Patent Application
20160060499
The present disclosure relates to a heat storage system.
A solar thermal power generation system is known, which concentrates (condenses) sunlight in a heat condensing (collecting) area to concentrate heat, and generates steam with this heat to drive a steam turbine for power generation. In general, the solar thermal power generation system is equipped with a heat storage system in order to supplement heat for power generation during night and in a time zone of insufficient sunlight, thereby suppressing a transient change in the electric power to be generated.
One of known heat storage systems used in the solar thermal power generation system or the like uses a molten salt, as a heat storage material (see Patent Literature 1, for example). The molten salt is a liquid-state salt, and referred to as a solar salt. The molten salt is a mixture of potassium nitrate (KNO3) and sodium nitrate (NaNO3), with the mass fraction of sodium nitrate being 0.6. This heat storage system stores the heat in the form of sensible heat.
However, when an amount of heat storage becomes large (e.g., 1 TJ), the heat storage system that relies upon the sensible heat needs a large heat storage vessel. This is not practical. To deal with it, i.e., to design the heat storage vessel with a practical size, there is a demand for a heat storage system that relies upon latent heat.
PATENT LITERATURE 1: Japanese Patent Application Laid-Open Publication No. 05-256591
In the conventional heat storage system that relies upon latent heat, however, the heat storage material, which becomes a solid phase during solidification, adheres to a heat transfer tube or pipe. This brings about a problem, i.e., the heat transfer drops.
In order to overcome this problem, the heat transfer tube may be arranged on the entire interior of the heat storage vessel to facilitate the heat transfer. However, when the heat storage vessel is large, an extremely large cost is required to arrange the heat transfer tube in the entire heat storage vessel. The heat storage vessel may be downscaled if the latent heat is utilized, as compared to the heat storage vessel that utilizes the sensible heat. In this case, however, the heat storage vessel would have the volume in the order of 1000 m3 when an amount of heat to be stored becomes about 1 TJ. Thus, it is not easy to arrange the heat transfer tube in the entire heat storage vessel.
In view of such facts, the present disclosure has an object to overcome the above-described problems, and provide a heat storage system that utilizes latent heat, and can reduce a decrease in heat transfer caused by a heat storage material in a solid phase.
The present disclosure is developed to achieve the above-mentioned object. A first aspect of the present disclosure provides a heat storage system having a minimum heat storage temperature Tmin, and including a mixed salt having a non-eutectic composition as a heat storage material. The mixed salt assumes a solid-liquid coexistence state at the minimum heat storage temperature Tmin.
a is a schematic view of a heat storage system according to one embodiment of the present disclosure, and
a and 7b is a set of graphs showing the changing temperature over time between the heat storage material and a metallic plate in Examples of the present disclosure. Specifically,
Now, an embodiment of the present disclosure will be described with reference to the accompanying drawings.
a is a schematic view of a heat storage system according to the embodiment of the present disclosure.
As shown in
The heat exchanger 4 on the cooling side (cooling heat exchanger) is supplied with a first heat medium having a low temperature to perform the heat exchange between the first heat medium and the heat storage material 2 thereby cooling the heat storage material 2. The temperature of the first heat medium becomes high upon the heat exchange. The cooling heat exchanger 4 feeds the first heat medium having a high temperature to a thermal load or the like. The cooling heat exchanger 4 has a heat transfer tube through which the first heat medium flows. The cooling heat exchanger 4 is only disposed in an upper area in the heat storage vessel 3.
The heat exchanger 5 on the heating side (heating heat exchanger) is supplied with a second heat medium having a high temperature to perform the heat exchange between the second heat medium and the heat storage material 2 thereby heating the heat storage material 2 for heat storage. The heating heat exchanger 5 is a plate-like heat exchanger, i.e., hot plate, which has a fluid passage therein to allow the second heat medium to flow in the fluid passage. The heating heat exchanger 5 is situated on a bottom of the heat storage vessel 3.
Although not shown, a stirring unit may be provided in the heat storage vessel 3 for stirring the heat storage material 2. Also, a peeling (exfoliating) unit may be provided in the heat storage vessel 3 for forcibly peeling the solid phase heat storage material 2 from the surface of the cooling heat exchanger 4.
It is assumed that this embodiment is applied to a high temperature system such as a solar thermal power generation system. In this embodiment, therefore, the minimum heat storage temperature Tmin is equal to or greater than 150 degrees C., and preferably equal to or greater than 200 degrees C. In one example to be described in the following description, the maximum heat storage temperature Tmax of the heat storage system 1 is 400 degrees C., and the minimum heat storage temperature Tmin is 250 degrees C.
In the heat storage system 1 of this embodiment, a mixed salt having a non-eutectic composition is used as the heat storage material 2. The mixed salt assumes a solid-liquid coexistence state at the minimum heat storage temperature Tmin.
The following example will describe a case where a two-component mixed salt, which is a mixture of potassium nitrate (KNO3) and sodium nitrate (NaNO3) mixed in a non-eutectic composition, is used as the heat storage material 2.
As depicted in
In this embodiment, the composition indicated by the bold broken line in
In this case, the heat storage material 2 starts assuming a solid phase at 274 degrees C. as the heat storage material 2 is gradually cooled from 400 degrees C., which is the maximum heat storage temperature Tmax. Upon further cooling, the heat storage material reaches 250 degrees C., which is the minimum heat storage temperature Tmin, while gradually increasing its solid phase rate (solid fraction). In the meantime, the solid phase appears on the cooling surface having the lowest temperature (surface of the heat transfer tube, i.e., the cooling heat exchanger 4), and the solid phase grows along the cooling surface. However, the solid phase does not stick onto the cooling surface, and therefore the solid phase falls off due to the flowing movement of the heat storage material 2 or the like. It should be noted that if the heat storage material is further cooled from 250 degrees C., which is the minimum heat storage temperature Tmin, the heat storage material 2 becomes the solid phase completely at 234 degrees C. In other words, the temperature zone indicated by the bold solid line in the drawing is the solid-liquid coexistence state.
The solid phase rate of the heat storage material 2 can be regulated by temperature. If the temperature range for the solid-liquid coexistence state is too narrow, it becomes difficult to regulate the solid phase rate to a desired value. Thus, the composition is preferably decided to allow the temperature range for the solid-liquid coexistence state to have one degree C. or more. It should be noted that it is difficult to regulate the solid phase rate by the temperature if the heat storage material assumes the solid-liquid coexistence state with difference substances in a solid phase and a liquid phase, as in Patent Literature 1.
As described above, when the two-component mixed salt having the non-eutectic composition is used as the heat storage material 2, the heat storage material 2 does not stick firmly onto the cooling surface (surface of the heat transfer tube of the cooling heat exchanger 4) when the heat storage material 2 solidifies and assumes the solid phase. Thus, the heat storage material 2 is easy to peel off.
It is considered that this is because the solid phase rate in the vicinity of the cooling surface locally increases as the solidification starts, and therefore the solidification proceeds while the liquid-phase molten salt having a relatively low melting point is penetrating between the cooling surface and the solid phase. It is also considered that this occurs because the solid-liquid coexistence area for the non-eutectic molten salt has a certain temperature range. Therefore, as the control is performed to gradually increase the solid phase from the liquid phase (i.e., to gradually lower the temperature), it is possible to suppress the sticking of the solidified (solid phase) heat storage material 2 onto the cooling surface.
Because the solid phase heat storage material 2 that peels off due to the flowing movement of the heat storage material 2, the stirring, or the like has a large specific weight than the liquid phase heat storage material 2, the solid phase heat storage material 2 precipitates on the bottom of the heat storage vessel 3. Thus, it is possible to efficiently cool the liquid phase heat storage material 2 by disposing the cooling heat exchanger 4 in the upper area of the heat storage vessel 3. As the heating heat exchanger 5 is disposed on the bottom of the heat storage vessel 3, the weight of the solid phase heat storage material 2 itself forcibly presses the solid phase heat storage material 2 against the heating heat exchanger 5. This makes it possible to efficiently heat the solid phase heat storage material 2.
Although the mixture of potassium nitrate and sodium nitrate is used as the heat storage material 2 in this embodiment, the present disclosure is not limited in this regard. Any mixed salt having a non-eutectic composition that takes the solid-liquid coexistence state at the minimum heat storage temperature Tmin may be used as the heat storage material 2.
For example, any of a mixture of CsNO3 and NaNO3, a mixture of LiNO3 and NaNO3 and a mixture of NaNO3 and RbNO3 may be used as the heat storage material 2 if Tmax is set to 400 degrees C. and Tmin is set to 250 degrees C. Also, a mixture of LiBr and NaNO3 or a similar mixture may be used as the heat storage material 2 if Tmin is set to 280 degrees C. Equilibrium diagrams of these mixtures are illustrated in
As shown in
A mixed salt having three or more components may also be used as the heat storage material 2 as long as the mixed salt has a non-eutectic composition and takes the solid-liquid coexistence state at the minimum heat storage temperature Tmin.
For example, a mixed salt of NaNO3, KNO3 and NaNO2, which is called “heat transfer salt (HTS),” is known as a three-component molten salt. The composition of HTS was changed from a generally used eutectic composition (NaNO3 was 7 mol %, KNO3 was 44 mol %, NaNO2 was 49 mol %, and the melting point was 142 degrees C.) to a non-eutectic composition (NaNO3 was 7 mol %, KNO3 was 70 mol %, and NaNO2 was 23 mol %) to carry out the solidification experiment. As a result, the heat storage material 2 having the solid phase peeled off the cooling surface in the form of small particles. It was confirmed that the solid phase became easy to peel off the cooling surface.
As described above, the heat storage system 1 of this embodiment uses, as the heat storage material 2, a mixed salt having a non-eutectic composition that becomes the solid-liquid coexistence state at the minimum heat storage temperature Tmin.
Accordingly, the heat storage material 2, which solidifies and becomes the solid phase, does not firmly stick onto the cooling surface, but becomes easy to peel off. Therefore, it is possible to suppress the deterioration of the heat transfer due to the solid phase heat storage material 2. As a result, it is possible to utilize the latent heat even if the heat transfer tube is not arranged in the entire heat storage vessel 3. A cost reduction and an increase in an amount of heat storage become possible.
In addition, because the heat storage material 2 does not firmly adhere to the cooling surface but peels off in the heat storage system 1, it is still possible to suppress the heat transfer deterioration even if the solid phase rate is set to a higher value at the minimum heat storage temperature Tmin than a conventional arrangement. This further increases the amount of heat storage.
In the heat storage system 1 that has the minimum heat storage temperature Tmin being 150 degrees C. or higher, no conventional heat storage material 2 can be used in the solid-liquid coexistence state and can suppress the adhesion of the solid phase onto the cooling surface. Thus, the present disclosure is considered to be able to significantly contribute to developments in the heat storage system 1 that is used in a high temperature range.
As such, the present disclosure can provide a heat storage system that can reduce a decrease in heat transfer caused by a heat storage material in a solid phase.
A second aspect of the present disclosure provides the heat storage system, wherein the heat storage material has a temperature range of one degree C. or more to assume the solid-liquid coexistence state.
A third aspect of the present disclosure provides the heat storage system, wherein the minimum heat storage temperature Tmin is equal to or greater than 150 degrees C.
The present disclosure is not limited to the above-described embodiment. It goes without saying that various changes and modifications may be made to the embodiment without departing from the scope and spirit of the present disclosure.
In order to confirm by experiments whether the solid phase sticks onto the cooling surface or can separate from the cooling surface, experiment equipment 61 was prepared as shown in
The experiment equipment 61 includes a beaker 63, a heat storage material 2 received in the beaker 63, and a metal plate 64 such that one end of the metal plate 64 is immersed in the heat storage material 2 and the other end of the metal plate 64 is exposed from the heat storage material 2 for cooling. The temperature of a heater 67 situated below the beaker 63 was gradually lowered, and how the solid phase was generated was observed while the temperature distribution of the metal plate 64 in its longitudinal direction and the temperature of the heat storage material 2 were being measured with a thermocouple 65 and a data logger 66. Although not shown, that end of the metal plate 64 which was exposed from the heat storage material 2 was covered with a heat insulation member in order to delay the generation of the solid phase for the sake of easier observation.
A mixture of potassium nitrate and sodium nitrate shown in
As the temperature of the heat storage material 2 was gradually decreased, the solid phase appeared in the vicinity of meniscus on the metal plate 64 where the temperature became the lowest. The solid phase grew along the surface of the metal plate 64, but did not stick onto the metal plate 64. The solid phase peeled off due to the flowing movement of the liquid phase heat storage material 2 as the liquid phase heat storage material was stirred. The solid phase which grew along the surface of the metal plate 64 was semi-transparent, and a dendrite-like concave-convex was observed. The convex portion had a lower transparency than the thin portion.
In the non-eutectic composition, the zone for the solid-liquid coexistence state has a certain temperature range, and has a unique solid phase rate (solid fraction) at that temperature. When the solidification starts, the solid phase rate in the vicinity of the surface of the metal plate 64 locally increases. Thus, it is assumed that the solidification of the liquid phase heat storage material proceeds while the liquid phase heat storage material 2 having a relatively low melting point is penetrating between the metal surface and the solid phase. It is therefore assumed that the heat storage material 2 having the solid phase does not stick onto the metal plate 64 until the temperature decreases sufficiently, and that the heat storage material is easy to peel off.
For comparison, on the other hand, a heat storage material having a eutectic composition was gradually cooled and observed. A solid phase was generated in the form of transparent and thin film on the surface of the metal plate 64 that was immersed in the heat storage material. The solid phase increased its thickness gradually, and did not peel off in spite of the flowing movement of the stirred liquid phase heat storage material.
As described above, when the heat storage material 2 had the non-eutectic composition, the solid phase generated on the metal surface peeled off due to the flowing movement of the stirred heat storage material 2 in the liquid phase whereas when the heat storage material had the eutectic composition, the solid phase did not peel off. It is assumed that the different adhesion of the solid phase onto the metal surface is caused by a fact that the solid-liquid coexistence region of the non-eutectic molten salt has a certain temperature range.
Therefore, when a mixed salt having a non-eutectic composition that takes a solid-liquid coexistence state at the minimum heat storage temperature Tmin is used as the heat storage material 2, the solid phase heat storage material 2 does not firmly adhere to the cooling surface but becomes easy to peel off. As such, it is possible to suppress the heat transfer deterioration due to the heat storage material 2 that has become the solid phase.
The embodiments of the present disclosure are not limited to those described above. The present disclosure includes any variations, applied examples, and equivalents embraced in the concepts of the present disclosure defined by the claims. Thus, the present disclosure should not be interpreted in a limited manner, but is applicable to any other technique falling within the scope of the concepts of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-105261 | May 2013 | JP | national |
This application is a Continuation of International Application No. PCT/JP2014/059293, filed on Mar. 28, 2014, claiming the priority of Japanese Patent Application No. 2013-105261, filed on May 17, 2013, the disclosures of both International Application and the Japanese Application are incorporated herein by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2014/059293 | Mar 2014 | US |
| Child | 14938948 | US |
