JP2017218492A - Chemical thermal storage material and heat storage container using chemical thermal storage material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical thermal storage material high in reaction speed around ordinary temperature (25°C) while having excellent heat generation and property capable of storing heat even at low heat storage temperature.SOLUTION: There is provided a chemical thermal storage material containing magnesium oxide and a second chemical heat storage material having heat storage temperature lower than the magnesium oxide and reaction speed at 25°C higher than the magnesium oxide, the second chemical heat storage material is arranged at a position of a supply side of a fluid which is a reaction medium and/or a position of a flow channel side of water from the magnesium oxide.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a chemical heat storage material, a chemical heat storage material that can repeat heat generation and heat storage by using a reversible reaction that releases reaction heat by the reaction between the reaction medium and the chemical heat storage material and absorbs heat by the reverse reaction of the above reaction. Relates to a heat storage container using

  Chemical heat storage materials are used for storing and using exhaust heat from engines, industrial plants, etc., because they have a large amount of heat storage per volume and have very little heat loss even after long-term storage of stored chemical heat storage materials. Is expected to be.

  Conventionally, calcium oxide has been used as a chemical heat storage material because of its large calorific value and fast reaction rate. That is, when calcium oxide generates heat during the hydration reaction, the calorific value is large and the reaction rate at normal temperature (25 ° C.) is also fast. Moreover, the calcium hydroxide produced | generated by the hydration reaction of calcium oxide accumulates heat with a dehydration reaction.

  However, in order to store heat accompanying the dehydration reaction of calcium hydroxide, there is a problem that the heat storage temperature needs to be a high temperature environment of 500 ° C. or higher. Thus, attempts have been made to lower the heat storage temperature by combining lithium chloride with calcium hydroxide. On the other hand, when a chemical heat storage material in which lithium chloride is combined with calcium hydroxide is transferred from a dehydration reaction to a hydration reaction, the hydration reaction may not proceed sufficiently due to aggregation of the chemical heat storage material. Are known. Thus, as a means for suppressing the aggregation of the chemical heat storage material, it has been proposed to further include a skeleton structure such as sepiolite in the chemical heat storage material in which lithium chloride is combined with calcium hydroxide (Patent Document 1). ).

  However, in Patent Document 1, as a chemical heat storage material, not only lithium chloride but also a skeleton structure is blended with calcium oxide, so that the heat storage amount and the heat generation amount per unit amount (unit volume) of the chemical heat storage material are reduced. There was a problem that. Moreover, since the chemical heat storage material of Patent Document 1 uses the dehydration reaction of calcium hydroxide, there is still a problem that the decrease in the heat storage temperature is insufficient.

JP 2014-24887 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and has a characteristic of being able to store heat even at an excellent calorific value and a low heat storage temperature, and has a high heat generation rate near room temperature (25 ° C.). An object is to provide a heat storage material.

  An aspect of the present invention includes magnesium oxide and a second chemical heat storage material having a heat storage temperature lower than that of the magnesium oxide and a reaction rate at 25 ° C. higher than that of the magnesium oxide, and the second chemical heat storage material includes The chemical heat storage material is disposed at a position closer to the supply side of the fluid (water) as a reaction medium and / or to a position closer to the flow path of the reaction fluid (water) than the magnesium oxide. In the present invention, water is supplied as a reaction medium to the chemical heat storage material, but excess water that does not contribute to the reaction can receive heat from the exothermic reaction and vaporize to function as a heat transport medium. it can.

  In the said aspect, magnesium oxide functions as a 1st chemical heat storage material. Further, the second chemical heat storage material is disposed at a position on the water supply side and / or on the water flow path side that contributes to the endothermic reaction and exothermic reaction of the chemical heat storage material, rather than magnesium oxide. That is, the positional relationship between magnesium oxide and the second chemical heat storage material in the chemical heat storage material is such that the second chemical heat storage material is disposed upstream of the water flow and the magnesium oxide is disposed downstream of the water flow. It has become a relationship. Thus, the chemical heat storage material has the second region and the first region.

  Therefore, first, the second chemical heat storage material, which has a higher reaction rate at normal temperature (25 ° C.) than magnesium oxide, quickly generates heat as it reacts with water. With the heat generation of the second chemical heat storage material, water further supplied to the chemical heat storage material is heated on the upstream side of the magnesium oxide (that is, the second region), and on the downstream side of the second chemical heat storage material. Supplied to the magnesium oxide in place. When heated water is supplied to the magnesium oxide, the magnesium oxide reacts to release reaction heat.

  In an aspect of the present invention, the second chemical heat storage material is at least one selected from the group consisting of zeolite, calcium chloride, magnesium chloride, strontium oxide, calcium sulfate, magnesium sulfate, sodium sulfate, silica gel, and lithium chloride. It is a chemical heat storage material that is a compound.

  An aspect of the present invention is a chemical heat storage material in which the magnesium oxide and the second chemical heat storage material are covered with a first diffusion layer. In the above aspect, water is diffused along the first diffusion layer, and water is supplied from the first diffusion layer to the chemical heat storage material.

  Aspects of the present invention include a housing having a water introduction portion for introducing water and a water vapor discharge portion for discharging water vapor, a chemical heat storage material housed in the housing, and the water provided in the housing. A flow path, and a first diffusion layer provided between the chemical heat storage material and the flow path, the chemical heat storage material is magnesium oxide, and the heat storage temperature is lower than the magnesium oxide, and A second chemical heat storage material having a reaction rate at 25 ° C. higher than that of the magnesium oxide, and the second chemical heat storage material is located on the water supply side and / or on the flow path side of the magnesium oxide. It is the thermal storage container arrange | positioned in the position.

  In the above aspect, water having a function as a reaction medium contributing to an endothermic reaction and an exothermic reaction of the chemical heat storage material is supplied from the water introduction portion to the inside of the flow path provided adjacent to the first diffusion layer, The water is supplied from the flow path to the first diffusion layer. Due to the capillary force of the first diffusion layer, the water moves to the entire surface and inside of the first diffusion layer. The water moved to the entire first diffusion layer reacts with the chemical heat storage material, and the heat stored in the chemical heat storage material is released as reaction heat. The water supplied to the inside of the flow path receives the reaction heat as it flows through the flow path from the water introduction part side to the water vapor discharge part side, becomes water vapor, and flows to the water vapor discharge part.

  The water vapor flowing to the water vapor discharge part is transported from the water vapor discharge part of the housing to a heat exchanger thermally connected to the heat utilization destination as a heat transport fluid for transporting the reaction heat.

  On the other hand, the heat outside the heat storage container can be transferred to the chemical heat storage material accommodated inside the housing through the wall surface of the housing of the heat storage container. The heat transferred to the inside of the housing is caused by the reaction that the reaction medium is desorbed from the chemical heat storage material that is released from the reaction heat due to the reaction. Store.

  In an aspect of the present invention, the second chemical heat storage material is at least one selected from the group consisting of zeolite, calcium chloride, magnesium chloride, strontium oxide, calcium sulfate, magnesium sulfate, sodium sulfate, silica gel, and lithium chloride. It is a heat storage container that is a compound.

  An aspect of the present invention is a heat storage container in which the first diffusion layer is a structure having a capillary structure. In the above aspect, the liquid phase fluid diffuses throughout the first diffusion layer by the capillary force of the first diffusion layer.

  An aspect of the present invention is a heat storage container in which a plurality of the flow paths are provided.

  An aspect of the present invention is a heat storage container in which the chemical heat storage material is covered with a first diffusion layer.

  Aspects of the present invention include a housing having a water introduction portion for introducing water and a water vapor discharge portion for discharging water vapor, a chemical heat storage material housed in the housing, and the water provided in the housing. A flow path, and a first diffusion layer provided between the chemical heat storage material and the flow path, the chemical heat storage material is magnesium oxide, and the heat storage temperature is lower than the magnesium oxide, and A second chemical heat storage material having a reaction rate at 25 ° C. higher than that of the magnesium oxide, and the second chemical heat storage material is located on the water supply side and / or on the flow path side of the magnesium oxide. A heat storage container disposed at a position, a heat transport fluid container containing water, connected to the water introduction part, a heat exchanger connected to the water vapor discharge part, and the heat transport fluid Connect the container and the heat exchanger A piping system for supplying water obtained by the heat exchanger to the heat transport fluid container, and a heat transport fluid circulation system, wherein the circulation system is in an airtight state and decompressed It is a heat storage device.

  An aspect of the present invention is a heat storage device in which a first heat transport fluid supply unit is provided between the heat storage container and the heat transport fluid container.

  An aspect of the present invention is a heat storage device in which a second heat transport fluid supply unit is provided between the heat exchanger and the heat transport fluid container.

  The aspect of this invention is a warming-up apparatus using the said thermal storage apparatus.

  Magnesium oxide has a lower heat storage temperature than calcium oxide (400 ° C. or less) and has a calorific value similar to that of calcium oxide, but the reaction rate near normal temperature (25 ° C.) is slower than calcium oxide and supplies water. It takes time to generate heat. However, the inventor has found that the reaction rate near room temperature (25 ° C.) can be improved by supplying water that contributes to the exothermic reaction of the chemical heat storage material to magnesium oxide in a heated state. Obtained.

  From the above, according to the aspect of the present invention, first, the second chemical heat storage material reacts with water and quickly generates heat, so that the water is heated upstream of the magnesium oxide (that is, the second region). The And the reaction rate in the normal temperature (25 degreeC) vicinity can be improved because the heated water is supplied to magnesium oxide from a 2nd area | region.

  According to the aspect of the present invention, the second chemical heat storage material is at least one selected from the group consisting of zeolite, calcium chloride, magnesium chloride, strontium oxide, calcium sulfate, magnesium sulfate, sodium sulfate, silica gel, and lithium chloride. Therefore, the fluid as the reaction medium generates heat more quickly on the upstream side of the magnesium oxide.

  According to the aspect of the present invention, since the chemical heat storage material is covered with the first diffusion layer, the shape change of the molded chemical heat storage material can be suppressed even when water is used as the reaction medium.

  According to the aspect of the present invention, water functions as a reaction medium for the chemical heat storage material, and also functions as a heat transport fluid (heat transport medium) for transporting the heat stored in the chemical heat storage material to the heat utilization destination. The reaction medium path and the heat transport fluid path do not have to be separate paths, and can be a single system. As described above, since the reaction medium path and the heat transport fluid path can be integrated into one system, the structure of the heat storage container and the piping path can be simplified. Moreover, since a liquid reacts with a chemical heat storage material instead of a gas, an excellent heat storage density, that is, an excellent heat generation amount and heat generation rate can be obtained.

  In addition, according to the aspect of the present invention, since the first diffusion layer is provided between the chemical heat storage material and the flow path, the water is smoothly and entirely supplied to the chemical heat storage material through the first diffusion layer. It spreads reliably. Therefore, the heat generation rate and heat generation efficiency of the chemical heat storage material are further improved.

It is side surface sectional drawing of the thermal storage container which concerns on the example of 1st Embodiment of this invention. It is side surface sectional drawing of the thermal storage container which concerns on the 2nd Embodiment of this invention. It is side surface sectional drawing of the thermal storage container which concerns on the 3rd Example of this invention. It is explanatory drawing of the thermal storage apparatus which concerns on the example of embodiment of this invention.

  The chemical heat storage material according to the first embodiment of the present invention will be described below. The above description is made with reference to the drawing of the heat storage container according to the first embodiment of the present invention using the chemical heat storage material according to the first embodiment.

  As shown in FIG. 1, the chemical heat storage material 12 according to the first embodiment has a first region 41 where magnesium oxide is disposed, a heat storage temperature lower than that of magnesium oxide, and a reaction rate at 25 ° C. is oxidized. And a second region 42 in which a second chemical heat storage material faster than magnesium is disposed. The first region 41 is a region mainly composed of magnesium oxide or made of magnesium oxide. The second region 42 is a region mainly composed of the second chemical heat storage material or made of the second chemical heat storage material.

  In the chemical heat storage material 12, the second region 42 is arranged in a manner in direct contact with the first region 41. Moreover, the chemical heat storage material 12 is an aspect in which powder is compression molded into a predetermined shape. Accordingly, in the first region 41, the magnesium oxide powder is compression-molded into a predetermined shape, and in the second region 42, the second chemical heat storage material powder is compression-molded into a predetermined shape. Although the compression shape of the chemical heat storage material 12, the first region 41, and the second region 42 is not particularly limited, the chemical heat storage material 12 has a rectangular cross-sectional shape on the side surface.

  A first wick structure 17 that is a first diffusion layer is disposed on the surface of the chemical heat storage material 12. The first wick structure 17 covers the chemical heat storage material 12 in contact with the entire outer surface of the chemical heat storage material 12. That is, the chemical heat storage material 12 is coated in a state in contact with the inner surface of the first wick structure 17. Since the chemical heat storage material 12 is covered with the first wick structure 17, the shape of the compression-molded chemical heat storage material 12 can be maintained even when water is used as a reaction medium, and the first wick is formed. The structure 17 also functions as a holding member having the shape of the chemical heat storage material 12.

  As shown in FIG. 1, the chemical heat storage material 12 covered with the first wick structure 17 is erected in the vertical direction. That is, the chemical heat storage material 12 covered with the first wick structure 17 is erected in a direction parallel to the direction of gravity. The second region 42 is provided at a position below the first region 41 in the direction of gravity.

  On the other hand, the liquid-phase heat transport fluid (water) L having a function as a reaction medium passes from the bottom of the casing 11 through the first wick structure 17 to the lower part of the casing 11 of the chemical heat storage material 12. Supplied to the side. That is, due to the capillary force of the first wick structure 17, the liquid-phase heat transport fluid L is transported from the lower side of the housing 11 to the chemical heat storage material 12 along the direction of gravity from the lower side to the upper side in the direction of gravity. Is done.

  Since the second region 42 is provided at a position below the first region 41 in the direction of gravity, the liquid phase heat transport fluid L transported to the lower side of the casing 11 of the chemical heat storage material 12 is First, the second region 42 is reached. That is, in the chemical heat storage material 12, the second region 42 is arranged at a position closer to the supply side of the liquid phase heat transport fluid L than the first region 41. The liquid-phase heat transport fluid L that has reached the second region 42 reacts quickly with the second chemical heat storage material, and the second chemical heat storage material releases the reaction heat H.

  Next, when the second chemical heat storage material releases the reaction heat H, the liquid-phase heat transport fluid L that is further supplied to the second chemical heat storage material via the first wick structure 17 is: Heating is performed at a position upstream of the first region 41 to raise the temperature. The heated liquid-phase heat transport fluid L is supplied to the first region 41. The heated liquid-phase heat transport fluid L is supplied to the first region of the magnesium oxide, so that the magnesium oxide is liquid-phase heat transport fluid L even when the temperature outside the casing is below room temperature (25 ° C.). It can react at a fast reaction rate. Accordingly, the magnesium oxide quickly releases the reaction heat H even at a temperature near room temperature. The liquid-phase heat transport fluid L heated by the heat generated by the second chemical heat storage material may be partially supplied to the first region 41 in a gas phase.

  The second chemical heat storage material is not particularly limited as long as the heat storage temperature is lower than that of magnesium oxide and the reaction rate at 25 ° C. is higher than that of magnesium oxide. For example, zeolite, calcium chloride, magnesium chloride, oxidation Examples include strontium, calcium sulfate, magnesium sulfate, sodium sulfate, silica gel, lithium chloride and the like. Among these, zeolite is preferable from the viewpoint of the calorific value (heat storage capacity).

  The ratio between the volume of magnesium oxide and the volume of the second chemical heat storage material in the chemical heat storage material 12 is not particularly limited, but is 1: 1 to 7: 1 from the balance between the reaction rate and the heat generation amount (heat storage amount). A range is preferred. By setting the volume of the magnesium oxide and the volume of the second chemical heat storage material to such a ratio, the supplied liquid-phase heat transport fluid L is sufficiently heated, and the rate of the exothermic reaction of magnesium oxide is improved. be able to.

  Next, the heat storage container according to the first embodiment of the present invention using the chemical heat storage material 12 according to the first embodiment will be described with reference to the drawings.

  As shown in FIG. 1, the heat storage container 1 according to the first embodiment includes a casing 11 that is a container having an internal space, and a chemical heat storage material 12 disposed inside the casing 11. A flow path 18 is formed in a portion of the housing 11 where the chemical heat storage material 12 and the first wick structure 17 are not provided.

  The casing 11 includes a water introduction part 13 for introducing a liquid phase heat transport fluid (water) L having a function as a reaction medium into the casing 11 and a gas phase heat transport fluid (water vapor) G. And a water vapor discharge portion 14 for discharging to the outside. The water introduction part 13 is a tubular body, and one end of the water introduction part 13 communicates with the lower part or the vicinity thereof in the internal space of the housing 11. The other end of the water introduction part 13 is connected to a heat transport fluid container (not shown) for storing the liquid phase heat transport fluid L. In the heat storage container 1, the water introduction portion 13 is inserted into the housing 11 from the outside of the upper portion (top plate portion) of the housing 11.

  The water vapor discharge unit 14 is a tubular body, and one end of the water vapor discharge unit 14 communicates with the upper part or the vicinity thereof in the internal space of the housing 11, and the other end of the water vapor discharge unit 14 is And a heat exchanger (not shown) capable of receiving heat from a gas phase heat transport fluid G having a function as a reaction medium. In the heat storage container 1, the water vapor discharge part 14 is installed in a mode extending in the vertical direction from the upper part (top plate part) of the casing 11, that is, in a direction parallel to the water introduction part 13.

  Although the cross-sectional shape of the side surface of the housing 11 is not particularly limited, the heat storage container 1 has a rectangular shape as shown in FIG.

  The number of installed chemical heat storage materials 12 according to the first embodiment is not particularly limited, even if it is one or more. In the heat storage container 1, the plurality of chemical heat storage materials 12 are arranged in parallel with each other. Moreover, the 1st wick structure 17 which coat | covers each chemical thermal storage material 12 is a mutually different body.

  In addition, the heat storage container 1 is provided with a second wick structure 19 that is a second diffusion layer that connects adjacent first wick structures 17 that are separate from each other. The second wick structure 19 has an end portion on the lower side in the gravitational direction among the portions extending in the direction parallel to the gravitational direction of the first wick structure 17 (that is, the lower end portion of the housing 11). ) Is arranged to connect. In the heat storage container 1, a gap is formed between the first wick structure 17 and the second wick structure 19 and the bottom of the housing 11. The gap serves as a liquid-phase fluid storage unit 20 for storing the liquid-phase heat transport fluid L supplied from the water introduction unit 13. On the other hand, among the portions extending in the direction parallel to the gravity direction of the first wick structure 17, the second upper end portion (that is, the upper end portion of the housing 11) has a second portion. The wick structure 19 is not provided.

  As shown in FIG. 1, the heat storage container 1 is a space portion between the first wick structures 17 adjacent to each other and extending in a direction parallel to the gravity direction, The space portion is a flow path 18. The chemical heat storage material 12 covered with the first wick structure 17 is erected in the vertical direction with respect to the bottom surface of the housing 11, so that the flow path 18 is formed in the housing 11. It extends in a direction perpendicular to the bottom surface. That is, the flow path 18 extends in a direction parallel to the direction of gravity. The first wick structure 17 extends in a direction parallel to the gravitational direction so that the lower end of the gravitational direction (that is, the lower end of the housing 11) is connected to the first wick structure 17. When the second wick structure 19 is disposed, the second wick structure 19 is formed at the end of the flow path 18 on the lower side in the gravity direction (that is, the lower end of the casing 11). Has been placed.

  The number of installed flow paths 18 is not particularly limited, whether it is one or more. In FIG. 1, corresponding to the fact that a plurality of chemical heat storage materials 12 covered with the first wick structure 17 are arranged. A plurality of flow paths 18 are also formed.

  As shown in FIG. 1, the liquid-phase heat transport fluid L is supplied from the water introduction unit 13 to the lower part of the housing 11. The liquid-phase heat transport fluid L supplied to the lower part of the casing 11 is stored in a predetermined amount in the liquid-phase fluid storage unit 20, and then from the lower part of the casing 11 through the second wick structure 19. It is supplied to the end of the flow path 18 on the lower side in the gravity direction (that is, the lower end of the casing 11). In addition, the liquid-phase heat transport fluid L stored in a predetermined amount in the liquid-phase fluid storage unit 20 is first supplied from the lower part of the housing 11 via the first wick structure 17 to the second of the chemical heat storage material 12. Are supplied to the region 42. Furthermore, the liquid phase heat transport fluid L is diffused from the second region 42 to the entire first region 41 by the capillary force of the first wick structure 17. At this time, since the liquid phase heat transport fluid L is heated in the second region 42, the liquid phase heat transport fluid L is heated from the second region 42 to the entire first region 41. Will be diffused.

  The liquid phase heat transport fluid L is supplied to the chemical heat storage material 12 and reacted to release the reaction heat H. Due to the reaction heat H released from the chemical heat storage material 12, a part of the liquid phase heat transport fluid L that has not reacted with the chemical heat storage material 12 is vaporized while moving in the flow path 18 to be in the gas phase. The heat transport fluid (water vapor) G of The gas phase heat transport fluid G that has undergone a phase change from the liquid phase to the gas phase is discharged from the water vapor discharge unit 14 provided at the top of the housing 11 to the outside of the heat storage container 1 and transports the reaction heat H to the heat utilization destination side. To do.

  In the heat storage container 1, the liquid-phase heat transport fluid L functions as a reaction medium for the chemical heat storage material 12, and transports the heat stored in the chemical heat storage material 12 to a heat utilization destination (heat transport medium). Therefore, the reaction medium path and the heat transport fluid path do not have to be separate paths, and can be made into one system.

  The first wick structure 17 and the second wick structure 19 are not particularly limited as long as they have a capillary structure. For example, a metal constructed by firing a powdered metal material. Members such as a sintered body and a metal mesh can be mentioned.

  The material of the housing | casing 11 is not specifically limited, For example, copper, aluminum, stainless steel etc. can be mentioned.

  Next, the chemical heat storage material according to the second embodiment of the present invention will be described. The above description is made with reference to the drawing of the heat storage container according to the second embodiment of the present invention using the chemical heat storage material according to the second embodiment.

  As described above, in the chemical heat storage material 12 according to the first embodiment, the second region 42 is provided at a position lower than the first region 41 in the direction of gravity, so that the second region 42 is The first region 41 is disposed at a position closer to the supply side of the liquid-phase heat transport fluid L than the first region 41. Instead of this, as shown in FIG. 2, the chemical heat storage material 22 according to the second exemplary embodiment has the second region 42 on the surface of the first region 41 that is parallel to the direction of gravity. Are stacked. That is, in the chemical heat storage material 22, the second region 42 is disposed between the first region 41 and the first wick structure 17.

  Since the chemical heat storage material 22 is coated in contact with the inner surface of the first wick structure 17, the second region 42 is located between the first region 41 and the first wick structure 17. Has been placed.

  Further, as shown in the heat storage container 2 according to the second embodiment of the present invention using the chemical heat storage material 22 according to the second embodiment in FIG. 2, the second region 42 is more than the first region 41. Is also arranged on the flow path 18 side.

  The liquid phase heat transport fluid L passes from the lower part of the casing 11 through the second wick structure 19 to the lower end of the first wick structure 17 in the direction of gravity (that is, the lower part of the casing 11). Side end). The liquid-phase heat transport fluid L supplied to the first wick structure 17 is caused by the capillary force of the first wick structure 17 from the lower side to the upper side in the direction of gravity. Will spread.

  Therefore, the liquid-phase heat transport fluid L is first supplied to the second region 42 disposed on the channel 18 side of the chemical heat storage material 22 via the first wick structure 17. The second chemical heat storage material supplied with the liquid-phase heat transport fluid L releases the reaction heat H with the reaction. Thereafter, the liquid-phase heat transport fluid L supplied to the chemical heat storage material 22 is transported from the second region 42 of the chemical heat storage material 22 to the first region 41 while receiving the reaction heat H and raising the temperature. Is done. Also in the chemical heat storage material 22 according to the second embodiment, the heated liquid-phase heat transport fluid L is supplied to the magnesium oxide in the first region, similarly to the chemical heat storage material 12 according to the first embodiment. Therefore, the magnesium oxide can react at a high reaction rate even when the outside of the housing 11 is near room temperature (25 ° C.), and can quickly release the reaction heat H.

  Next, the chemical heat storage material according to the third embodiment of the present invention will be described. The above description is made with reference to the drawing of the heat storage container according to the third embodiment of the present invention using the chemical heat storage material according to the third embodiment.

  As shown in FIG. 3, in the chemical heat storage material 32 according to the third embodiment, the second region 42 is provided at a position below the first region 41 in the gravitational direction, and further, with respect to the gravitational direction. It is also arranged on the surface of the first region 41 in the parallel direction, that is, between the first wick structure 17 and the first region 41.

  That is, as shown in the heat storage container 3 according to the third embodiment of the present invention using the chemical heat storage material 32 according to the third embodiment in FIG. 3, the direction parallel to the gravity direction of the first region 41. The second region 42 disposed on the surface of the first region 41 is disposed closer to the flow path 18 than the first region 41.

  In the chemical heat storage material 32 according to the third embodiment, the liquid-phase heat transport fluid L is first arranged on the supply side of the liquid-phase heat transport fluid L and the flow path 18 side than the first region 41. The second chemical heat storage material is supplied to the second region 42 and releases the reaction heat H. Thereafter, the liquid-phase heat transport fluid L supplied to the chemical heat storage material 32 further receives the reaction heat H, rises in temperature, and is transported from the second region 42 to the first region 41. Accordingly, even in the chemical heat storage material 32 according to the third embodiment, the heated liquid-phase heat transport fluid L is supplied to the magnesium oxide in the first region. Even at a temperature in the vicinity of (25 ° C.), the reaction occurs at a high reaction rate, and the reaction heat H is quickly released.

  Next, an embodiment of a heat storage device using a heat storage container equipped with the chemical heat storage material of the present invention will be described with reference to the drawings. Here, a heat storage device using the heat storage container 1 according to the first embodiment of FIG. 1 will be described as an example.

  As shown in FIG. 4, in the heat storage device 100 according to the embodiment of the present invention, the end of the water introduction part 13 opened in the housing 11 of the heat storage container 1 is the first heat transport fluid supply means. It is connected to the heat transport fluid container 101 via a first piping system 102 provided with one valve 103. The heat transport fluid container 101 contains a liquid phase heat transport fluid (water) L having a function as a reaction medium that contributes to the endothermic reaction and exothermic reaction of the chemical heat storage material 12. In the heat storage device 100, the heat transport fluid container 101 is installed at a position higher than the heat storage container 1, so that by opening the first valve 103, the liquid heat transport fluid L is converted into the heat transport fluid container 101. Then, it flows into the liquid phase fluid storage unit 20 provided below the heat storage container 1 through the water introduction unit 13. The liquid-phase heat transport fluid L that has flowed into the liquid-phase fluid reservoir 20 is generated by the first wick structure 17 and the second wick structure by the capillary force of the first wick structure 17 and the second wick structure 19. It is transported to the surface and inside of the body 19.

  The liquid-phase heat transport fluid L transported into the first wick structure 17 reacts with the chemical heat storage material 12, and the reaction heat H is released from the chemical heat storage material 12. On the other hand, a part of the liquid-phase heat transport fluid L that has not reacted with the chemical heat storage material 12 receives and vaporizes the reaction heat H released from the chemical heat storage material 12, and the gas-phase heat transport fluid G and Become. The gas phase heat transport fluid G is discharged as a heat transport fluid from the water vapor discharge portion 14 of the housing 11 to the second piping system 104 via the upper end portion of the housing 11 of the flow path 18.

  As shown in FIG. 4, the end of the water vapor discharge unit 14 of the heat storage container 1 is connected to a condenser 106 that is a heat exchanger via a second piping system 104. The gas phase heat transport fluid G discharged from the water vapor discharge portion 14 of the heat storage container 1 to the second piping system 104 moves in the direction of the condenser 106 in the second piping system 104, and the condenser 106. To be introduced. The condenser 106 changes the phase from the gas phase heat transport fluid G to the liquid phase heat transport fluid L by cooling the gas phase heat transport fluid G introduced from the second piping system 104.

  Along with the phase change, the gas phase heat transport fluid G releases latent heat. The released latent heat is transported to a heat utilization destination (for example, a warming device) (not shown) that is thermally connected to the condenser 106. Thus, in the heat storage device 100, the reaction medium of the chemical heat storage material 12 is also used as a heat transport fluid for transporting the reaction heat H released from the chemical heat storage material 12 to a heat utilization destination.

  Furthermore, the heat storage device 100 includes a third piping system 107 that connects the condenser 106 and the heat transport fluid container 101. The liquid-phase heat transport fluid L condensed by the condenser 106 is returned from the condenser 106 to the heat transport fluid container 101 via the third piping system 107. Further, the third piping system 107 is provided with a second valve 108 which is a second heat transport fluid supply means.

  The heat storage device 100 includes a first piping system 102, a second piping system 104, and a third piping system 107, respectively, from the heat transport fluid container 101 to the heat storage container 1, and from the heat storage container 1 to the condenser 106, A circulation system in which a heat transport fluid having a function as a reaction medium circulates from the condenser 106 to the heat transport fluid container 101 is formed. The circulatory system is in an airtight state and is depressurized. That is, the circulation system has a loop heat pipe structure. The heat transport fluid container 101 is installed at a position higher than the heat storage container 1.

  Therefore, the capillary force of the first wick structure 17 and the second wick structure 19 and the relative force can be compared without using a device (for example, a pump) for circulating the heat transport fluid accommodated in the circulation system. The temperature difference between the heat storage container 1 having a high temperature and the condenser 106 which is a heat exchanger having a relatively low temperature, and the vapor pressure difference of the heat transport fluid between the heat storage container 1 and the condenser 106. The heat transport fluid can smoothly circulate through the circulation system of the heat storage device 100.

  Next, an operation example when heat is stored in the heat storage container 1 using the components of the heat storage device 100 of FIG. 4 will be described. At the time of heat storage of the heat storage container 1, the first valve 103 of the heat storage device 100 is closed and the second valve 108 is opened, so that the heat storage container 1 receives heat from the external environment of the heat storage container 1. When the heat storage container 1 receives heat from the external environment, the chemical heat storage material 12 releases the gas phase heat transport fluid G. The gas phase heat transport fluid G released from the chemical heat storage material 12 passes through the first wick structure 17 and is discharged into the internal space of the heat storage container 1, that is, the flow path 18. The gas phase heat transport fluid G released into the flow path 18 is condensed via the second piping system 104, the condenser 106, and the third piping system 107, and transported as a liquid to the heat transport fluid container 101. .

  After the heat storage in the heat storage container 1 is completed, the second valve 108 is also closed to confine the liquid phase heat transport fluid L in the heat transport fluid container 101. In the heat storage device 100 of the present invention, the second chemical heat storage material having a heat storage temperature lower than that of magnesium oxide is disposed in the second region, that is, the water supply side position and / or the flow path side position. For this reason, even when the heat of the external environment of the heat storage container 1 is received and stored, the gas-phase heat transport fluid G can be smoothly discharged to the flow path 18 and the heat storage efficiency can be improved.

  On the other hand, when the heat stored in the heat storage container 1 is transported from the heat storage container 1 to the heat utilization destination side, the first valve 103 of the heat storage device 100 is opened and the liquid heat transport fluid L is stored in the heat storage container. 1, and the second valve 108 is also opened to open the circulation system of the heat storage device 100, thereby operating the heat storage device 100.

  Next, an example of a warming device using the heat storage device of the present invention will be described. For example, by mounting a heat storage container of a heat storage device on an exhaust pipe connected to an internal combustion engine (engine or the like) mounted on a vehicle, heat in exhaust gas flowing through the exhaust pipe can be stored in the heat storage container. By disposing the heat storage container so that the outer surface of the housing of the heat storage container is in direct contact with the exhaust gas flowing in the exhaust pipe, the heat storage container can be thermally connected to the heat source.

  Heat derived from the exhaust gas stored in the heat storage container is transported from the heat storage container to the heat exchanger in the circulation system of the heat storage device, and further transported from the heat exchanger to the warming device of the internal combustion engine that is the heat utilization destination. .

  Next, another embodiment of the present invention will be described. In the heat storage container according to the first to third embodiments, the flow path is provided in a direction parallel to the direction of gravity in response to the chemical heat storage material being erected in a direction parallel to the direction of gravity. However, the arrangement direction of the chemical heat storage material and the flow path is not particularly limited. For example, the chemical heat storage material and the flow direction may extend at an inclination angle other than the orthogonal direction with respect to the gravity direction. (That is, it may extend in the horizontal direction).

  Further, in the heat storage container according to the first to third embodiments, the second wick structure which is the second diffusion layer is provided. However, the liquid phase heat transport fluid is supplied to the fluid flow path. The second diffusion layer may not be provided depending on the amount of heat storage container used. Further, in the heat storage container according to the first to third embodiments, the entire chemical heat storage material is covered with the first wick structure that is the first diffusion layer, but depending on the use state of the heat storage container. The first diffusion layer may cover a part of the chemical heat storage material.

  The chemical heat storage material, the heat storage container, and the heat storage device of the present invention can be used in a wide range of fields because the calorific value and heat transport amount can be improved with a simple configuration, for example, exhaust heat from engines, industrial plants, etc. The utility value is high in the field of recovery, storage and use of wastewater, especially in the field of collecting, storing and using exhaust heat mounted on a vehicle.

1, 2, 3 Heat storage container 11 Housing 12, 22, 32 Chemical heat storage material 13 Water introduction part 14 Water vapor discharge part 17 First wick structure 18 Channel 19 Second wick structure 41 First region 42 First 2 region 100 heat storage device 101 heat transport fluid container 106 condenser

Claims (12)

Magnesium oxide and a second chemical heat storage material having a heat storage temperature lower than that of the magnesium oxide and a reaction rate at 25 ° C. higher than that of the magnesium oxide,
The chemical heat storage material in which the second chemical heat storage material is disposed at a position closer to the water supply side and / or to a position closer to the water flow path than the magnesium oxide.   The second chemical heat storage material is at least one compound selected from the group consisting of zeolite, calcium chloride, magnesium chloride, strontium oxide, calcium sulfate, magnesium sulfate, sodium sulfate, silica gel, and lithium chloride. The chemical heat storage material described in 1.   The chemical heat storage material according to claim 1 or 2, wherein the magnesium oxide and the second chemical heat storage material are covered with a first diffusion layer. A housing having a water introduction portion for introducing water and a water vapor discharge portion for discharging water vapor, a chemical heat storage material housed in the housing, the water flow path provided in the housing, and the chemical A first diffusion layer provided between the heat storage material and the flow path,
The chemical heat storage material includes magnesium oxide and a second chemical heat storage material having a heat storage temperature lower than that of the magnesium oxide and a reaction rate at 25 ° C. higher than that of the magnesium oxide.
The heat storage container in which the second chemical heat storage material is arranged at a position on the water supply side and / or a position on the flow path side with respect to the magnesium oxide.   The second chemical heat storage material is at least one compound selected from the group consisting of zeolite, calcium chloride, magnesium chloride, strontium oxide, calcium sulfate, magnesium sulfate, sodium sulfate, silica gel, and lithium chloride. A heat storage container according to 1.   The heat storage container according to claim 4 or 5, wherein the first diffusion layer is a structure having a capillary structure.   The heat storage container according to any one of claims 4 to 6, wherein a plurality of the flow paths are provided.   The heat storage container according to any one of claims 4 to 7, wherein the chemical heat storage material is covered with a first diffusion layer. A housing having a water introduction portion for introducing water and a water vapor discharge portion for discharging water vapor, a chemical heat storage material housed in the housing, the water flow path provided in the housing, and the chemical A first diffusion layer provided between the heat storage material and the flow path, the chemical heat storage material is magnesium oxide, the heat storage temperature is lower than the magnesium oxide, and the reaction rate at 25 ° C. A second chemical heat storage material that is faster than the magnesium oxide, and the second chemical heat storage material is disposed at a position on the water supply side and / or a position on the flow path side with respect to the magnesium oxide. A heat storage container,
A heat transport fluid container containing the water, connected to the water introduction unit;
A heat exchanger connected to the water vapor outlet;
A piping system for connecting the heat transport fluid container and the heat exchanger, and supplying water obtained by the heat exchanger to the heat transport fluid container;
A heat transport fluid circulation system with
A heat storage device in which the circulation system is in an airtight state and is depressurized.   The heat storage device according to claim 9, wherein first heat transport fluid supply means is provided between the heat storage container and the heat transport fluid container.   The heat storage device according to claim 9 or 10, wherein a second heat transport fluid supply means is provided between the heat exchanger and the heat transport fluid container.   A warm-up device using the heat storage device according to any one of claims 9 to 11.

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