JPH0663674B2 - Energy conversion method and device using hydrogen storage metal - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention produces a metal hydride mainly from a hydrogen storage metal and hydrogen used in a hydrogen storage / transportation system or an energy recovery / power conversion system. The present invention relates to an energy conversion method and an energy conversion device using a reaction and its reverse reaction.

(Prior Art) As a conventional energy conversion method utilizing a storage reaction of hydrogen accompanied by heat generation when a metal hydride is produced from a hydrogen storage metal and hydrogen and a hydrogen release reaction accompanied by the opposite heat absorption thereof, for example, , A container provided with a packed bed filled with particles of a hydrogen storage metal inside, and a plurality of heat transfer tubes arranged at intervals in the packed bed, using cold water as a heat medium in the heat transfer tube or Hot water is flown, the metal particles are cooled or heated through the heat transfer tube, and hydrogen gas is circulated in the packed bed to cause hydrogen absorption or desorption reaction in the metal particles, or pressurization of the hydrogen gas. Alternatively, the metal particles are decompressed to cause an occlusion reaction and a desorption reaction, and the reaction heat generated thereby is used to heat or cool a heat medium through a heat transfer tube to convert energy (JP-A-60- No. 101398),
Also, using a container in which a heat transfer tube is arranged in a coil shape,
The container is filled with a suspension of particles of a hydrogen storage metal suspended in oil, and the suspension is cooled or heated through a heat medium flowing through the heat transfer tube, and hydrogen gas is added to the suspension. Injecting hydrogen to cause a hydrogen absorption reaction and a hydrogen desorption reaction, or to convert energy by pressurizing or depressurizing hydrogen gas as described above to heat or cool the heat medium via a heat transfer tube JP-A-58-217401) is known.

(Problems to be Solved by the Invention) In the former invention, heat exchange is performed by bringing the metal particles of the packed bed into contact with the heat transfer tube, but the heat transfer tube is in direct contact with the filled metal. There is a problem that the heat exchange efficiency is deteriorated because it is only a part of the particles.

On the other hand, in the latter invention, the heat exchange efficiency is somewhat improved because the suspension in which the metal particles are suspended and the heat transfer tube come into contact with each other, but the hydrogen gas blown into the suspension becomes bubbles. There is a problem that the temperature rises in the suspension, the contact between the metal particles and hydrogen becomes insufficient, and the reaction efficiency deteriorates.

An object of the present invention is to provide an energy conversion direction and an energy conversion device using a hydrogen storage metal that improves the heat exchange efficiency, which is the above problem, and also improves the reaction efficiency.

(Means for Solving the Problems) The present invention proposes a conversion method for achieving the above-mentioned object, and an energy conversion method utilizing a reaction for producing a metal hydride from a hydrogen storage metal and hydrogen and an opposite reaction. The container is provided with a packing layer filled with a large number of small pieces of hydrogen storage metal, and the hydrogen gas is occluded or released by circulating hydrogen gas through the packing layer, and the packing layer is heated from above. The feature is that the medium is poured.

Further, the present invention proposes a conversion device for carrying out the conversion method, which is an energy conversion device utilizing a reaction of producing a metal hydride from a hydrogen storage metal and hydrogen, and a reaction thereof. A filling layer filled with a large number of small pieces of hydrogen storage metal is provided in the container, a connection port of the hydrogen pipe is provided at the upper part of the container, and a heat medium outlet is provided at the lower part, and the filling layer is provided inside the container. And a discharge port for pouring the heat medium onto the packed bed.

(Operation) Hydrogen gas is circulated from the connection port of the hydrogen pipe to the packed bed and the cooled heat medium is poured from the discharge port to the packed bed, and the heat of reaction is absorbed from the small pieces of the hydrogen storage metal constituting the packed bed. To cause a hydrogen occlusion reaction, or a high-pressure hydrogen gas is circulated from the connection port to the packed bed to cause an exothermic action by the hydrogen occlusion reaction in the small pieces and at the same time a heating medium is poured into the packed bed, The heating medium is heated for the heat source. On the other hand, with respect to the metal hydride produced by this reaction, a heated heat medium is poured into the packed bed to supply reaction heat to the small pieces of the metal hydride to cause a hydrogen release reaction, or from the connection port. Hydrogen gas is sucked to cause an endothermic action by the hydrogen releasing reaction in the small pieces, and the heat medium is poured into the packed bed to cool the heat medium for a cold heat source.

In this way, by pouring a liquid heat medium into a packed bed filled with a large number of small pieces of hydrogen-absorbing metal and circulating hydrogen gas, the heat medium sew gaps between the small pieces and their surfaces are sewn. At the same time, hydrogen gas is accompanied by the heat medium, or freely sewn through the gaps between these small pieces and flows. Therefore, the heat medium is brought into direct contact with each small piece of the hydrogen storage metal, and heat exchange can be performed by using the entire surface area of each small piece as a heat transfer area. Also, hydrogen gas is also included in each small piece. The total surface area can be used as the reaction area to carry out the occlusion / release reaction.

(Example) With reference to FIG. 1, reference numeral 1 denotes a container, and the container 1 is filled with a large number of small pieces S of a hydrogen storage metal in the upper and lower perforated plates 2 and 2 in the middle thereof. Layer 3 is provided and the container 1
A connection port 4a of the hydrogen pipe 4 and a liquid heat medium outlet 5 are provided in the lower part of the container, and the heat medium is placed inside the container 1 above the packed layer 3 to dispose the heat medium. It is configured by providing a shower head 6 which is a discharge port that pours into the filling port 3, and causes hydrogen gas to flow from the connection port 4a to the packed layer 3 to cause the hydrogen gas occlusion reaction or desorption reaction on the hydrogen storage metal small lumps S. And the filling layer 3 from the shower head 6
The heating medium and the small pieces S are poured onto the heating medium.
Are directly contacted with each other for heat exchange, and further, a circulation circuit 7 for communicating the shower head 6 and the outlet 5 is provided outside the container 1, and a circulation pump 8 is provided in the circulation circuit 7. With the heat exchanger 10 connected to the external pipe 9,
The heat medium poured into the packed bed 3 is guided from the lower part of the container to the circulation circuit 7, passed from the circulation pump 8 through the heat exchanger 10 to the shower head 6, and in the heat exchanger 10, hot water is supplied to the external pipe 9. , Cold water or intermediate water is introduced to exchange heat with the heat medium.

In this case, a stable solution of water, an organic solvent, silicon or the like is used as the heat medium, and the small pieces S of the hydrogen storage metal are spherical or have a Raschig ring, a slotted ring, an interstitial ring of about 10 to 50 mm. A molded product such as a rock saddle, terraret, pole ring, lessing ring, or magmaphone packing is used.

With the above configuration, in the case of causing the hydrogen storage metal to perform the storage reaction or the release reaction, the hydrogen gas is circulated in the packed bed 3 and cold water is introduced into the external pipe 9 to cool the heat medium. Is poured into the packed bed 3 to absorb the heat of reaction from the small piece S to occlude hydrogen, and conversely the external pipe 9
Hot water is introduced to heat the heating medium to supply heat of reaction to the small piece S to release hydrogen.

Further, when heat is recovered from the hydrogen storage alloy, the hydrogen gas in the packed bed 3 is pressurized to cause the small lumps S to carry out a hydrogen storage reaction to generate an exothermic effect, and the heating medium is supplied to the packed bed. 3, the heating medium is heated to heat the intermediate water introduced into the external pipe 9 for a heat source, and conversely, the hydrogen gas is depressurized to cause an endothermic action by the release reaction in the small lump S, The heat medium is cooled and the intermediate water introduced into the external pipe 9 is cooled for a cold heat source.

In this case, if a small piece S of the hydrogen-absorbing metal molded into the Raschig ring shape or the Silotted ring shape as described above is used, the hydrogen gas circulates in the packed bed 3 or the heat medium flows down. It is possible to form a sufficient gap that does not result in the above, and to increase the surface area of the small lump S to increase the heat exchange area with the heat medium and the reaction area with the hydrogen gas.

Next, as a second embodiment of the present invention, a hot / cold water supply apparatus using the above apparatus will be described with reference to FIG.

This device is provided with a pair of the devices used in the first embodiment, and the first container 1a and the second container 1b are connected by a hydrogen pipe 4 with a sluice valve 11 interposed therebetween, and both external pipes 9 are connected to each other. The heat source pipe 9a and the cold heat source pipe 9b
Intermediate heat source pipes 12a and 12b are connected to a and 9b, respectively, and a plurality of switching valves 13 provided in the heat source pipe 9a and the intermediate heat source pipe 12a, or the cold heat source pipe 9b and the intermediate heat source pipe 12b as appropriate. I am trying to switch.

When this apparatus is applied to, for example, a cooling and heating system that uses midnight power, hot water heated using midnight power is guided to the heat source pipe 9a to cause a hydrogen release reaction on the first container 1a side. The released hydrogen gas is guided to the second container 1b side through the hydrogen pipe 4 and blown into the second container 1b to cause the hydrogen storage reaction on the second container 1b side. At the same time, the hydrogen storage reaction occurs. The heat of reaction is exchanged with the intermediate water at room temperature introduced into the intermediate heat source pipe 12b on the second container 1b side to be discarded, and the releasing reaction and the occlusion reaction are completed and both containers 1
When a and 1b are in an equilibrium state, the sluice valve of the hydrogen pipe 4
Close 11 to complete the air conditioning preparation stage.

In the daytime cooling / heating stage, first, the sluice valve 11 is opened to open the second container 1b in the high pressure state to the first container in the low pressure state.
Hydrogen gas is flown into 1a to cause an occlusion reaction on the first container 1a side to heat the heat medium, and to cause a release reaction on the second container 1b side to cool the heat medium,
In summer, the reaction heat from the first container 1a side is transferred to the intermediate heat source pipe 12a.
From the cold heat source pipe 9b on the second container 1b side to obtain cold water for cooling, and in the winter, the reaction heat on the second container 1b side is discarded as cold water from the intermediate heat source pipe 12b. Hot water for heating is obtained from the heat source pipe 9a on the side of the 1st container 1a. However, the hot water in summer may be used for hot water supply, or may be stored in a heat storage tank (not shown) and used as hot water for the midnight power.

FIG. 3 shows a modification of the hot / cold water supply device as a third embodiment of the present invention.

In this embodiment, four devices used in the first embodiment are provided for continuous operation, and the first container 1a and the third container 1c dedicated to the release reaction and the second container 1b dedicated to the occlusion reaction and A fourth container 1d is provided, and a small lump piece S of a hydrogen storage metal is stacked inside each container 1a, 1b, 1c, 1d without using the perforated plates 2 and 2 to form a filling layer 3, 1st container 1a and 4th container 1d
And the second container 1b and the third container 1c are connected by hydrogen pipes 4 and 4, and the heat medium and the small pieces S are separated on the outlet 5 side of each container 1a, 1b, 1c, 1d. The separator 14 for
To each of the first container 1a and the second container 1b, and between the third container 1c and the fourth container 1d, respectively, connecting the conveying pipes 15 communicating the outlet 5 side and the upper side, and the conveying pipes 15 The small lumps S are transferred from one container to the other container by the transfer device 16 installed in the container, and the heat exchanger 10a of the first container 1a is provided with the heat source pipe 12a and the second container 1b. Heat exchanger 10b
The heat source pipe 9b is connected to the heat exchanger 10c of the third container 1c, the heat source pipe 9c is connected to the cold heat source pipe 9c, and the heat exchanger 10d of the fourth container 1d is connected to the intermediate heat source pipe 12d.

According to this supply device, the first container 1a and the fourth container 1d are mainly used in the preparation process, and the second container 1b and the third container 1c are used in the cooling and heating process, that is, using the exhaust heat to raise the temperature. The heated hot water is introduced into the heat source pipe 12a on the first container 1a side to cause a hydrogen release reaction in the first container 1a, and the released hydrogen gas is introduced into the fourth container 1d through the hydrogen pipe 4 to 4 containers
1d is allowed to perform a hydrogen storage reaction, and at the same time, the heat of reaction due to this storage reaction is discarded from the intermediate heat source pipe 12d on the side of the fourth container 1d, and the release reaction and storage reaction as a preparatory step are performed by both containers 1a and 1d. Is done.

On the other hand, in the cooling and heating process, hydrogen gas is caused to flow from the third container 1c into the second container 1b, and the release reaction is generated in the third container 1c.
In the summer, the reaction heat of the second container 1b side is discarded as warm water from the warm heat source pipe 9b, and the cold heat source pipe 9c of the third container 1c side cools the cooling water for cooling. And in the winter season, on the contrary, the third container 1c
The reaction heat on the side is discarded as cold water from the cold heat source pipe 9c, and hot water for heating is obtained from the warm heat source pipe 9b on the second container 1b side.

Since the above reaction cycle is gradually and continuously operated, the first container 1a, the second container 1b, and the third container 1a, 1b, and 3rd container are operated by the respective conveyors 16 during the operation of the reaction cycle or immediately before the completion of the reaction cycle. The small pieces S are exchanged between the 1c and the fourth container 1d, and this series of operations is repeated to continuously obtain hot water and cold water.

In this way, the container can be configured for storage and discharge, and the pipes can be configured for heat source, cold heat source, warm heat source, and intermediate heat source, respectively, without complicated valve switching. Also, the container and the piping can be made of thermally suitable materials.

In this embodiment, the warm water from the intermediate heat source pipe 12d on the side of the fourth container 1d may be used for heating without being discarded, or in the winter from the cold heat source pipe 9c on the side of the third container 1c. If the cold water to be discarded is used for cooling, it is particularly useful for a building having a computer room that needs cooling even in winter.

(Effects of the Invention) As described above, according to the present invention, the hydrogen gas is circulated in the packed bed filled with a large number of small pieces of the hydrogen storage metal, and the heat medium is poured from above the packed bed to generate heat. It has an effect that the exchange efficiency can be improved and the cost can be reduced, and the reaction efficiency can be improved and the reaction time can be shortened to be applied to many other purposes.

[Brief description of drawings]

FIG. 1 is a system diagram of an energy conversion device embodying the present invention, FIG. 2 is a system diagram of a hot / cold water supply device using the energy conversion device according to a second embodiment of the present invention, and FIG. It is a system diagram of the modification of the said hot / cold water supply apparatus which is the 2nd Example of this invention. 1 ... Container 3 ... Packed bed 4 ... Hydrogen piping 5 ... Outflow port 6 ... Shower head S ... Small piece

Claims (2)

[Claims] 1. A method of energy conversion utilizing a reaction for producing a metal hydride from a hydrogen storage metal and hydrogen and vice versa, which is a packed bed in which a large number of small pieces of hydrogen storage metal are filled in a container. And a hydrogen gas is circulated through the packed bed to occlude or release the hydrogen gas, and a heating medium is poured into the packed bed from above. . 2. An energy conversion device utilizing a reaction for producing a metal hydride from a hydrogen storage metal and hydrogen and vice versa, which is a packed bed in which a large number of small pieces of the hydrogen storage metal are filled in a container. A discharge port for pouring the heat medium into the filling layer by arranging a hydrogen pipe connection port in the upper part of the container and a heat medium outlet in the lower part, and being located above the filling layer inside the container. An energy conversion device using a hydrogen storage metal.