JP2012172902A - Heat transfer system and heat exchanger type reactor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat transfer system that has superior heat transfer capability, and reactivity in ammonia immobilization and desorption caused by physical adsorption.SOLUTION: A heat transfer system 100 comprises: two or more reactors including a first heat exchanger type reactor 20; which has a laminate 30 with two heat storage material molding bodies containing physical adsorption material and a support sandwiched between the two heat storage material molding bodies, and a reaction chamber 24 having a contact area between the inner wall that contains the laminate 30 and the heat storage material molding; and an ammonia plumbing 10 that connects with the two or more reactors and circulates ammonia between the two or more reactors. Making use of a difference in ammonia pressure generated between the two or more reactors, ammonia is transported from one reactor to another.

Description

  The present invention relates to a heat transport device and a heat exchange reactor.

  In recent years, there has been a strong demand for reducing carbon dioxide emissions, and it is necessary to promote energy saving and waste heat utilization. For this purpose, it is necessary to develop a highly efficient heat storage technology, and a promising candidate is a chemical heat storage technology that can store heat for a long time with a large amount of heat storage per unit volume or unit mass.

One chemical heat storage technique is the immobilization of ammonia to a metal salt (ammine complex formation reaction / coordination reaction). For example, it is known that chlorides of alkaline earth metals and transition metals absorb and release ammonia, and generate heat and absorb heat at that time (see, for example, Non-Patent Document 1).
In addition, a solid phase reactor that maintains the pressure of the ammonia gas released from the metal chloride ammine complex charged inside by the supply of the heating source, and supply of cooling water to the ammonia gas connected to the solid phase reactor There is known a chemical heat storage device provided with a condenser that condenses by (see, for example, Patent Document 1).
Furthermore, an ammonia storage body obtained by mixing 8 to 20 wt% aluminum powder or carbon fiber with CaCl ₂ .8NH ₃ or SrCl ₂ .8NH ₃ is known (see, for example, Patent Document 2). ).

Bull.Chem.Soc.Jpn.77 (2004) 123

JP-A-6-109388 International Publication No. 2010/025948 Pamphlet

By the way, as a heat storage material using ammonia immobilization (occlusion) and desorption reaction, it is conceivable to use a physical adsorption material utilizing a physical adsorption reaction instead of a metal chloride utilizing a coordination reaction. .
Regardless of whether a metal chloride or a physical adsorbent is used as the heat storage material, if a powder heat storage material is used, sufficient heat exchange cannot be performed, and ammonia is immobilized (occlusion) and desorbed. There is a problem that the reactivity of is reduced. For this reason, it is important to structure the heat storage material, that is, to use the heat storage material as a molded body (heat storage material molded body).
However, it has been clarified that when a heat storage material molded body containing a physical adsorbent is used, the reactivity of ammonia fixation and desorption may decrease.
In Patent Documents 1 and 2, there is no description regarding the heat transportability of ammonia, and no description regarding the reactivity of immobilization (occlusion) and desorption by physical adsorption.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a heat transport device that is excellent in heat transport properties and excellent in reactivity of immobilization and desorption of ammonia by physical adsorption.
Another object of the present invention is to provide a heat exchange type reactor excellent in reactivity of immobilization and desorption of ammonia by physical adsorption.

  The heat transport device according to the first aspect of the present invention includes two heat storage material molded bodies including a physical adsorbent that stores heat when ammonia is desorbed and dissipates heat when ammonia is fixed by physical adsorption, and A laminate having a support sandwiched between two heat storage material molded bodies, and a first heat exchange mold having a reaction chamber in which the laminate is housed and an inner wall has a contact portion with the heat storage material molded body Two or more reactors including a reactor, and ammonia piping for connecting the two or more reactors and flowing ammonia between the two or more reactors, between the two or more reactors Heat is transported by transporting ammonia from one side to the other by utilizing the difference in ammonia pressure generated in the process.

  In the heat transport device according to claim 1, since heat is transported between two or more reactors along with transport of ammonia vapor having a high vapor pressure, pressure loss due to the flow of ammonia vapor in the pipe is suppressed, As a result, heat transportability is improved.

  Further, in the present heat transport apparatus, the heat exchange reactor includes a heat storage material molded body including a physical adsorbent that stores heat when ammonia is desorbed and dissipates heat when ammonia is fixed by physical adsorption. . For this reason, compared with the case where a powdered heat storage material is used, the reactivity (both reaction rate and reaction amount) at the time of immobilization and desorption of ammonia is excellent.

Furthermore, the reaction chamber in the first heat exchange reactor has an inner wall having a contact portion with the heat storage material molded body.
Thereby, since the efficiency of heat exchange between the heat storage material molded body and the heat exchange reactor is improved, the reactivity of immobilization and desorption of ammonia by physical adsorption is improved.

  Thus, according to the heat transport apparatus of claim 1, the heat transport property is improved, and the reactivity of immobilization and desorption of ammonia by physical adsorption is improved.

  A heat transport device according to a second aspect of the present invention is the heat transport device according to the first aspect, wherein a valve is provided in the ammonia pipe, and the difference in ammonia pressure is adjusted by opening and closing the valve. Thereby, since the difference in ammonia pressure can be more effectively maintained, the heat transportability can be further improved. That is, by closing the valve, the difference in ammonia pressure can be maintained for a long time, and by opening the valve, ammonia can be transported and the stored heat can be used efficiently.

  A heat transport device according to a third aspect of the present invention is the heat transport device according to the first or second aspect, wherein the first heat exchange reactor is further between the heat storage material molded body. A heat medium passage through which a heat medium for heat exchange flows. Thereby, since heat exchange can be performed efficiently between the heat medium and the heat storage material molded body, the contact thermal resistance at the contact surface (heat transfer surface) between the reaction chamber wall and the heat storage material molded body is improved. .

  The heat transport device according to claim 4 is the heat transport device according to any one of claims 1 to 3, wherein the first heat exchange reactor has two or more reaction chambers. And a heat medium passage disposed at least between the reaction chambers and through which a heat medium that exchanges heat with the heat storage material molded body flows. Thereby, since heat exchange can be performed efficiently between the heat medium and the heat storage material molded body, the contact thermal resistance at the contact surface (heat transfer surface) between the reaction chamber wall and the heat storage material molded body is improved. .

  The heat transport device according to claim 5 is the heat transport device according to any one of claims 1 to 4, wherein one of the two or more reactors is fixed. The dead volume is 1% or less with respect to the volume of the maximum amount of ammonia at 25 ° C. and 1 atmosphere. Thereby, since more quantity of ammonia which distribute | circulates the inside of a heat transport apparatus can be ensured, heat transport property can be improved more. In particular, it is possible to more effectively suppress delays in the transport of ammonia and heat during initial operation.

  The heat transport device according to the invention described in claim 6 is the heat transport device according to any one of claims 1 to 5, further storing heat when ammonia is desorbed to fix the ammonia. And a second heat exchange reactor having a heat storage material containing a metal chloride or a physical adsorbent that dissipates heat and a reaction chamber in which the heat storage material is stored. Thereby, the efficiency of heat exchange and heat transport can be further improved.

  A heat transport device according to a seventh aspect of the present invention is the heat transport device according to any one of the first to sixth aspects, wherein the physical adsorbent contains activated carbon. Thereby, the reactivity of the immobilization and desorption of ammonia by physical adsorption is further improved.

  The heat transport apparatus according to an eighth aspect of the present invention is the heat transport apparatus according to any one of the first to seventh aspects, wherein the heat storage material molded body includes a binder. Thereby, since the shape of the said heat storage material molded object is more effectively maintained, the reactivity of fixation and desorption of ammonia by physical adsorption is further improved.

  A heat transport device according to a ninth aspect of the present invention is the heat transport device according to the eighth aspect, wherein the binder contains trimethyl cellulose. Thereby, since the shape of the said heat storage material molded object is more effectively maintained, the reactivity of fixation and desorption of ammonia by physical adsorption is further improved.

A heat transport device according to a tenth aspect of the present invention is the heat transport device according to any one of the first to ninth aspects, wherein the support is a corrugated plate or a porous plate. Thereby, since the flow path of ammonia vapor can be ensured between the two heat storage material molded bodies in the laminate, the reactivity of immobilization and desorption of ammonia in the heat exchange reactor is further improved.
For example, a corrugated metal plate (corrugated metal fin) can be used as the corrugated plate. Moreover, as said porous body sheet | seat, porous body ceramics, a foam metal, a metal mesh, and a punching metal sheet can be used.

A heat transport device according to an eleventh aspect of the present invention is the heat transport device according to any one of the first to tenth aspects, wherein the support is a thermal expansion type support that expands by heat, or An ammonia expansion type support that expands when ammonia is occluded. As a result, the expansion of the support can increase the contact pressure between the heat storage material molded body and the support and the inner wall of the reaction chamber and can further reduce the contact thermal resistance. The reactivity of immobilization and desorption is further improved.
As the thermal expansion support, for example, vermiculite can be used.
As said ammonia expansion type support body, a metal chloride molded object sheet | seat can be used, for example.

A heat exchange type reactor according to the invention of claim 12 is a heat storage material molded body comprising two physical adsorbents that store heat when ammonia is desorbed and dissipate heat when ammonia is fixed by physical adsorption. And a laminate having a support sandwiched between the two heat storage material molded bodies, and a reaction chamber in which the laminate is housed and an inner wall has a contact portion with the heat storage material molded body.
According to the heat exchange reactor according to the twelfth aspect of the invention, the reactivity of immobilization and desorption of ammonia by physical adsorption is improved.
The heat exchange reactor according to the invention described in claim 12 is particularly suitable as the first heat exchange reactor in the heat transport device according to any one of claims 1 to 11.

ADVANTAGE OF THE INVENTION According to this invention, the heat transport apparatus excellent in heat transport property and excellent in the fixation | immobilization of ammonia and the reactivity of desorption | desorption by physical adsorption can be provided.
In addition, according to the present invention, it is possible to provide a heat exchange type reactor excellent in reactivity of immobilization and desorption of ammonia by physical adsorption.

It is the figure which showed typically the heat transport apparatus which concerns on embodiment of this invention. It is the figure which showed typically the heat exchange type reactor which concerns on embodiment of this invention. It is the figure which showed typically the heat exchange type | mold reactor which concerns on another embodiment of this invention. It is a saturated vapor pressure curve of ammonia (NH ₃₎ and water _(H 2 O). It is the graph which showed the relationship between thermal storage temperature (degreeC) and thermal storage density (kJ / kg) about each metal chloride. It is the graph which showed the relationship between reaction time and the adsorption rate in Example 1 and a comparative example. It is a figure which shows notionally the unrestrained type heat exchange reactor which concerns on a comparative example.

  Hereinafter, a heat transport device and a heat exchange reactor according to an embodiment of the present invention will be described with reference to the drawings.

FIG. 1 is a diagram schematically showing a heat transport device 100 according to an embodiment of the present invention.
As shown in FIG. 1, the heat transport device 100 includes a first heat exchange reactor 20, a second heat exchange reactor 120, a first heat exchange reactor 20, and a second heat exchange. And an ammonia pipe 10 for connecting the mold reactor 120.

FIG. 2 is a diagram schematically showing the first heat exchange reactor 20 in FIG.
As shown in FIG. 2, the first heat exchange reactor 20 includes a housing 22, a plurality of heat medium channels 26 provided in the housing 22, and a plurality of reaction chambers provided in the housing 22. 24 and a laminated body 30 accommodated in each reaction chamber 24.
In the housing 22, the reaction chambers 24 and the heat medium flow paths 26 are alternately arranged. The reaction chamber 24 and the heat medium flow path 26 are separated from each other with a partition wall therebetween. With these configurations, heat exchange can be performed between the heat medium M <b> 1 supplied from the outside and the heat storage material molded body in the reaction chamber 24. In this embodiment, the reaction chamber 24 and the heat medium flow path 26 are each a prismatic space having a flat rectangular opening end. In this embodiment, in the first heat exchange reactor 20, the opening direction of the reaction chamber 24 (ammonia flow direction) and the opening direction of the heat medium flow channel 26 (heat medium flow direction) are orthogonal in a side view. It is configured as a direct flow type heat exchange reactor.

As in the example of the first heat exchange reactor 20, the first heat exchange reactor in the present invention has two or more reaction chambers in which the heat storage material molded bodies are housed, and the heat medium flow Preferably, the path is at least arranged between the reaction chambers, and has two or more reaction chambers and two or more heat medium flow paths, and the reaction chambers and the heat medium flow paths are alternately arranged. It is more preferable that the configuration is made.
The number of reaction chambers 24 and heat medium channels 26 in the first heat exchange reactor 20 is not particularly limited, and the amount of heat input to and output from the first heat exchange reactor 20 and the area of the heat transfer surface. It can be appropriately set in consideration of (contact area between the reaction chamber wall and the heat storage material molded body).
Moreover, as a material of the housing | casing 22, the material with high heat conductivity, such as a metal (for example, stainless steel, aluminum, aluminum alloy etc.), and ammonia corrosion resistance is suitable.

As shown in FIG. 2, the laminate 30 includes two heat storage material molded bodies (a heat storage material molded body 32A and a heat storage material molded body 32B; hereinafter, these are collectively referred to as “heat storage material molded bodies 32A and 32B”). And a support 34 sandwiched between the heat storage material molded bodies 32A and 32B. In FIG. 2, the heat storage material molded body 32 </ b> A, the support body 34, and the heat storage material molded body 32 </ b> B are separately illustrated in order to make the configuration of the stacked body 30 easier to see.
However, the configuration of the laminate in the present invention may be any configuration having at least a three-layer configuration of such a heat storage material molded body / support / heat storage material molded body. Other configurations in which material molded bodies and supports are alternately arranged and the outermost layer is a heat storage material molded body (for example, heat storage material molded body / support body / heat storage material molded body / support body / heat storage material molded body) 5 layers structure, etc.).

Each of the heat storage material molded bodies 32A and 32B includes a physical adsorbent that stores heat when ammonia is desorbed by an endothermic reaction and dissipates heat when ammonia is fixed by a physical adsorption reaction that is an exothermic reaction.
A heat storage material molded body containing a physical adsorbent can adsorb (immobilize) and desorb ammonia with a small amount of heat similar to the evaporation / condensation latent heat of ammonia. It has an advantage of excellent controllability of separation.
A preferred form of the physical adsorbent will be described later.

As the support 34, it is preferable to use a support that can circulate ammonia gas in a direction along the surface of the support 34 (for example, a direction of a white arrow in FIG. 2). Thereby, since the flow path of the ammonia vapor can be secured between the two heat storage material molded bodies, the ammonia gas (NH ₃ ) supplied from the ammonia pipe 10 can be supplied to a wide range of the heat storage material molded bodies 32A and 32B. . Furthermore, ammonia adsorbed in a wide range of the heat storage material molded bodies 32A and 32B can be discharged toward the ammonia pipe 10 through the support 34.
Specifically, it is preferable to use a corrugated plate or a porous plate as the support 34.
When a porous plate is used as the support 34, ammonia passes through the porous plate.
When a corrugated plate is used as the support 34, ammonia gas passes through a gap formed between the corrugated plate and the heat storage material molded body.
FIG. 3 conceptually shows the first heat exchange reactor 20 and the laminate 40 accommodated in the first heat exchange reactor 20 particularly when the corrugated plate 36 is used as a support. It is a figure. The configuration other than the corrugated plate 36 as a support is the same as that shown in FIG.
When the corrugated plate 36 is used as the support, ammonia passes through the gap formed between the corrugated plate 36 and the heat storage material molded bodies 32A and 32B in the laminate 40 (in the direction of the white arrow in FIG. 3). ).

In addition, as the support in the present invention, it is also preferable to use a thermal expansion support that expands by heat or an ammonia expansion support that expands when ammonia is occluded.
As a result, the contact pressure between the heat storage material molded body and the support and the inner wall of the reaction chamber can be increased by the expansion of the support, and the contact thermal resistance can be further reduced. The reactivity of immobilization and desorption is further improved.

  As the thermal expansion support, for example, vermiculite can be used.

As said ammonia expansion type support body, a metal chloride molded object sheet | seat can be used, for example.
The metal chloride in the ammonia-expanded support is preferably an alkali metal chloride, an alkaline earth metal chloride, or a transition metal chloride. LiCl, MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl ₂ MnCl ₂ , CoCl ₂ , or NiCl ₂ is more preferable.
The metal chloride may be contained singly or in combination of two or more kinds in the ammonia expansion type support.

Further, as shown in FIG. 1, in the heat transport apparatus 100, the first heat exchange reactor 20 and the ammonia pipe 10 include a plurality of reaction chambers 24 and ammonia pipes in the first heat exchange reactor 20. 10 is connected via a header member 28 (for example, a manifold or the like) that communicates with 10 in an airtight state. Thereby, ammonia can be circulated between the plurality of reaction chambers 24 and the ammonia pipe 10 in an airtight state.
In FIG. 1, in order to make the configuration of the first heat exchange reactor 20 and the second heat exchange reactor 120 easier to see, the header member 28, the following header member 29A, the following header member 29B, and the following header are shown. The member 128, the following header member 129A, the following header member 129B, the following heat medium pipe 27A, the following heat medium pipe 27B, the following heat medium pipe 127A, and the following heat medium pipe 127B are represented by two-dot chain lines.

Further, as shown in FIG. 1, the heat exchange reactor 20 is connected to the heat medium pipe 27A via a header member 29A (for example, a manifold or the like) and via a header member 29B (for example, a manifold or the like). And connected to the heat medium pipe 27B. The plurality of heat medium flow paths 26 in the heat exchange type reactor 20 are communicated with the heat medium pipe 27A in an airtight state by the header member 29A, and are communicated with the heat medium pipe 27B in an airtight state by the header member 29B. ing. Thereby, the heat medium flow path 26 in the heat exchange reactor 20 and the outside of the heat transport apparatus 100 (hereinafter also simply referred to as “external” or “outside of the system”) through the heat medium pipe 27A and the heat medium pipe 27B. The heat medium M1 can be circulated between the two.
As the heat medium M1, a fluid usually used as a heat medium such as alcohol such as ethanol, water, oils, a mixture thereof, or the like can be used.

  As shown in FIG. 1, the ammonia pipe 10 is provided with a valve V1 (valve) so that the difference in ammonia pressure can be adjusted by opening and closing the valve V1. Thereby, the difference between the ammonia pressure on the first heat exchange reactor 20 side and the ammonia pressure on the second heat exchange reactor 120 side can be more effectively maintained. That is, the difference in ammonia pressure can be maintained for a long time by maintaining the valve V1 in a closed state, and then the one heat exchange reactor side is opened from the other heat exchange reactor side by opening the valve V1. Can transport ammonia. In this way, the heat stored on one heat exchange reactor side can be efficiently utilized on the other heat exchange reactor side.

As shown in FIG. 1, in the heat transport apparatus 100, the second heat exchange reactor 120 is similar to the first heat exchange reactor 20 in a housing 122, a plurality of reaction chambers 124, and each reaction. This is a heat exchange type reactor provided with a laminated body 130 housed in the chamber 124 and a plurality of heat medium channels 126. About the structure of the laminated body 130, and the structure in the 2nd heat exchange reactor 120, it is the same as that of the structure of the laminated body 30 and the structure in the 1st heat exchange reactor 20, respectively. The header members 128, 129A and 129B and the heat medium pipes 127A and 127B connected to the second heat exchange reactor 120 are connected to the first heat exchange reactor 20, respectively. The header members 28, 29A and 29B and the heat medium pipes 27A and 27B have the same configuration. As the heat medium M2 supplied into the second heat exchange reactor 120, a fluid usually used as a heat medium such as alcohol such as ethanol, water, oils, a mixture thereof, or the like can be used.
Although not shown, outside the heat transport device 100, the flow path of the heat medium M1 and the flow path of the heat medium M2 are independent of each other.
However, the second heat exchange reactor 120 is shown in FIG. 1 as long as the reactor can exchange ammonia and heat with the first heat exchange reactor 20 by fixing and desorbing ammonia. The form is not limited.
In particular, the heat storage material included in the second heat exchange reactor 120 is preferably a heat storage material molded body from the viewpoint of ammonia immobilization and desorption reactivity (reaction rate and reaction amount). Especially, the heat storage material molded object containing the below-mentioned chemical heat storage material, or the heat storage material molded object containing a physical adsorption material is preferable.

  Further, the heat transport apparatus 100 includes an ammonia supply means (not shown) for supplying ammonia into the apparatus, an exhaust means (not shown) for exhausting the inside of the apparatus, and an ammonia pressure in the apparatus. The pressure measuring means (not shown) or the like may be connected.

  Next, an example of heat transport performed by the heat transport apparatus 100 will be described.

(Heat dissipation)
First, the heat supplied to the first heat exchange reactor 20 is transported to the second heat exchange reactor 120, and the transported heat is radiated from the second heat exchange reactor 120 to the outside. An example of usage will be described. In this example, the first heat exchange type reactor 20 is a heat input side reactor, and the second heat exchange type reactor 120 is a heat output side reactor.

In this example, first, as an initial state, ammonia in the heat transport apparatus 100 (hereinafter also referred to as “inside of the system”) is collected on the first heat exchange reactor 20 side, and in the first heat exchange reactor 20. Ammonia is fixed to the heat storage material molded body containing the physical adsorbent, and then the valve V1 is closed. An example of a specific method for setting the heat transport apparatus 100 to the initial state is the same as the “regeneration” method described later.
Heat is supplied to the first heat exchange reactor 20 by circulating a heat medium M1 having a predetermined temperature (for example, −30 ° C. to 10 ° C.). The supplied heat is stored in the first heat exchange reactor 20. The circulation of the heat medium M1 having the predetermined temperature is preferably maintained through heat dissipation and regeneration.
In the second heat exchange reactor 120, a heat medium M2 for releasing heat toward an external heat utilization target is circulated.
In this state, the ammonia pressure on the first heat exchange reactor 20 side is higher than the ammonia pressure on the second heat exchange reactor 120 side.

  Next, when the valve V1 is opened, ammonia is transported from the first heat exchange reactor 20 having a high ammonia pressure toward the second heat exchange reactor 120 having a relatively low ammonia pressure. At this time, in the first heat exchange reactor 20, ammonia is desorbed from the heat storage material molded body in the first heat exchange reactor 20 by an endothermic reaction. The endothermic reaction is maintained by maintaining the flow of the heat medium M1 at the predetermined temperature (for example, −30 ° C. to 10 ° C.) to the first heat exchange reactor 20 (that is, the first heat exchange reaction). By maintaining a supply of heat to the mold reactor 20).

  The ammonia that has reached the second heat exchange reactor 120 by the transport of ammonia is fixed to the heat storage material molded body housed in the second heat exchange reactor 120 by an exothermic reaction. The heat medium M2 is heated by this exothermic reaction, and the heated heat medium M2 is radiated toward an external heating target.

  As described above, the heat supplied to and stored in the first heat exchange reactor 20 accompanying the transport of ammonia from the first heat exchange reactor 20 to the second heat exchange reactor 120. Is transported to the second heat exchange reactor 120 side and radiated from the second heat exchange reactor 120.

(Regeneration)
When the above heat radiation is continued and ammonia in the first heat exchange reactor 20 is reduced, the ammonia in the system is collected again on the first heat exchange reactor 20 side, and the first heat exchange reactor 20 is collected. By fixing ammonia in the heat storage material molded bodies 32A and 32B in the mold reactor 20, the heat transport device 100 is regenerated to the initial state.
As a specific example of the regeneration, the circulation of the heat medium M1 at the predetermined temperature (for example, −30 ° C. to 10 ° C.) to the first heat exchange reactor 20 with the valve V1 opened. A method in which the heat medium M2 maintained at a high temperature (for example, 60 ° C. to 100 ° C.) is circulated through the heat medium flow path 126 in the second heat exchange reactor 120 while being maintained is preferable.
Thereby, ammonia is desorbed from the second heat exchange reactor 120 by an endothermic reaction, and ammonia is transported from the second heat exchange reactor 120 side to the first heat exchange reactor 20 side. .
The ammonia that has reached the first heat exchange reactor 20 is fixed to the heat storage material molded bodies 32A and 32B in the reaction chamber 24 of the first heat exchange reactor 20 by an exothermic reaction.
The exothermic reaction is maintained, for example, by maintaining the flow of the heat medium M1 at the predetermined temperature (for example, −30 ° C. to 10 ° C.) to the first heat exchange reactor 20 (that is, the first heat Maintaining the supply of heat to the exchange reactor 20).

In the heat transport apparatus 100, the above heat dissipation and regeneration can be repeated.
In the heat radiation and regeneration, an example is shown in which heat is supplied to the reactor by circulation of a heat medium. However, heat may be supplied to the reactor by a temperature adjustment mechanism (not shown).

As described above, the heat transport device of the present embodiment is a device that transports heat between two or more reactors as ammonia is transported due to the difference in ammonia pressure.
FIG. 4 is a saturated vapor pressure curve of ammonia (NH ₃ ) and water (H ₂ O).
As shown in FIG. 4, ammonia exhibits a high saturated vapor pressure even at a relatively low temperature compared to water. For example, even in the range of −30 ° C. to 0 ° C., an ammonia vapor pressure at an atmospheric pressure level can be secured. For this reason, according to the heat transport device of the present embodiment, the pressure loss accompanying the flow of ammonia vapor in the pipe can be suppressed even under a relatively low temperature condition, so that the heat transport property is excellent. For example, according to the heat transport apparatus of the present embodiment, heat transport can be performed over a long distance (for example, 1000 mm to 5000 mm, and further 2000 mm to 5000 mm).

Moreover, the heat transport apparatus 100 of this embodiment distribute | circulates ammonia between two or more reactors in which the heat storage material which heat-stores, when it desorbs ammonia, and thermally radiates when ammonia is fixed was accommodated. This is a device that transports heat.
For this reason, it has the following advantages compared with a chemical heat storage device (for example, a chemical heat storage device described in JP-A-6-109388) provided with a condenser for condensing ammonia gas as an essential component.
That is, in the heat transport apparatus 100 of this embodiment, the condenser is not an essential component, and a mechanism for controlling the gas / liquid phase change is not essential. A simple configuration can be obtained by connecting with ammonia piping.
In addition, in a chemical heat storage device equipped with a condenser for condensing ammonia gas as an essential component, the conditions for the pressure and cooling temperature of ammonia gas in the condenser are used to condense (liquefy) ammonia gas with a high vapor pressure. It is necessary to adjust to a sufficient condition, and the operation condition is likely to be restricted (the range of selection of the operation condition is likely to be narrow).
On the other hand, in the heat transport apparatus 100 of the present embodiment, the condenser is not an essential component, and two or more reactors are connected by ammonia piping, so that the operating conditions are not easily restricted.

(Heat storage material)
Next, the heat storage material accommodated in the reactor in the heat transport apparatus 100 of this embodiment will be described.
The heat storage material molded body accommodated in the first heat exchange reactor is a heat storage material molded body containing a physical adsorbent as described above.
As described above, the heat storage material (preferably the heat storage material molded body) housed in the second heat exchange reactor is a heat storage material molded body including a chemical heat storage material or a heat storage material molded body including a physical adsorbent. Is preferred.
In the present invention, since at least the first heat exchange reactor uses a heat storage material molded body containing a physical adsorbent that requires a smaller amount of heat for immobilization and desorption of ammonia than the chemical heat storage material, at least the first heat exchange reactor is used. The controllability of immobilization and desorption of ammonia in one heat exchange reactor can be improved, and the controllability of the heat transport device can be improved.

  On the other hand, in the case where the heat storage material molded body including the chemical heat storage material is used in the second heat exchange reactor, the heat storage density of the second heat exchange reactor can be further increased, and the entire heat transport device The heat storage density as can be made higher.

In particular, in the present invention, the heat storage material molded body containing a physical adsorbent is used in the first heat exchange reactor, and the heat storage material molded body containing a chemical heat storage material is used in the second heat exchange reactor. In some cases, it has the following advantages.
In this combination, a chemical heat storage material having a large amount of heat required for immobilization and desorption of ammonia compared to a physical adsorption material, and a small amount of heat required for immobilization and desorption of ammonia compared to a chemical heat storage material. And a physical adsorbent having properties. For this reason, even when supplying a small amount of heat to the reactor side including the physical adsorbent using the difference in the amount of reaction heat between the reactors, a larger amount of heat can be obtained on the reactor side including the chemical heat storage material. Can do.
For example, the amount of heat required for immobilization and desorption of 1 mol of ammonia is 40 kJ / mol for a chemical heat storage material (for example, LiCl, MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl ₂ , MnCl ₂ , CoCl ₂ , NiCl ₂ , etc.). While it is ˜60 kJ / mol, it is 20 kJ / mol to 30 kJ / mol for a physical adsorbent (for example, activated carbon, mesoporous silica, zeolite, silica gel, clay mineral, etc.).
For example, in the above-mentioned “heat dissipation”, a heat storage material molded body including a physical adsorbent is used as the heat storage material molded body housed in the first heat exchange reactor 20, and the second heat exchange reactor 120 is used. In the second heat exchange reactor 120, the temperature of the heat supplied to the first heat exchange reactor 20 by using a heat storage material molded body containing a chemical heat storage material as the heat storage material molded body housed in The heat at a temperature about 30 ° C. higher than that can be radiated.

-Physical adsorbent-
Next, the physical adsorbent contained in at least the heat storage material molded bodies 32A and 32B in the first heat exchange reactor 20 will be described.
The physical adsorbent may be included in the second heat exchange reactor 120 as necessary.

A porous body can be used as the physical adsorbent.
The porous body is preferably a porous body having pores of 10 nm or less from the viewpoint of further improving the reactivity of immobilization and desorption of ammonia by physical adsorption.
The lower limit of the pore size is preferably 0.5 nm from the viewpoint of production suitability and the like.
The porous body is a primary particle aggregate obtained by agglomerating primary particles having an average primary particle diameter of 50 μm or less from the viewpoint of further improving the reactivity of fixation and desorption of ammonia by physical adsorption. Some porous bodies are preferred.
The lower limit of the average primary particle diameter is preferably 1 μm from the viewpoint of production suitability and the like.

Specific examples of the porous body include activated carbon, mesoporous silica, zeolite, silica gel, clay mineral and the like. Among these, activated carbon is preferable from the viewpoint of further improving the reactivity of immobilization and desorption of ammonia.
As the activated carbon, it is preferable to use activated carbon having a specific surface area by a BET method of 800 m ² / g to 2500 m ² / g (more preferably 1800 m ² / g to 2500 m ² / g).
The clay mineral may be an uncrosslinked clay mineral or a crosslinked clay mineral (crosslinked clay mineral). Examples of the clay mineral include sepiolite.

The heat storage material molded body in the present embodiment may contain one kind of physical adsorbent or two or more kinds. It is preferable that the heat storage material molded body in the present embodiment includes a physical adsorbent containing at least activated carbon.
Moreover, it is preferable that the thermal storage material molded object in this embodiment contains a binder in addition to the said physical adsorption material. Since the shape of the said heat storage material molded object is more effectively maintained when the heat storage material molded object in this embodiment contains a binder, the reactivity of fixation and desorption of ammonia by physical adsorption improves more.

The binder is preferably at least one water-soluble binder.
Examples of the water-soluble binder include polyvinyl alcohol and trimethyl cellulose. Among these, trimethyl cellulose is preferable.

The heat storage material molded body in the present embodiment may contain other components other than the physical adsorbent and the binder, if necessary.
The content of the physical adsorbent in the heat storage material molded body is preferably 80% by volume or more, and 90% by volume or more, from the viewpoint of maintaining higher immobilization and desorption reactivity of ammonia. Is more preferable.
The content of the binder in the heat storage material molded body is preferably 5% by volume or more and more preferably 10% by volume or more from the viewpoint of more effectively maintaining the shape of the heat storage material molded body. .

The heat storage material molded body in the present embodiment may contain other components other than the physical adsorbent and the binder, if necessary.
Examples of other components include heat conduction aids such as carbon fibers.

Further, the method for producing the heat storage material molded body in the present embodiment is not particularly limited. For example, a physical adsorbent, a mixture containing a physical adsorbent and a binder, or a slurry thereof, such as pressure molding, extrusion molding, etc. The method of shaping | molding by a well-known shaping | molding means is mentioned.
Examples of the molding pressure include 20 MPa to 100 MPa, and 20 MPa to 40 MPa is preferable.

Next, the reaction chamber in the first heat exchange reactor will be described.
An inner wall of the reaction chamber 24 in the first heat exchange reactor has a contact portion with the heat storage material molded bodies 32A and 32B.
That is, the heat storage material molded bodies 32A and 32B are kept in contact with the inner wall of the reaction chamber 24 and the surface of the support 34, respectively.
With this configuration, heat exchange between the first heat exchange type reactor and the heat storage material molded body can be more effectively performed through the inner wall of the reaction chamber 24. Desorption reactivity is improved.
Here, if the contact is not maintained, the efficiency of heat exchange between the first heat exchange reactor and the heat storage material molded body is lowered, and the reaction of immobilization and desorption of ammonia by physical adsorption is performed. (Refer to a comparative example described later).

Moreover, although the heat storage material molded object containing a physical adsorption material (for example, the heat storage material molded object containing activated carbon) does not have the volume expansion width as the ammonia expansion type support body containing the above-mentioned metal chloride, Volume expansion is observed.
Therefore, if the contact is not maintained, the heat storage material molded body repeatedly expands and contracts during repeated use, so that the heat storage material molded body is cracked (including cracks) and pulverized, and ammonia is fixed and removed. The reactivity of separation decreases.
Like this embodiment, the fall of this reactivity can also be suppressed by making the heat storage material molded object, the surface of a support body, and the inner wall of a reaction chamber contact.

  From the viewpoint of further improving the reactivity of immobilization and desorption of ammonia by physical adsorption as described above, and from the viewpoint of suppressing cracks (including cracks) and pulverization during repeated use, the inner wall of the reaction chamber is a heat storage material. It is preferable to be in contact with the entire one main surface of the molded body. That is, it is preferable that the heat storage material molded body is sandwiched between the inner wall of the reaction chamber and the support surface.

Next, an example of a method for housing a laminate including two heat storage material molded bodies in the reaction chamber in the present embodiment will be described.
As a storage method, for example, a method including the following steps 1 to 3 is suitable.
(Step 1) First, two heat storage material molded bodies to which ammonia is not fixed are prepared.
Specifically, a physical adsorbent, a mixture containing a physical adsorbent and a binder, or a slurry thereof is molded by pressure molding, extrusion molding, or the like to obtain a heat storage material molded body.
The volume of the heat storage material molded body is smaller than the volume of the space determined by the inner wall of the reaction chamber and the surface of the support (the space in which the heat storage material molded body is to be filled), and ammonia is fixed in step 3 to be described later. The volume is adjusted so that the heat storage material molded body and the inner wall of the reaction chamber are in contact with each other.
(Step 2) Next, a laminate having a structure in which the support is sandwiched between the two heat storage material molded bodies prepared in Step 1 is prepared, and the laminate is accommodated in the reaction chamber.
(Step 3) Next, ammonia is fixed to the two heat storage material molded bodies accommodated in the reaction chamber.
According to the above method, the surface of the two heat storage material molded bodies is applied to the inner wall of the reaction chamber and the surface of the support body by utilizing the phenomenon that the two heat storage material molded bodies undergo volume expansion due to fixation of ammonia. It can be contacted effectively.
The heat storage material molded body containing the physical adsorbent in the present embodiment (for example, the heat storage material molded body containing activated carbon) does not have the volume expansion width of the ammonia expansion type support including the metal chloride described above, but is fixed with ammonia. Since the volume expansion due to the formation is recognized, the contact can be effectively performed.
Here, once the surface of the heat storage material molded body comes into contact with the inner wall of the reaction chamber, volume shrinkage is suppressed even when ammonia is subsequently desorbed from the heat storage material molded body. In this case, ammonia is desorbed from the inside of the heat storage material molded body while maintaining the contact.

  In the above method, by using the above-mentioned ammonia expansion type support or the above-mentioned thermal expansion type support as the support, not only the heat storage material molded body but also the support can be expanded in step 3, so that the heat storage The surface of the molded material can be brought into contact more effectively with the inner wall of the reaction chamber and the surface of the support.

-Chemical heat storage material-
It is preferable that the heat storage material (preferably heat storage material molded body) accommodated in the second heat exchange reactor 120 includes a chemical heat storage material. The heat storage material accommodated in the second heat exchange reactor 120 may contain one kind of chemical heat storage material or two or more kinds.
The chemical heat storage material has a property that the heat storage density is higher than that of the physical adsorption material.
For this reason, when the heat storage material molded body containing the chemical heat storage material is used in the second heat exchange reactor, the heat storage density of the second heat exchange reactor can be further increased, and the heat transport device The heat storage density as a whole can be further increased.

The chemical heat storage material is preferably a metal chloride, more preferably an alkali metal chloride, an alkaline earth metal chloride, or a transition metal chloride from the viewpoint of increasing the heat storage density in the reactor. LiCl, MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl ₂ , MnCl ₂ , CoCl ₂ or NiCl ₂ are particularly preferred.
One kind of the chemical heat storage material may be contained in the heat storage material molded body, or two or more kinds thereof may be contained.

FIG. 5 shows the relationship between the heat storage temperature (° C.) and the heat storage density (kJ / kg) for each metal chloride of LiCl, MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl ₂ , MnCl ₂ , CoCl ₂ , and NiCl _2. FIG.
The heat storage temperature (° C.) shows an example of the temperature at which ammonia can be desorbed for each metal chloride. The heat storage density (kJ / kg) indicates the amount of heat (kJ) that can be stored by desorption of ammonia per 1 kg of each metal chloride.

As shown in FIG. 5, LiCl, MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl ₂ , MnCl ₂ , CoCl ₂ , and NiCl ₂ exhibit a high heat storage density of about 800 kJ / kg to 1400 kJ / kg. The heat storage temperature varies depending on the type of metal chloride, and is in the range of about 30 ° C to 220 ° C.
In the present embodiment, the type of metal chloride can be appropriately selected according to the operating ammonia pressure and the operating temperature. Therefore, the range in which the operating ammonia pressure and the operating temperature can be selected in accordance with the heat utilization target is expanded.
For example, BaCl ₂ , CaCl ₂ , SrCl ₂ can be selected when lowering the operating temperature of the heat transport device, and NiCl ₂ can be selected when increasing the operating temperature of the heat transport device. it can.

When the heat storage material in this invention contains the said metal chloride, this heat storage material may contain other components other than the said metal chloride.
Examples of other components include binder components such as alumina and silica, and heat conduction aids such as carbon fibers.
However, in the case where the heat storage material in the present invention contains the metal chloride, from the viewpoint of further improving the heat storage density, the content of the metal chloride in the heat storage material is preferably 60% by mass or more, and 80% by mass. The above is more preferable.

Moreover, when shape | molding the thermal storage material containing a chemical thermal storage material in a thermal storage material molded object, there is no limitation in particular about the shaping | molding method, For example, thermal storage material containing a chemical thermal storage material (and other components, such as a binder as needed) A method of molding (or slurry containing the heat storage material) by a known molding means such as pressure molding or extrusion molding may be used.
Examples of the molding pressure include 20 MPa to 100 MPa, and 20 MPa to 40 MPa is preferable.
About the method of accommodating the thermal storage material molded object containing a chemical thermal storage material in a reaction chamber, the method similar to the method of accommodating the thermal storage material molded object containing the physical adsorption material mentioned above in a reaction chamber can be used.

(Preferred form of heat transport device)
Next, the preferable form of the heat transport apparatus of this invention from the viewpoint of having the effect of this invention more effectively is demonstrated.

In the heat transport device of the present invention, from the viewpoint of improving heat transport properties and reducing transport delay of ammonia during initial operation, the maximum amount of ammonia that can be stored in one of two or more reactors is as follows: It is preferable to make the dead volume of the heat transport device as small as possible.
Here, the dead volume of the heat transport device represents an effective volume within a range in which ammonia can flow in the heat transport device.
In the heat transport device of the present invention, since most of the dead volume is the volume of the ammonia pipe, the volume of the ammonia pipe is made as small as possible within the allowable range of pressure loss in the ammonia pipe, and the dead volume of the heat transport device is made as small as possible. It is desirable to do.

Specifically, in the heat transport device of the present invention, the dead volume is 1% or less with respect to the volume at 25 ° C. and 1 atm of the maximum amount of ammonia that can be immobilized in one of the two or more reactors. It is more preferable that
When the dead volume is in the above range, it is possible to secure a larger amount of ammonia flowing through the heat transport apparatus, so that the transportability of ammonia and the transportability of heat are further improved. Furthermore, by setting the dead volume within the above range, it is possible to more effectively suppress delays in the transport of ammonia and heat during the initial operation.
Here, the “maximum amount of ammonia that can be stored in one reactor” represents the maximum amount of ammonia that can be immobilized by a reactor having the largest amount of ammonia that can be immobilized among two or more reactors. The “maximum amount of ammonia that can be stored in one reactor” is preferably equal to the total amount of ammonia stored in the heat transport device.
For example, as an example of the heat transport apparatus of the present invention, in a reactor having the largest amount of ammonia that can be immobilized among two or more reactors, the maximum amount of ammonia that can be immobilized at 25 ° C. and 1 atm. In an example in which the volume is 100 times the volume of the heat storage material accommodated in the reactor and the maximum amount of ammonia is stored in the reactor, the dead volume of the heat transport device is set to the maximum amount. It is possible to obtain a heat transport capacity of 90% or more with respect to the heat transport capacity when two or more reactors are directly connected by adjusting the volume of ammonia to 1% or less at 25 ° C. and 1 atmosphere. is there.

  Moreover, there is no limitation in particular in the dead volume of the heat transport apparatus of this invention, For example, it can be 10 mL-10L. The dead volume is preferably 100 mL to 10 L, more preferably 500 mL to 10 L, and particularly preferably 1 L to 10 L.

Moreover, there is no limitation in particular in the length of the ammonia piping in this invention, For example, it can be 10 mm-5000 mm.
In the heat transport apparatus of the present invention, heat is transported along with transport of ammonia having a high vapor pressure, so the length of the ammonia piping can be 1000 mm to 5000 mm, and further 2000 mm to 5000 mm.
A preferable inner diameter of the ammonia pipe will be described later.

Moreover, as operating temperature of the heat transport apparatus of this invention, it can be set as -30 degreeC-250 degreeC.
The ammonia pressure (operating ammonia pressure) in the heat transport apparatus of the present invention can be set to 0.1 atm to 10 atm, for example.

The inside diameter of the ammonia pipe in the present invention is preferably 1 mm to 100 mm, more preferably 5 mm to 100 mm, still more preferably 7 mm to 100 mm, and particularly preferably 10 mm to 100 mm. When the inner diameter of the ammonia pipe is 1 mm or more (more preferably 10 mm or more), the pressure loss of ammonia can be further suppressed, and the heat output can be further improved.
When the inner diameter of the ammonia pipe is 100 mm or less, the enlargement of the apparatus can be further suppressed.
From the viewpoint of further suppressing the increase in size of the apparatus, the upper limit of the inner diameter of the ammonia pipe is more preferably 50 mm, and the upper limit of the inner diameter of the ammonia pipe is particularly preferably 30 mm.

  Next, experimental results (examples and comparative examples) regarding the reaction rate (adsorption rate) between the heat storage material molded body and ammonia will be described with reference to FIGS. 6 and 7.

[Example 1]
As Example 1, a heat transport device having the configuration of the heat transport device 100 of the present embodiment was prepared.
First, according to the method including the above steps 1 to 3, the laminates 30 were respectively stored in the reaction chambers 24 in the first heat exchange reactor 20.
Specifically, first, 100 parts by mass of powdered activated carbon (average primary particle size 5 μm, specific surface area 2000 m ² / g by BET method), 5 parts by mass of trimethylcellulose, and 100 parts by mass of water are mixed to form a slurry. Got.
Next, the obtained slurry was pressure-molded at a pressure of 40 MPa to obtain a heat storage material molded body.
Next, a laminated body having a structure in which a support was sandwiched between the two obtained heat storage material molded bodies was produced, and the obtained laminated body was stored in the reaction chamber 24.
As the support, a stainless porous sheet of 15 mm × 15 mm × thickness 0.5 mm was used.
Thereafter, ammonia was fixed to the heat storage material molded body in the reaction chamber 24, thereby bringing the heat storage material molded body into contact with the inner wall of the reaction chamber 24 and the surface of the support 34.
Furthermore, by repeating the immobilization and desorption of ammonia to the heat storage material molded body in the reaction chamber 24, the contact state and affinity with ammonia are stabilized, and the heat storage material molding in the reaction chamber 24 is performed. The body was made into the heat storage material molded body 32A and 32B in this embodiment.

Here, the size of the heat storage material molded bodies 32A and 32B in the reaction chamber 24 (equal to the size of the space determined by the inner wall of the reaction chamber 24 and the surface of the support 34) was 15 mm × 15 mm × thickness 3 mm.
Further, the size of the support in the reaction chamber 24 was 15 mm × 15 mm × thickness 0.5 mm, which was the same size as before being stored in the reaction chamber 24.
The material of the housing 22 of the first heat exchange reactor 20 was SUS304, and the number of reaction chambers 24 in the first heat exchange reactor 20 was 30.
Water was used as the heat medium M1.

In Example 1, the conditions of the first heat exchange reactor 20 are an operating temperature of 5 ° C., an NH ₃ pressure of 4 atm, and a reaction volume of 4 mL.
The operating temperature is the temperature of the heat medium M1 in the first heat exchange reactor 20.
The NH ₃ pressure is the ammonia pressure on the first heat exchange reactor 20 side when the valve V1 is closed and the operating temperature is reached.

In Example 1, the configuration of the second heat exchange reactor 120 is the same as the configuration of the first heat exchange reactor 20 except that a CaCl ₂ molded body was used as the heat storage material molded body. . The CaCl ₂ compact was produced by pressure molding CaCl ₂ powder at a pressure of 40 MPa.

Using the heat transport device 100 according to Example 1 obtained as described above, an experiment on the reaction rate (adsorption rate) between the heat storage material molded body and ammonia was performed.
First, the valve V1 is opened in the heat transport device 100 according to the first embodiment, and the heat medium M1 (water) having a high temperature (60 ° C.) is supplied to the heat medium flow path 26 of the first heat exchange reactor 20. It was made to distribute | circulate and operation which desorbs ammonia from the thermal storage material molding 32A and 32B was performed. This operation was performed until the amount of ammonia desorbed from the heat storage material molded bodies 32A and 32B became zero, and the heat storage material molded bodies 32A and 32B in this state were used as molded bodies in the initial state. Thereafter, the valve V1 was closed.
The fact that the ammonia desorption amount was zero was confirmed by the fact that the pressure change due to ammonia desorption from the first heat exchange reactor 20 during heating was zero.

Next, a low-temperature (5 ° C.) heat medium M1 (water) is circulated through the heat medium flow path 26 of the first heat exchange reactor 20, and the valve V1 is opened to thereby form an initial molded body. On the other hand, an operation of immobilizing ammonia (physical adsorption) was performed.
The elapsed time from the opening of the valve V1 was defined as the reaction time, and the adsorption rate (relative value) of ammonia in the heat storage material molded body was determined for each reaction time.
Here, the adsorption rate (relative value) of ammonia is a relative value when the ammonia adsorption amount in the ammonia-saturated compact is 1.0 and the ammonia adsorption amount in the initial compact is 0.0. As sought.

FIG. 6 shows the relationship between the reaction time and the ammonia adsorption rate (relative value) in Example 1 (solid line in FIG. 6).
As shown in FIG. 6, in Example 1, the ammonia adsorption rate (relative value) was 0.62 at a reaction time of 100 seconds, and the ammonia adsorption rate (relative value) was 0.82 at a reaction time of 200 seconds. Showed adsorption behavior.

[Comparative Example]
Next, as a comparative example, a heat transport apparatus was prepared in which the first heat exchange reactor 20 of the heat transport apparatus 100 of the present embodiment was replaced with an unconstrained heat exchange reactor 220.
FIG. 7 is a diagram conceptually showing an unconstrained heat exchange reactor 220 according to a comparative example.
As shown in FIG. 7, in the unconstrained heat exchange reactor 220, a heat storage material molded body 232, a reaction chamber 224 in which one heat storage material molded body 232 is stored, and a heat medium M11 are circulated. A heat medium flow path 226.
As the heat storage material molded body 232, a molded body obtained by molding a mixture of the same material as in the example into a disk shape of φ10 mm × thickness 3 mm under the same conditions as in the example was used.
The volume of the reaction chamber 224 was sufficiently larger than the volume of the heat storage material molded body 232 so that the inner wall of the reaction chamber 224 did not contact the heat storage material molded body 232. In this way, the external dimensions of the heat storage material molded body 232 were not physically restricted (constrained) by the inner wall of the reaction chamber 224.
The reaction chamber 224 and the heat medium flow path 226 are configured to be separated from each other with a partition wall 250 therebetween. With this configuration, heat exchange can be performed between the heat medium M11 and the heat storage material molded body 232 in the reaction chamber 224.
The unrestrained heat exchange reactor 220 as described above was connected to the ammonia pipe so that ammonia could be circulated between the reaction chamber 224 and the ammonia pipe in an airtight state.

Using the heat transport device according to the comparative example, the same operation as in the example was performed.
FIG. 6 shows the relationship between the reaction time and the adsorption rate in the examples (broken line in FIG. 6).
As shown in FIG. 6, in the comparative example, the ammonia adsorption rate was lower than that in the example. This is because the surface of the heat storage material molded body 232 and the inner wall of the reaction chamber 224 are not in contact with each other, and the efficiency of heat exchange between the heat medium and the heat storage material molded body is reduced as compared to the example. It is.

[Example 2]
Next, as Example 2, the following experiment was performed.
Prepare CaCl ₂ sheets of the same size as the support prepared in Example 1, but replacing the CaCl ₂ sheets prepared support in the same manner as in Example 1 to prepare a heat transport apparatus according to Embodiment 1 The same evaluation as in Example 1 was performed.
The CaCl ₂ sheet was produced by press molding CaCl ₂ powder at a pressure of 40 MPa.
Example 2 showed an ammonia adsorption rate (relative value) of 0.65 at a reaction time of 100 seconds, an ammonia adsorption rate (relative value) of 0.85 at a reaction time of 200 seconds, and then a behavior in which ammonia was further adsorbed. .
Thus, in Example 2, compared with Example 1, the ammonia adsorption rate (relative value) was further improved.
The reason for this is that by using a CaCl ₂ sheet that is an ammonia expansion type support, the contact pressure between the heat storage material molded body and the support and the inner wall of the reaction chamber is higher, and the contact thermal resistance is further reduced. This is because the reactivity of immobilization and desorption of ammonia by physical adsorption was further improved.

Example 3
Next, as Example 3, the following experiment was performed.
A vermiculite sheet (3M interlam mat) having the same size as the support prepared in Example 1 was prepared, and the same procedure as in Example 1 was performed except that the support in Example 1 was replaced with the prepared vermiculite sheet. Then, a heat transport device was produced and evaluated in the same manner as in Example 1.
Example 3 showed an ammonia adsorption rate (relative value) of 0.68 at a reaction time of 100 seconds, an ammonia adsorption rate (relative value) of 0.90 at a reaction time of 200 seconds, and then a behavior in which ammonia was further adsorbed. .
Thus, in Example 3, compared with Example 1, the ammonia adsorption rate (relative value) was further improved.
The reason for this is that by using a vermiculite sheet which is a thermal expansion type support, the contact pressure between the heat storage material molded body, the support and the inner wall of the reaction chamber is higher, and the contact thermal resistance is further reduced. This is because the reactivity of immobilization and desorption of ammonia by physical adsorption was further improved.

As mentioned above, although the heat transport apparatus and heat exchange type reactor which concern on embodiment of this invention were demonstrated, this invention is not limited to the said embodiment.
For example, in the heat transport apparatus 100 according to the above embodiment, only two reactors (the first heat exchange reactor 20 and the second heat exchange reactor 120) are connected by the ammonia pipe 10. However, at least one of the other reactors other than the second heat exchange reactor 120 may be further connected to the first heat exchange reactor 20 by an ammonia pipe. At this time, the first heat exchange reactor 20 and two or more reactors may be connected by one ammonia pipe having a branch, or the first heat exchange reactor 20 and the two reactors. The above reactors may be connected independently by two or more ammonia pipes having no branch. Moreover, the 1st heat exchange type | mold reactor 20 and three or more reactors may be connected by one or more ammonia piping which has a branch, and one or more ammonia piping which does not have a branch.
As other reactors, for example, similarly to the first heat exchange reactor 20 and the second heat exchange reactor 120, heat is stored when ammonia is desorbed and heat is released when ammonia is fixed. A reactor in which a heat storage material to be stored is stored can be used.

  Moreover, in the heat transport apparatus 100 according to the embodiment, each heat exchange reactor and the ammonia pipe are connected via a header member, but each heat exchange reactor and the ammonia pipe are connected via a header member. Instead, they may be directly connected in an airtight state. Further, a heat exchange reactor integrated with the header member may be used, and the heat exchange reactor and the ammonia pipe may be connected in an airtight state.

  Moreover, in the heat transport apparatus 100 according to the above embodiment, the valve V1 (valve) is provided in the ammonia pipe 10, but the valve V1 may be omitted. Even when the valve V1 is omitted, heat is supplied to at least one of the first heat exchange reactor 20 and the second heat exchange reactor 120 to connect the first heat exchange reactor 20 side and the first heat exchange reactor 20 side. A difference in ammonia pressure can be caused between the two heat exchange reactors 120 and ammonia and heat can be transported by this difference in ammonia pressure.

Further, in the heat transport device 100 according to the above embodiment, each heat exchange type reactor includes a heat medium flow path. However, as the heat exchange type reactor, instead of the heat medium flow path (or the heat medium flow) A reactor equipped with temperature control means such as a heater may be used in addition to the path. Heat can be supplied to the entire reactor by this temperature control means.
Moreover, in the heat transport apparatus 100 according to the above-described embodiment, pressure adjusting means (not shown) may be further provided in at least one place of the ammonia pipe 10. As the pressure adjusting means, means having a function of further increasing the difference in ammonia pressure in the heat transport device by an external force can be used. Specifically, known means such as a pressure pump and a compressor (compressor, etc.) Can be used. By operating the pressure adjusting means, ammonia can be transported (that is, heat can be transported more effectively).

DESCRIPTION OF SYMBOLS 10 Ammonia piping 20,120 Reactor 24,124,224 Reaction chamber 26,126,226 Heat-medium flow path 30,40,130 Laminated body 32A, 32B, 232 Thermal storage material molded body 34 Support body 36 Corrugated plate 100 Heat transport Apparatus 220: Unrestrained heat exchange reactor

Claims (12)

Two heat storage material molded bodies containing a physical adsorbent that stores heat when ammonia desorbs and releases heat when ammonia is fixed by physical adsorption, and a support sandwiched between the two heat storage material molded bodies And two or more reactors including a first heat exchange type reactor having a reaction chamber in which the laminate is housed and an inner wall has a contact portion with the heat storage material molded body,
An ammonia pipe that connects the two or more reactors and circulates ammonia between the two or more reactors;
With
A heat transport device for transporting heat by transporting ammonia from one side to the other by utilizing a difference in ammonia pressure generated between the two or more reactors.   The heat transport device according to claim 1, wherein a valve is provided in the ammonia pipe, and a difference in ammonia pressure is adjusted by opening and closing the valve.   3. The heat transport device according to claim 1, wherein the first heat exchange reactor further includes a heat medium passage through which a heat medium that exchanges heat with the heat storage material molded body flows. 4.   The first heat exchange type reactor has two or more reaction chambers, and is disposed between at least the reaction chambers, and a heat medium flow through which a heat medium that exchanges heat with the heat storage material molded body flows. The heat transport device according to any one of claims 1 to 3, further comprising a path.   The dead volume is 1% or less with respect to the volume at 25 ° C. and 1 atm of the maximum amount of ammonia that can be immobilized in one of the two or more reactors. The heat transport device according to item.   Furthermore, a second heat having a heat storage material containing a metal chloride or a physical adsorbent that stores heat when ammonia is desorbed and dissipates heat when ammonia is fixed, and a reaction chamber in which the heat storage material is stored. The heat transport apparatus according to any one of claims 1 to 5, comprising an exchange reactor.   The heat transport apparatus according to claim 1, wherein the physical adsorbent includes activated carbon.   The heat transport device according to any one of claims 1 to 7, wherein the heat storage material molded body includes a binder.   The heat transport device according to claim 8, wherein the binder contains trimethylcellulose.   The heat transport device according to any one of claims 1 to 9, wherein the support is a corrugated plate or a porous plate.   The heat transport device according to any one of claims 1 to 10, wherein the support is a thermal expansion support that expands by heat or an ammonia expansion support that expands when storing ammonia. .   Two heat storage material molded bodies containing a physical adsorbent that stores heat when ammonia desorbs and releases heat when ammonia is fixed by physical adsorption, and a support sandwiched between the two heat storage material molded bodies And a heat exchange reactor having a reaction chamber in which the laminate is housed and an inner wall has a contact portion with the heat storage material molded body.

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