange heat and to switch. on the other hand,
In the first working pair, the container 2 filled with MB2 having a high equilibrium decomposition pressure is connected to the temperature TL by pipes 17 and 18, respectively.
The container 4 filled with MB2 in the second working pair is connected to the low temperature heat medium 8 and the medium temperature heat medium 6 by conduits 19 and 20 in a heat exchangeable and switchable manner. It is connected to the heating medium 6 in a heat exchangeable and switchable manner.

The connection between each container and the heat source or heating medium is switched by a control valve such as a solenoid valve (not shown). The device is a four-cylinder device with two working pairs.

The operation of the above device will be explained with reference to the cycle diagram shown in FIG. In addition, in FIG. 2, a single medium-temperature heating medium 6 is shown, and the vessels 1, 2, 3, and 4 are all connected to this single medium-temperature heating medium, but there is no single medium-temperature heating medium. For example, in the first working pair, vessel 1 is connected to a medium-temperature heating medium at a temperature TMI, vessel 2 is connected to a medium-temperature heating medium at a temperature TM2 different from TMI, and in the second working pair Both containers 3 and 4 may be connected to a medium-temperature heating medium at a temperature TM2. FIG. 3 shows a cytal diagram in which each vessel is thus connected to a respective intermediate temperature heating medium.

First, in the first working pair, when the container 11 is connected to the first high temperature driving heat source to heat the MHI to the temperature THI, and the dollar container 2 is connected to the medium temperature heating medium to maintain the MB2 at the temperature TM2, the MH
Point I endothermically expels hydrogen (point A), this hydrogen reaches the container 2 through the communication pipe 9, and MB2 exothermically stores it (point B).

At the same time, in the second working pair, Yong! 3 is connected to a medium-temperature heating medium at a temperature of TM2, and a container 14 is connected to a low-temperature heating medium at a temperature of TL to endothermically release hydrogen from MB2 (point C), which reaches the container 3 through a communication pipe 10. If the MB2 is exothermically occluded (point H), cold output can be obtained in the low temperature heat medium (point C). This cold output can be used for cooling, for example. Further, the thermal output (point B) due to hydrogen storage of MB2 and the thermal output (point H) due to hydrogen storage of MB2 can be used, for example, for hot water supply, as necessary.

Next, after hydrogen transfer is completed in each working pair, the first
In the working pair, when vessel 1 is connected to a medium-temperature heat medium at a temperature TMI and vessel 2 is connected to a low-temperature heat medium, the MHI in the vessel
Due to the pressure difference between the equilibrium decomposition pressures of Cold heat output can be obtained in the low-temperature heat medium (point C), and hot heat output can be obtained in the medium-temperature heat medium (point D) due to heat generation due to hydrogen absorption of MHI. The cold output can be used, for example, for cooling, and the thermal output can be used, for example, for heating or hot water supply.

At the same time, in the second working pair, when the vessel 3 is connected to a second high-temperature driving heat source to heat MB2 to a temperature TH2, and the vessel 84 is connected to a medium-temperature heat medium at a temperature TM2 to cool it, MB2 absorbs heat. MB2 exothermically absorbs this hydrogen (point B). If the heat generated by hydrogen absorption in MB2 is also required, it can be obtained as heat output in the intermediate temperature heat medium (point B).

0 The clockwise cycle is thus completed and a new cycle begins again by connecting each container to the original heat source or heat transfer medium.

As described above, according to the first metal hydride device of the present invention, it is possible to obtain cold output and/or thermal output by using two types of high-temperature heat sources with varying temperatures as described above.

In addition, in the present invention, the MHI in the first working pair
The hydrogen transfer from MH3 to MH3 (A-B) is completed, and the hydrogen transfer from MH3 to MH2 (C-+H
) is completed, heat exchange is performed by circulating an appropriate heat medium through the pipe 21 between MHI at temperature TH1 and MH2 at temperature TM2, and MH2 is preheated to around the intermediate temperature between THI and 7M2. This is thermoeconomically advantageous because the heat supply from the driving heat source for heating MH2 to temperature TH2 in the next step can be reduced. At the same time, since the MHI can be pre-cooled, the efficiency of acquiring cold output is also increased. Similarly, for metal hydrides with a high equilibrium decomposition pressure, heat exchange is performed by circulating an appropriate heating medium between MH3 at temperature TM2 and MHI13 at temperature TL through the pipe 22, and each MH3 is transferred to the next It is thermoeconomically advantageous to preheat or precool the water in preparation for this step.

Also, in the first working pair, hydrogen transfer (CD) from MH3 to MHI is completed, and in the second working pair, MH
When the hydrogen transfer from 2 to MH3 (E→B) is completed, heat is exchanged between MH2 at temperature TH2 and MHI at temperature TML, and MH3 at temperature TM2 and M at temperature TL are exchanged.
It is advantageous to preheat or precool the respective metal hydride by exchanging heat with H3.

In the device temperature cycle explained above, the MHI is 4.7 T as LaNi AI MH2.
O, λ11 LaNi,, At,, 5, and as MH3 La
When using N t r, 4, the temperature of the heat source and heating medium can be set to approximately 1 as follows.

Input TH1 = 100°C (first high temperature drive heat source) TH2 = 80°C (second high temperature drive 2 heat source) Output TL1 = 10°C (cold output) TM1 =
45° C. (thermal output) 7M2 = 30° C. (atmospheric temperature) Therefore, a cooling output of about 10° C. and a thermal output of about 45° C. can be obtained, and it can be suitably used in an air conditioning hot water supply system.

Next, the case where the device of the present invention is used for heating and hot water supply will be explained with reference to the cycle diagram shown in FIG.

The main parts of the device are the same as those in Fig. 2, but in addition to the high-temperature drive heat source at temperature TH (reference number 7 is the same as reference number 5), there are also solar heat at temperature TL2 and temperature TLI. (<TL2), for example, two types of low-temperature heat sources are used, including the atmosphere. Therefore, in this apparatus for heating and hot water supply, the reference number 8 in FIG. 2 means two types of low-temperature heat sources.

In this device, MHI with a small equilibrium cracking pressure and MH3 with a large equilibrium cracking pressure constitute the first working pair, and MH2 with the next smallest equilibrium cracking pressure and MH3 with the highest equilibrium cracking pressure form the second working pair. The configuration 3 is the same as the device of FIG. 2, so that the first working pair constitutes a cycle from point A-4B→C-+D, and the second working pair forms a cycle from point E-+F-40. - Configure the H cycle. According to this cycle, in the first working pair, MHI is heated by a high temperature heat source at temperature TH, and from MHI to MH
Hydrogen transfer to No. 3 occurs, and the heat generated at this time (point B) can be obtained as thermal output for heating and hot water supply. MH3, which has absorbed hydrogen in this way, is then connected to a low-temperature heating medium at temperature TLI, while MHI, which has released hydrogen, is at temperature TM1.
Here, hydrogen transfer from MH3 to MHI occurs, and the thermal output (point D) due to hydrogen storage in MHI can be used for heating and hot water supply.

In the second working pair, MH2 is similarly heated by a high temperature heat source at temperature TH, resulting in hydrogen transfer from MH2 to MH3. As a result, a thermal output (point F) that can be used for heating and hot water supply can be obtained from MH3. MH3, which has absorbed hydrogen, is then heated by a low-temperature heat source, such as solar heat, at a temperature TL2, while M and H2, which have released hydrogen, are cooled by a medium-temperature heat source at a temperature TMI, and hydrogen transfer from MB2 to MB2 is performed. Here, the thermal output (point H) obtained by hydrogen storage of MB2 can be provided for heating and hot water supply.

When using the same combination of La--Ni metal hydrides as described above in the above-described apparatus, the temperatures of the Atami and the heating medium can be specifically set approximately as follows.

Input TH1=110℃ (high temperature heat 1l) TL2=
30℃ (solar heat) TLl=, 0℃ (atmosphere) Output 7M1= 50℃ (heating and hot water) TM2
= 40℃ (hot water supply) In the device that operates according to the cycle diagram shown in Figure 6 above, a low-temperature heat source of two poles, called temperature wings, is used.
Either one operates one of the actuating pairs, which makes it possible to effectively utilize inexpensive thermal energy such as solar heat, and also allows heat to be pumped up from the atmosphere, which is advantageous in terms of thermoeconomics. It is.

In the conventional device, if solar heat could not be used, hydrogen transfer from G to H was not possible, but according to the device of the present invention, the thermal output at temperature TM2 from point B, which is inferior in quality as thermal output. By giving MB2 at point G, hydrogen transfer of G-4H can be performed.

Next, a case will be described in which the first metal hydride device of the present invention is driven in a counterclockwise cycle. The first working pair consisting of MHI and MB2 performs a cycle from point A-4B to C-D, and is driven by the first medium-temperature heating medium at temperature TMI and the second medium-temperature heating medium at temperature TM2, and produces a thermal output (point Give A). On the other hand, the second operating pair consisting of MB2 and MB2 is at point E
-F-4D → H cycle is carried out, driven by the first intermediate temperature heating medium at temperature TMI and the second intermediate temperature heating medium at temperature TM2, and the temperature T
Give the thermal output of H (point E).

In this left-turn recycle, high temperature thermal output can be obtained from points A and E using, for example, two low-quality medium-temperature driven heat sources.

1.6 In left-turn recycling, it is also possible to use a low-temperature heat source such as liquefied natural gas to extract a larger amount of cold output than a medium-temperature heat medium.

In the above device and cycle, the two working pairs are:
It is constructed by combining 211 blades MHI and MB2 with small equilibrium cracking pressure with MB2 with large equilibrium cracking pressure, but MB2 with small equilibrium cracking pressure is combined with the true MHI and MB2 of 24 m with high equilibrium cracking pressure. They can also be combined to form two working pairs.

The second metal hydride device of the present invention uses 3@metal hydrides with different equilibrium decomposition pressures in the operating temperature range, and connects two closed containers filled with 211 metal hydrides with different equilibrium decomposition pressures to hydrogen. At least two working pairs are provided, and a first metal hydride having a large equilibrium decomposition pressure is filled into a closed container of one of the first working pairs, and the equilibrium A second metal hydride with the next highest decomposition pressure is filled into one closed container of the second working pair, and a third metal hydride with the lowest equilibrium decomposition pressure is charged into the remaining one of the first and seventh working pairs. It is characterized by being filled in a closed container.

This device is constructed in FIG. 2, with containers 1.2.3 and 4 filled with MB2, MHI, MB2, and MB2, respectively, and the heat source and heat medium connections are the same as in FIG.

FIG. 6 shows a clockwise cycle of such a metal hydride device, in which the first working pair consisting of MHI and MB2 is moved from point A to B-C-D by the hot first driving heat source at temperature THI.
The cycle is performed to give the cold output at temperature TL (point C) and the thermal output at temperature TMI (point D). MB2 to MHI
The thermal output of the MHI that accompanies the hydrogen transfer to the hydrogen can be effectively used as needed, but it may also be released into the atmosphere at a temperature TM2 (<TMI), for example. Further, the second working pair consisting of MB2 and MB2 performs a cycle from point B-+F→G→H by the high temperature second drive heat source at temperature TH2, and the temperature T
Give the cold and heat output of L. Temperature T due to hydrogen absorption of MB2
The way the heat is released in M2 (points F and H) can be effectively used as described above, but it may also be released outside the system. In this way, the cold output at temperature TL can be used for cooling, and the thermal output at temperature TM1 (and temperature TM2) can be used for heating and hot water supply.

FIG. 7 shows a cycle diagram when two types of low-temperature driving heat sources are used in the second metal hydride apparatus of the present invention. That is, the first working pair performs a cycle of points A→B4C→D, and Mn3 is heated by the high temperature driving heat source (point A) at temperature TH and the first low temperature heat m (point C) at temperature TLI, Each provides a thermal output at a medium-temperature heating medium (points and B), while the second working pair provides a thermal output at points A-4F-4G-+H.
Mn3 is heated to high temperature drive heat ml (point A)
and a second low-temperature heat ml (point G) at temperature TL2, respectively, giving a thermal output in the medium-temperature heating medium (points H and F), the thermal output thus obtained being used for space heating and/or hot water supply. can do.

In addition, in Figure 7, solar heat is expressed at point G as in Figure 4.
The heat contained in the atmosphere can be pumped up at point C.

9 The case of driving the counterclockwise cycle in this second device will be explained with reference to FIG. First, in the first working pair, the container 82 is connected to the first medium-temperature driving heat/' strainer to heat the MHI to the temperature TMI, and the container I is connected to the high-temperature heating medium to maintain the Mn3 at the temperature TH. , MHI releases hydrogen endothermically (point D), and Mn3 absorbs this hydrogen exothermically (point A). On the other hand, in the second working pair, when the container 4 is connected to a low-temperature heating medium at a temperature TL and the container 3 is connected to an intermediate-temperature heating medium to cause hydrogen to be released endothermically from Mn3 (point F), this hydrogen is exothermically occluded by Mn2 (point G).

Next, in the first working pair, when MHI is switched to a low-temperature heating medium and connected, and Mn3 is switched to and connected to a medium-temperature heating medium at a temperature TM2, Mn3 endothermically releases hydrogen (point B).
, this hydrogen is occluded by MHI (point C). On the other hand, in the second working pair, when Mn2 is switched to the second medium-temperature heating medium and connected to heat it to temperature TM2, and Mn3 is switched to and connected to the high-temperature heating medium, Mn2 endothermically releases hydrogen. point H), and Mn3 absorbs this hydrogen exothermically (point A). Therefore, it is possible to obtain thermal output due to hydrogen absorption of Mn3.

Thus, when a counterclockwise cycle is completed, a new cycle is started by connecting each container to the original heat source or heating medium.Using two medium temperature heat sources with different temperatures, such as zero or more. As a result, higher temperature thermal output can be obtained.

In this counterclockwise cycle, as described above, after the hydrogen transfer between the containers is completed, heat is exchanged between the high temperature container and the low temperature container to preheat the low temperature metal turbine, and the high temperature It is advantageous to pre-cool the metal hydride in preparation for the next stage.

The third device of the present invention, which uses four types of metal hydrides with different equilibrium decomposition pressures, uses four types of metal hydrides with different equilibrium decomposition pressures in the operating temperature range.
Two sealed containers filled with metal hydrides of No. 411 are connected so that hydrogen can move to form a working pair, and at least two pairs of these working pairs are provided, and a first metal hydride having the lowest equilibrium decomposition pressure is formed. is charged into one closed container of the first working pair, and a second metal hydride, which has the next lowest equilibrium decomposition pressure, is charged into one closed container of the second working pair. A large third metal hydride is filled into the remaining closed container of the first or second working pair, and a fourth metal hydride having the next highest equilibrium decomposition pressure is charged into the remaining closed container of the second or first working pair. It is characterized by being filled with.

A cycle diagram as an example of the operation of this device is shown in FIG. The illustrated device has a capacity of 1.2.3 in FIG.
and rJ4 are filled with yHl, Mn3, Mn2 and Mn4, respectively, and the connections with the heat source and heat medium are the same as in the case shown in FIG. It will also be clear that the cycles of the first and second actuating pairs and the resulting outputs are also the same as in FIG. In addition, in FIG. 9, the hydrogen transfer (C'→D') is shown by the dashed arrow;
, 7M2, TL and TL2, the thermal output at the same temperature TM2 is 4 at points B, F, H and D.
It will be easy to understand what can be derived from the points. According to the metal hydride device of the present invention, as described above, it is possible to effectively utilize driving heat sources of 21i or more having different temperatures at the same time to obtain thermal output and/or cold output. It has a coefficient of performance of 1,000,000 and excellent thermoeconomic efficiency.

[Brief explanation of the drawing]

Fig. 1 is a cycle diagram showing the operation of a conventional metal hydride device, Fig. 2 is a circuit configuration diagram showing an embodiment of the metal hydride device of the present invention, and Figs. 3 to 9 are device of the present invention. FIG. 2 is a cycle diagram showing the operation of FIG. 1.2.3.4... Sealed container, 5.6.7.8... Heat source or heat medium, 9.10... Communication pipe, 1112... Control valve, 13.14.15. 16.17.18.19.20.2
1.22...Pipeline, MHI, MH2, MH3, MH4...Metal hydride. Patent applicant: Sekisui Chemical Co., Ltd. 11 Representative: Mototoshi Fujinuma 3 Figure 1 Figure 23'! hγ Ti'li 7;412;17271
Busha J each TH7M2 μfI 7a2 TL1 φ Etch' THL Katana/27M1 7M2?

Claims (1)

[Claims] (Using three types of metal hydrides with equilibrium decomposition pressures in the 11 operating temperature range, hydrogen moves through two closed containers filled with two cages of metal hydrides with different equilibrium decomposition pressures. At least two working pairs are provided, and a first metal hydride having a low equilibrium decomposition pressure is filled into a sealed container of one of the first working pairs, and equilibrium decomposition is performed. A second metal hydride with the next lowest pressure is filled into one closed container of the second working pair, and a third metal hydride with a higher equilibrium decomposition pressure is filled into the remaining closed containers of the first and second working pairs. (2) Using three types of metal hydrides that have equilibrium decomposition pressures in the operating temperature range, two types of metal hydrides with different equilibrium decomposition pressures are used. Two filled closed containers are connected so that hydrogen can move to form a working pair, and at least two working pairs are provided, and a first metal hydride having a high equilibrium decomposition pressure is placed in the first working pair. A second metal hydride having the next highest equilibrium decomposition pressure is charged into one closed container of the second working pair, and a third metal hydride having the lowest equilibrium decomposition pressure is charged into the first closed container. A metal hydride device characterized in that the remaining closed container is filled with a second working pair and a second working pair. Two sealed containers filled with two different types of metal hydrides are communicated so that hydrogen can move to form a working pair, and this working pair is made up of at least two
A first metal hydride with the lowest equilibrium decomposition pressure is filled into one closed container of the first working pair, and a second metal hydride with the next lowest equilibrium decomposition pressure is charged into the second metal hydride with the lowest equilibrium decomposition pressure. One closed container is filled with a third metal hydride having the highest equilibrium decomposition pressure, and the remaining closed container of the first or second working pair is filled with a fourth metal hydride having the next highest equilibrium decomposition pressure. the second
Or a metal hydride device, characterized in that the remaining closed container of the first working pair is filled.