JP2014044000A - Heat exchange type reactor and adsorption type heat pump - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat exchange type reactor that is excellent in efficiency of heat exchange between an absorption material compact and a heat medium, and improves reaction speed of adsorption-desorption reaction of an adsorbate to an adsorption material.SOLUTION: A heat exchange type reactor includes: a housing 22 in which a reaction chamber 24 capable of storing an adsorption material compact and a heat medium flow passage 26 in which a heat medium flows are alternately arranged; and adsorption material compacts 32A and 32B that is stored in the reaction chamber 24, has a heat transfer surface S performing heat exchange with the heat medium, and contains an adsorption material that discharges heat when an adsorbate is adsorbed and that stores heat when the adsorbate is desorbed and a fibrous heat conductive material whose axial direction crosses with respect to the heat transfer surface.

Description

  The present invention relates to a heat exchange reactor and an adsorption heat pump.

In a heat transport system such as an adsorption heat pump, a heat exchange type reactor that includes an adsorbent and uses adsorption / desorption reaction of adsorbate (water, ammonia, etc.) to the adsorbent is used.
In such a heat exchange reactor, the temperature of the adsorbent changes due to the adsorption heat and desorption heat associated with the adsorption / desorption reaction, thereby changing the equilibrium relationship and inhibiting the subsequent adsorption / desorption reaction. The reaction rate of the desorption reaction may decrease. As means for improving the reaction rate of this adsorption / desorption reaction, it is known that means for improving the thermal conductivity of the adsorbent layer containing the adsorbent is effective. As one of such means, a means is known in which an adsorbent layer containing an adsorbent further contains a heat conductive material such as a metal fin or carbon fiber as a heat transfer promoting material (for example, Non-patent document 1).

Journal of the Heat Transfer Society of Japan Vol.45, No.192, The Japan Heat Transfer Society, July 2006, p.20-51

However, in the method using metal fins as the heat transfer promoting material, it is necessary to increase the surface area of the metal fins in order to improve the reaction rate, thereby causing a problem that the density of the adsorbent decreases.
Moreover, the effect of improving the reaction rate of the adsorption / desorption reaction may not be sufficiently obtained simply by using a fibrous heat conductive material such as carbon fiber as the heat transfer promoting material.
The present invention has been made in view of the above, and is a heat exchange reactor that is excellent in the efficiency of heat exchange between the adsorbent molded body and the heat medium, and has improved the reaction rate of the adsorption / desorption reaction in the adsorbent molded body. It is another object of the present invention to provide an adsorption heat pump and to achieve the object.

Specific means for solving the above-described problems are as follows.
That is, the heat exchange reactor according to the first invention includes a reaction chamber capable of accommodating an adsorbent molded body, a housing in which heat medium flow paths through which the heat medium flows are alternately arranged, and the reaction An adsorbent which is housed in a chamber and has a heat transfer surface for exchanging heat with the heat medium, radiates heat when the adsorbate is adsorbed, and stores heat when the adsorbate is desorbed, and the direction of the axis Comprises an adsorbent molded body containing a fibrous thermal conductive material that intersects the heat transfer surface.

In the first invention, an adsorbent molded body having a higher density of the adsorbent than the powder adsorbent is used, and heat transfer of the adsorbent molded body is performed between the adsorbent molded body and the heat medium. Heat exchange takes place via the surface. Specifically, heat is dissipated from the adsorbent compact to the heat medium with the adsorbate adsorption reaction to the adsorbent, and is supplied from the heat medium with the adsorbate desorption (desorption) reaction from the adsorbent. The accumulated heat is stored in the adsorbent molded body. Here, the efficiency of the heat exchange is improved by alternately arranging the reaction chambers including the adsorbent molded body and the heat medium flow path.
Furthermore, the adsorbent molded body contains a fibrous heat conductive material in which the axial direction (that is, the length direction of the fibrous heat conductive material) intersects the heat transfer surface. This improves the efficiency of heat exchange between the inside of the adsorbent molded body and the heat medium. By this heat exchange, adsorption heat is efficiently released from the inside of the adsorbent molded body toward the heat medium during adsorption, and desorption heat is efficiently supplied from the heat medium toward the inside of the adsorbent molded body during desorption. Therefore, the problem that the adsorption / desorption reaction is hindered by the heat of adsorption and the heat of desorption is reduced.
Further, the density of the adsorbent can be maintained higher than that in the case where metal fins are used in the adsorbent molded body instead of the fibrous heat conductive material.
As described above, according to the first invention, the reaction rate of the adsorption / desorption reaction in the adsorbent molded body can be improved.

  In contrast, even when an adsorbent molded body containing an adsorbent and a fibrous thermal conductive material is used, the direction of the axis of the fibrous thermal conductive material and the heat transfer surface intersect. If not (that is, the direction of the axial center and the heat transfer surface are parallel), it is difficult to improve the efficiency of heat exchange between the inside of the adsorbent molded body and the heat medium. The effect is insufficient.

  In the heat exchange reactor according to the first aspect of the present invention, the fibrous heat conductive material preferably has an axis direction of 45 ° or more with respect to the heat transfer surface. Thereby, the efficiency of heat exchange between the inside of the adsorbent molded body and the heat medium is further improved, and the reaction rate is further improved.

In the heat exchange reactor according to the first aspect of the invention, 80% by number or more of the fibrous heat conductive material contained in the adsorbent molded body has an axial direction relative to the heat transfer surface. Is preferably 70 ° or more.
Here, “80% by number or more of the fibrous thermal conductive material contained in the adsorbent molded body has an axial direction of 70 ° or more with respect to the heat transfer surface” The axial center direction of the majority (80% by number or more) of the fibrous heat conductive material contained in the adsorbent molded body is aligned to some extent so as to be substantially perpendicular (70 ° or more) to the heat transfer surface. It means that
Thereby, since the efficiency of heat exchange between the heat medium and the inside of the adsorbent molded body is further improved, the reaction rate of the adsorption / desorption reaction is further improved.
Furthermore, compared to the case where the direction of the axial center of the heat conductive material is random, the spring back when producing the adsorbent molded body can be suppressed, so the density of the adsorbent in the adsorbent molded body is further improved. Can be made. Here, the spring back refers to a phenomenon in which when the adsorbent molded body is molded, the volume of the adsorbent molded body once reduced by pressurization returns when the pressure is released.

  In the heat exchange reactor according to the first aspect of the present invention, the heat conductive material preferably has an aspect ratio of 10 or more. Thereby, the efficiency of heat exchange between the heat medium and the inside of the adsorbent molded body can be further improved, and the reaction rate of the adsorption / desorption reaction can be further improved.

  In the heat exchange type reactor according to the first aspect of the invention, the adsorbent molded body is a flat adsorbent molded body that contacts the wall surface of the reaction chamber, and the heat transfer surface is a contact surface with the wall surface. It is preferable. Thereby, since heat exchange between the adsorbent molded body and the heat medium can be performed more efficiently, the reaction rate of the adsorption / desorption reaction is further improved.

  In the heat exchange type reactor according to the first invention, it is preferable that the heat conductive material is an inorganic material. Thereby, the efficiency of heat exchange between the heat medium and the inside of the adsorbent molded body can be further improved, and the reaction rate of the adsorption / desorption reaction can be further improved.

  In the heat exchange type reactor according to the first aspect of the present invention, the heat conductive material is preferably carbon fiber. Thereby, the efficiency of heat exchange between the heat medium and the inside of the adsorbent molded body can be further improved, and the reaction rate of the adsorption / desorption reaction can be further improved.

  In the heat exchange reactor according to the first invention, the adsorbent is preferably at least one selected from the group consisting of activated carbon, mesoporous silica, zeolite, silica gel, and clay mineral.

  In the heat exchange reactor according to the first aspect of the present invention, the thermal conductivity in the direction of the axis is preferably 2 W / (m · K) or more. Thereby, the efficiency of heat exchange between the heat medium and the inside of the adsorbent molded body can be further improved, and the reaction rate of the adsorption / desorption reaction can be further improved.

In the heat exchange reactor according to the first invention, the amount of the thermally conductive material in the adsorbent molded body is 1% by volume to 30% by volume with respect to the total amount of the adsorbent molded body. preferable.
When the amount of the heat conductive material is 1% by volume or more, the effect of heat transfer by the heat conductive material can be further improved.
When the amount of the heat conductive material is 30% by volume or less, the density of the adsorbent involved in the adsorption / desorption reaction is maintained higher.
The content is more preferably 1% by volume to 20% by volume, and particularly preferably 5% by volume to 20% by volume.

Next, the adsorption heat pump according to the second invention comprises the heat exchange reactor according to the first invention.
The adsorption heat pump according to the second invention includes a heat exchange reactor (first invention) having a high reaction rate of the adsorbate adsorption / desorption reaction in the adsorbent molded body, and the reaction rate is reduced. Since heat loss is suppressed, heat utilization efficiency is excellent.

  According to the present invention, there is provided a heat exchange reactor and an adsorption heat pump that are excellent in the efficiency of heat exchange between an adsorbent molded body and a heat medium, and have improved the reaction rate of adsorbate adsorption / desorption with respect to the adsorbent. Can be provided.

It is the figure which showed typically the adsorption type heat pump 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. 2 is a cross-sectional optical microscope image of an adsorbent molded body a in Example 1. FIG. 3 is a cross-sectional optical microscope image of an adsorbent molded body b in Example 2. FIG. It is a cross-sectional optical microscope image of the adsorbent molded object c in Example 3. In Examples 1-3 and Comparative Example 1 is a graph showing the relationship between the reaction time and the desorption rate of the NH ₃ desorption reaction. It is a graph which shows the heat conductivity of the thickness direction of an adsorbent molded object in Examples 1-3 and the comparative example 1. FIG.

  Hereinafter, a heat exchange reactor and an adsorption heat pump according to an embodiment of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments.

FIG. 1 is a diagram schematically showing an adsorption heat pump provided with a heat exchange type reactor according to an embodiment of the present invention.
As shown in FIG. 1, an adsorption heat pump 100 includes a heat exchange reactor 20, which is a heat exchange reactor according to an embodiment of the present invention, an evaporation condenser 40, a heat exchange reactor 20, and an evaporation condensation. And a pipe 10 for connecting the container 40.
Thereby, the ammonia gas (NH ₃ ) supplied from the evaporative condenser 40 to the heat exchange reactor 20 is adsorbed to the adsorbent molded body in the heat exchange reactor 20, or in the heat exchange reactor 20. The ammonia gas (NH ₃ ) desorbed (desorbed) from the adsorbent molded body can be recovered in the evaporative condenser 40. The adsorption heat pump 100 operates according to the pressure difference between the heat exchange reactor 20 and the evaporative condenser 40 by ammonia gas (NH ₃ ) traveling between the two. For details of the principle of operation of the adsorption heat pump, see, for example, page 20 of “Thermal Transfer Journal of the Heat Transfer Society of Japan Vol. 45, No. 192” (Japan Heat Transfer Society, July 2006) Refer to page 21.
In this embodiment, NH ₃ is used as the adsorbate, but other adsorbates such as water and lower alcohols (for example, alcohols having 1 to 6 carbon atoms) are used instead of NH _3. May be.

FIG. 2 is a diagram schematically showing the heat exchange reactor 20 in FIG.
As shown in FIG. 2, the heat exchange reactor 20 includes a housing 22, a plurality of heat medium channels 26 provided in the housing 22, a plurality of reaction chambers 24 provided in the housing 22, 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 efficiently between the heat medium M1 supplied from outside and discharged to the outside and the adsorbent 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 heat exchange type reactor 20, the opening direction of the reaction chamber 24 (NH ₃ 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.

In the heat exchange reactor 20, the number of reaction chambers 24 and heat medium channels 26 is not particularly limited, and the amount of heat input to and output from the heat exchange reactor 20 and the area of the heat transfer surface of the adsorbent molded body. Is set as appropriate.
The material of the housing 22 is a material having high thermal conductivity and corrosion resistance to the adsorbate (NH ₃ etc.) such as metal (for example, stainless steel, aluminum, aluminum alloy, etc.). Is preferred.

As shown in FIG. 2, the laminated body 30 includes two adsorbent molded bodies (adsorbent molded bodies 32A and adsorbent molded bodies 32B; hereinafter, these are collectively referred to as “adsorbent molded bodies 32A and 32B”). And a support body 34 sandwiched between the adsorbent molded bodies 32A and 32B. In FIG. 2, the adsorbent molded body 32 </ b> A, the support 34, and the adsorbent molded body 32 </ b> B are illustrated separately in order to make the configuration of the stacked body 30 easier to see.
However, the configuration of the laminated body may be a configuration having at least a three-layer configuration of such an adsorbent molded body / support / adsorbent molded body. In addition to the three-layer configuration, for example, an adsorbent molded body And other supports in which the outermost layer is an adsorbent molded body (for example, five layers of adsorbent molded body / support body / adsorbent molded body / support body / adsorbent molded body) Configuration, etc.).
Further, in the reaction chamber 24, an adsorbent molded body may be accommodated as a single unit instead of the laminated body. When the adsorbent molded body is stored as a single unit in the reaction chamber 24, the adsorbate is formed between the pipe 10 and the reaction chamber 24 by using an adsorbent molded body provided with an adsorbate flow path. It is preferable that a flow path that can circulate is secured.

Each of the adsorbent molded bodies 32A and 32B has a heat transfer surface for exchanging heat with the heat medium M1, and releases heat when NH ₃ (adsorbate) is adsorbed, so that NH ₃ (adsorbate) is desorbed. And an adsorbent that stores heat when it is heated, and a fibrous heat conductive material whose axial center intersects the heat transfer surface.
In this embodiment, the adsorbent molded body 32 </ b> A is a flat molded body, and one main surface of the adsorbent molded body 32 </ b> A serves as a heat transfer surface S, and the heat transfer surface S and the inner wall of the reaction chamber 24. (The same applies to the configuration of the adsorbent molded body 32B).

  Hereinafter, the adsorbent molded body (for example, the adsorbent molded bodies 32A and 32B) in the present invention will be further described.

-Adsorbent-
The adsorbent molded body contains at least one adsorbent.
The adsorbent is not particularly limited as long as the adsorbate can be adsorbed and desorbed. The adsorbent is preferably a porous body.
The porous body is preferably a porous body having pores of 10 nm or less from the viewpoint of further improving the reactivity of the adsorption / desorption reaction.
The lower limit of the size of the pores is preferably 0.2 nm and more preferably 3 nm from the viewpoint of production suitability and the like.
The porous body is preferably a porous body that is a primary particle aggregate obtained by aggregating primary particles having an average primary particle diameter of 50 μm or less from the viewpoint of further improving the reactivity of the adsorption / desorption reaction.
The lower limit of the average primary particle diameter is preferably 1.0 μm from the viewpoint of production suitability and the like.

Specific examples of the adsorbent include activated carbon, mesoporous silica, zeolite, silica gel, clay mineral and the like.
As the activated carbon, activated carbon having a specific surface area by a BET method of 800 m ² / g or more and 4000 m ² / g or less (more preferably 1000 m ² / g or more and 2000 m ² / g or less) is preferable.
As the mesoporous silica, mesoporous silica having a specific surface area by a BET method of 500 m ² / g or more and 1500 m ² / g or less (more preferably 700 m ² / g or more and 1300 m ² / g or less) is preferable.
As the zeolite, a zeolite having a specific surface area by the BET method of 50 m ² / g or more and 1000 m ² / g or less (more preferably 100 m ² / g or more and 1000 m ² / g or less) is preferable.
As the silica gel, the specific surface area by BET method of 100 m ² / g or more 1500 m ² / g or less (more preferably, 300 meters ² / g or more 1000 m ² / g or less) of silica gel is preferably.
The clay mineral may be an uncrosslinked clay mineral or a crosslinked clay mineral (crosslinked clay mineral). Examples of the clay mineral include sepiolite, smectite clay (saponite, montmorillonite, hectorite, etc.), 4-silicon mica, mica, vermiculite, and the like. Of these, sepiolite is preferable.

The adsorbent molded body may contain the adsorbent (preferably the porous body) alone or in combination of two or more.
In the present embodiment, the type of adsorbent (preferably the porous body) can be appropriately selected according to operating conditions such as operating temperature.

  The packing density of the adsorbent in the adsorbent shaped body is preferably 0.10 g / mL to 0.80 g / mL. When the packing density is 0.10 g / mL or more, the amount of adsorbate involved in the adsorption / desorption reaction can be increased. When the packing density is 0.80 g / mL or less, the migration resistance of the adsorbate in the adsorbent molded body can be further reduced.

  The content of the adsorbent in the adsorbent molded body is preferably 50% by volume or more, and 60% by volume or more, based on the total amount of the adsorbent molded body, from the viewpoint of improving the reactivity of the adsorption / desorption reaction. More preferably, it is particularly preferably 70% by volume or more.

-Fibrous heat conductive material-
The adsorbent molded body contains at least one fibrous heat conductive material whose axial center intersects the heat transfer surface of the adsorbent molded body.

Since the adsorbent contained in the adsorbent molded body generally has a low thermal conductivity (the thermal conductivity of a general adsorbent is, for example, 0.05 W / (m · K) to 0.25 W / ( m · K)), in an adsorbent molded body containing an adsorbent, the temperature of the adsorbent changes due to the adsorption heat and desorption heat associated with the adsorption / desorption reaction, thereby changing the equilibrium relationship and the subsequent adsorption / desorption reaction. May be inhibited.
In this regard, in the present invention, the adsorbent molded body further includes a fibrous heat conductive material in which the direction of the axis intersects the heat transfer surface of the adsorbent molded body. Through the heat conductive material, heat exchange between the inside of the adsorbent molded body and the heat medium (for example, the heat medium M1) is efficiently performed. By this heat exchange, adsorption heat is efficiently released from the inside of the adsorbent molded body toward the heat medium during adsorption, and desorption heat is efficiently supplied from the heat medium toward the inside of the adsorbent molded body during desorption. The Therefore, according to the present invention, the problem that the adsorption / desorption reaction is inhibited by the heat of adsorption and desorption is alleviated, and the reaction rate of the adsorption / desorption reaction of the adsorbate in the adsorbent molded body is improved.

The aspect ratio (fiber length / fiber diameter) of the fibrous heat conductive material is preferably 10 or more, more preferably 15 or more, from the viewpoint of more effectively achieving the above effects.
The aspect ratio is preferably 500 or less, more preferably 300 or less, and particularly preferably 100 or less, from the viewpoint of maintaining a higher packing density of the adsorbent.

Although there is no restriction | limiting in particular in the fiber length of the said fibrous heat conductive material, 10 micrometers-1000 micrometers are preferable, 10 micrometers-500 micrometers are more preferable, 100 micrometers-300 micrometers are especially preferable.
Although there is no restriction | limiting in particular in the fiber diameter of the said fibrous heat conductive material, 0.01 micrometer-100 micrometers are preferable, 0.1 micrometer-100 micrometers are more preferable, and 1 micrometer-50 micrometers are especially preferable.

The fibrous heat conductive material is preferably an inorganic material from the viewpoint of more effectively achieving the above effects, and is composed of metal fiber and carbon fiber (hereinafter also referred to as “CF”). More preferred is at least one selected from the group.
About a metal fiber and a carbon fiber, a preferable aspect ratio and preferable fiber length are the ranges mentioned above, respectively.
Examples of the metal fibers include aluminum fibers and copper fibers.
As the fibrous heat conductive material, carbon fiber is particularly preferable.

  Among the carbon fibers, carbon fibers having an aspect ratio of 10 to 500 and a fiber length of 10 μm to 500 μm (more preferably 100 μm to 300 μm) are particularly preferable.

  The thermal conductivity in the axial direction of the fibrous thermal conductive material is not particularly limited as long as it is higher than the thermal conductivity of the adsorbent, but for example, 1.0 W (m · K) or more. 2.0 W / (m · K) or more is preferable.

In the adsorbent molded body, the direction of the axial center of the thermally conductive material is not particularly limited except that it intersects the heat transfer surface of the adsorbent molded body, and a plurality of thermally conductive materials The direction of the axis may be a random direction with respect to the heat transfer surface.
However, from the viewpoint of further improving the efficiency of the heat exchange and further improving the reaction rate of the adsorption / desorption reaction, a preferred form of the adsorbent molded body is the axial direction of the fibrous thermal conductive material. Is a form including at least a fibrous heat conductive material having an angle of 45 ° or more with respect to the heat transfer surface. The adsorbent molded body of this form may include a fibrous heat conductive material whose axis is less than 45 ° with respect to the heat transfer surface (for example, a fibrous heat conductive material). For example, the direction of the axis of the material is random with respect to the heat transfer surface).
Here, the direction of the axial center of the fibrous heat conductive material is 45 ° or more with respect to the heat transfer surface.
It means that the minimum angle among the angles formed by the direction of the axis and the heat transfer surface is 45 ° or more (the same applies to the meanings of “70 ° or more” and “80 ° or more” below). .

In the present invention, the most preferable form from the viewpoint of further improving the efficiency of the heat exchange and further improving the reaction rate of the adsorption / desorption reaction is the most fibrous thermal conductivity contained in the adsorbent molded body. This is a form in which the direction of the axis of the material is aligned to some extent so as to be substantially perpendicular to the heat transfer surface.
Specifically, 80% by number or more (preferably 90% by number or more, more preferably 95% by number or more) of the fibrous thermal conductive material contained in the adsorbent molded body is in the direction of the axis. However, the form which is 70 degrees or more (more preferably 80 degrees or more) with respect to the said heat-transfer surface is especially preferable.
Furthermore, in this embodiment, compared to the case where the direction of the axis of the heat conductive material is random, it is possible to suppress the spring back when the adsorbent molded body is produced. The density can be further improved, and the reaction rate can be further improved.
The angle formed between the direction of the axis and the heat transfer surface is ideally 90 ° (vertical), but does not necessarily need to be exactly 90 ° (vertical).

The amount of the heat conductive material in the adsorbent molded body is preferably 1% by volume to 30% by volume, more preferably 1% by volume to 20% by volume, and more preferably 5% by volume with respect to the total amount of the adsorbent molded body. ˜20% by volume is particularly preferred.
The effect by the said heat conductive material is more effectively show | played as the said content is 1 volume% or more.
When the content is 30% by volume or less, the amount of adsorbate involved in the adsorption / desorption reaction can be increased.

-Other ingredients-
The adsorbent molded body may contain other components other than those described above.
Examples of other components include a binder and a pore former.
The binder is preferably at least one water-soluble binder.
Examples of the water-soluble binder include polyvinyl alcohol, trimethyl cellulose, carboxymethyl cellulose (CMC) and the like. Among these, trimethyl cellulose is preferable.
The content of the binder is preferably 1 to 5% by volume and more preferably 1 to 2% by volume with respect to the total amount of the adsorbent shaped body.

-Method for producing adsorbent molded body-
Moreover, there is no restriction | limiting in particular about the method of producing the said adsorption material molded object (formation), Well-known shaping | molding, such as pressure molding and extrusion molding, the mixture (for example, slurry) containing the said adsorption material and the said heat conductive material The method of shape | molding by a means is mentioned.
Examples of the molding pressure include 20 MPa to 100 MPa, and 20 MPa to 40 MPa is preferable.

As a method for producing an adsorbent molded body in which the direction of the axial center of 80% by number or more of the fibrous heat conductive material contained in the adsorbent molded body is 70 ° or more with respect to the heat transfer surface. Examples of the method include the following first method and second method.
In the first method and the second method described below, in the molding of the adsorbent molded body by extrusion molding, the axis direction of the fibrous thermal conductive material is easily aligned in a direction substantially parallel to the extrusion direction. This is a method that uses properties.
Here, “the direction of the axis of the heat conductive material is substantially parallel to the direction of extrusion” means that the angle formed between the direction of the axis and the direction of extrusion is 30 ° or less (preferably 20 ° or less). .
In the first method, first, a columnar molded body in which the direction of the axis of the heat conductive material is aligned in a direction substantially parallel to the extrusion direction at the time of extrusion molding was obtained by extrusion molding, and then obtained. In this method, an adsorbent molded body is obtained as a flat molded body by cutting a columnar molded body along a plurality of planes perpendicular to the extrusion direction during extrusion molding.
The second method was obtained by first producing a plurality of flat plate-like molded bodies in which the direction of the axis of the heat conductive material is aligned in a direction substantially parallel to the extrusion direction at the time of extrusion molding by extrusion molding. A plurality of plate-shaped molded bodies are stacked and bonded to obtain a columnar molded body, and the obtained columnar molded body is cut by a plurality of planes perpendicular to the extrusion direction at the time of extrusion molding. It is a method of obtaining an adsorbent molded body as a shaped molded body.

Next, as illustrated in FIG. 2, the stacked body 30 includes a support 34.
The support 34 is a member for circulating NH ₃ (adsorbate) in the direction along the surface of the support 34 (the direction of the white arrow in FIG. 2). As such a support 34, for example, a porous plate can be used.
The support 34, it is possible to secure the flow passage of NH ₃ between two adsorbent molded article, the NH ₃ supplied from the pipe 10 can be supplied to a wide range of adsorbent shaped bodies 32A and 32B. Furthermore, NH ₃ adsorbed in a wide range of the adsorbent molded bodies 32A and 32B can be released toward the pipe 10 via the support 34.

Further, as shown in FIG. 1, in the adsorption heat pump 100, the heat exchange reactor 20 and the pipe 10 communicate the plurality of reaction chambers 24 and the pipe 10 in the heat exchange reactor 20 in an airtight state. It is connected via a header member 28 (for example, a manifold). Thereby, ammonia can be circulated between the plurality of reaction chambers 24 and the pipe 10 in an airtight state.
In FIG. 1, in order to make the configuration of the heat exchange reactor 20 easier to see, the header member 28, the following header member 29A, the following header member 29B, the following heat medium pipe 27A, and the following heat medium pipe 27B are It is represented by a dotted line.

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 M1 can be circulated between the heat medium flow path 26 in the heat exchange reactor 20 and the outside of the adsorption heat pump 100 (heat utilization target) through the heat medium pipe 27A and the heat medium pipe 27B. It has become.
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.

  Further, as shown in FIG. 1, the pipe 10 in the adsorption heat pump 100 is provided with a valve V1 (valve). By opening and closing the valve V1, the heat exchange reactor 20 side and the evaporation condenser 40 side are connected. The difference in ammonia pressure can be adjusted. Thereby, the difference between the ammonia pressure on the heat exchange reactor 20 side and the ammonia pressure on the evaporation condenser 40 side can be more effectively maintained. That is, the difference in ammonia pressure can be maintained for a long time by keeping the valve V1 closed, and then ammonia can be transported from one to the other by opening the valve V1.

  In this embodiment, there is no restriction | limiting in particular in the structure of the evaporative condenser 40, It can be set as the structure of a well-known evaporative condenser. In this embodiment, an evaporator and a condenser may be used instead of the evaporation condenser 40.

The adsorption heat pump 100 may be connected to an exhaust means for exhausting the inside of the apparatus, a pressure measuring means for measuring the ammonia pressure in the apparatus, and the like.
In addition, the heat exchange reactor according to the present embodiment can be used not only for the adsorption heat pump but also for other heat transport systems. Examples of other heat transport systems include at least a heat transport system having a configuration in which the heat exchange reactor of the present invention and a heat exchange reactor containing a chemical heat storage material are connected by a pipe. .

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited by the Example shown below. In the following, “wt%” represents mass%, and “vol%” represents volume%.

[Example 1]
≪Measurement of NH ₃ desorption rate≫
<Preparation of adsorbent molded body a>
First, 60 parts by mass of powdered activated carbon (average primary particle size 5 μm, specific surface area 2000 m ² / g by BET method) as an adsorbent and carbon fiber (CF) (mild product ( Nippon Graphite Fiber Co., Ltd. XN-100); fiber length 200 μm, fiber diameter 10 μm, aspect ratio 20) 40 parts by mass, trimethylcellulose 5 parts by mass, and water 100 parts by mass were mixed to obtain a slurry.
The obtained slurry was subjected to extrusion molding (extrusion pressure: 40 MPa) using a mold having an opening of 20 mm × 3 mm, and seven plate-shaped molded bodies having a size of 20 mm × 20 mm × thickness 3 mm were produced.
Next, seven flat plate-shaped molded bodies were bonded with an adhesive (carboxymethylcellulose (CMC)) so as to overlap in the thickness direction, thereby obtaining a columnar molded body.
The obtained columnar molded body was cut along a plurality of planes perpendicular to the extrusion direction in extrusion molding to obtain a flat plate-shaped molded body having a thickness of 3 mm. One side of the obtained flat molded body was scraped to adjust the size, and an adsorbent molded body a having a size of 20 mm × 20 mm × thickness 3 mm was obtained. In the adsorbent molded body a, a 20 mm × 20 mm surface was used as a heat transfer surface.
In the adsorbent molded body a, the packing density of activated carbon is 0.32 g / mL, and the ratio of CF to the entire adsorbent molded body a is 10% by volume.

The obtained adsorbent molded body a was cut in the thickness direction, and the obtained cross section was observed with an optical microscope (magnification 3000 times).
FIG. 3 is a cross-sectional optical microscope image of the adsorbent molded body a.
FIG. 3 shows the heat transfer surface S and the approximate direction of the axis of the CF (double-sided arrow).
As shown in FIG. 3, most of the CF contained in the adsorbent molded body a was aligned in a direction in which the direction of the axial center was substantially perpendicular to the heat transfer surface S. Specifically, 95% by number or more of CF contained in the adsorbent molded body a has an axial direction of 70 ° or more with respect to the heat transfer surface.

<Production of heat exchange reactor>
A heat exchange reactor having the same configuration as that of the heat exchange reactor 20 shown in FIG. Details are shown below.
First, a housing 22 (material: SUS304) having two reaction chambers 24 was prepared.
Next, a laminate 30 having a structure in which the support 34 was sandwiched between the adsorbent molded bodies a (two sheets) was produced, and the obtained laminate 30 was accommodated in each reaction chamber 24. As the support 34, a stainless steel porous sheet having a size of 20 mm × 20 mm × thickness 0.5 mm was used.

<Measurement of NH ₃ desorption rate>
Using the heat exchange reactor, an experimental machine was prepared in which the evaporative condenser 40 was replaced with an NH ₃ chamber in the adsorption heat pump 100 shown in FIG. In this experimental machine, connect the NH ₃ gas cylinder in NH ₃ chamber, experimental flight (NH ₃ chamber, the heat exchange reactor of the reaction chamber, and in the pipe; same hereinafter.) Was to be able to supply the NH ₃ to . Furthermore, to connect the vacuum pump and a pressure gauge to NH ₃ chamber, to adjust the NH ₃ pressure of NH ₃ in the chamber, and to allow exhaust experimental flight.
In this experimental machine, the volume of the heat exchange reactor was 6.0 mL, and the NH ₃ chamber volume was 2.2 L.

The NH ₃ desorption rate was measured as follows.
First, as a preparatory stage, with the valve V1 opened, water (heat medium M1) with a liquid temperature of 6 ° C. and a flow rate of 60 mL / min is circulated through the heat medium flow path 26 of the heat exchange reactor 20 and in the experimental machine Then, NH ₃ was supplied to the adsorbent molded body a in the reaction chamber 24 to adsorb NH ₃ . This operation was performed until adsorption equilibrium was reached. Then, closing the valves V1, the pressure was reduced to NH ₃ pressure of NH ₃ in the chamber 2 atm.
Then, by opening the valve V1 while maintaining the flow of the fluid temperature and the amount of liquid water (heat medium M1), the NH ₃ desorbed (desorption) from the adsorbent molded article a in the reaction chamber 24, NH ₃ Transported to chamber.
By observing the pressure rise in the NH ₃ chamber due to transportation of the NH _3, it was determined the kinetics of desorption reaction of NH ₃ (the relationship between the reaction time and the desorption rate). Here, the elapsed time from when the valve V1 was opened was defined as the reaction time.
The measurement results are shown in FIG.
6 and 7, the measurement result of the first embodiment is also described as “CF substantially vertical” for convenience.

≪Measurement of thermal conductivity of adsorbent molded body≫
Three types of samples for measuring thermal conductivity (adsorbent molded bodies) of φ20 mm × thickness 2 mm, φ20 mm × thickness 3 mm, and φ20 mm × thickness 4 mm were produced by the same method as the production of the adsorbent molded product a ( In any sample, the surface of φ20 mm is the heat transfer surface).
For each sample, the thermal conductivity in the thickness direction (direction perpendicular to the heat transfer surface) is measured by a steady method, and the average value of the measurement results in each sample is measured in the thickness direction in the first embodiment. Conductivity was used.
The measurement results are shown in FIG.

[Example 2]
≪Measurement of NH ₃ desorption rate≫
The slurry used in Example 1 was subjected to extrusion molding (extrusion pressure 40 MPa) using a mold having an opening of 20 mm × 3 mm to prepare an adsorbent molded body b having a size of 20 mm × 20 mm × thickness 3 mm.
In the adsorbent molded body b, the packing density of activated carbon is 0.32 g / mL, and the ratio of CF to the entire adsorbent molded body b is 10% by volume.
The obtained adsorbent molded body b was observed with an optical microscope in the same manner as the adsorbent molded body a in Example 1.
FIG. 4 is a cross-sectional optical microscope image of the adsorbent molded body b.
FIG. 4 shows the heat transfer surface S and the approximate direction of the axis of the CF (double-sided arrow).
As shown in FIG. 4, the adsorbent molded body b includes a CF whose axial direction intersects the heat transfer surface S, but in any CF, the axial direction and the heat transfer surface S are included. The angle formed by the angle was 30 ° or less.

Next, the NH ₃ desorption rate was measured in the same manner as in Example 1 except that the adsorbent molded body a in Example 1 was changed to the adsorbent molded body b.
The measurement results are shown in FIG.
6 and 7, the measurement result of the present Example 2 is also described as “CF substantially horizontal” for convenience.

≪Measurement of thermal conductivity of adsorbent molded body≫
Three types of samples for measuring thermal conductivity (adsorbent molded bodies) of φ20 mm × thickness 2 mm, φ20 mm × thickness 3 mm, and φ20 mm × thickness 4 mm were produced by the same method as the production of the adsorbent molded body b ( In any sample, the surface of φ20 mm is the heat transfer surface).
Using each sample, the thermal conductivity in the thickness direction was measured in the same manner as in Example 1.
The measurement results are shown in FIG.

Example 3
≪Measurement of NH ₃ desorption rate≫
The slurry used in Example 1 was pressure-molded (molding pressure 40 MPa) to prepare an adsorbent molded body c having a size of 20 mm × 20 mm × thickness 3 mm.
In the adsorbent molded body c, the packing density of activated carbon is 0.32 g / mL, and the ratio of CF to the entire adsorbent molded body c is 10% by volume.
The obtained adsorbent molded body c was observed with an optical microscope in the same manner as the adsorbent molded body a in Example 1.
FIG. 5 is a cross-sectional optical microscope image of the adsorbent molded body c.
As shown in FIG. 5, in the adsorbent molded body c, the direction of the CF axial center was a random direction. The adsorbent molded body c also contained CF having an axial direction of 45 ° or more with respect to the heat transfer surface.

Next, the NH ₃ desorption rate was measured in the same manner as in Example 1 except that the adsorbent molded body a in Example 1 was changed to the adsorbent molded body c.
The measurement results are shown in FIG.
In FIG. 6 and FIG. 7, the measurement result of the third embodiment is also described as “CF random” for convenience.

≪Measurement of thermal conductivity of adsorbent molded body≫
Three types of heat conductivity measurement samples (adsorbent molded bodies) of φ20 mm × thickness 2 mm, φ20 mm × thickness 3 mm, φ20 mm × thickness 4 mm are produced by pressure molding similar to the production of the adsorbent molded body c. (In each sample, the surface of φ20 mm is the heat transfer surface).
Using each sample (CF 10 vol%; activated carbon packing density 0.32 g / mL), the thermal conductivity in the thickness direction was measured in the same manner as in Example 1.
Furthermore, the amount of activated carbon and CF contained in the slurry was changed to 40 parts by mass of activated carbon and 60 parts by mass of CF, and the same thermal conductivity was measured as above (CF 15 vol%; packing density of activated carbon 0.26 g / mL). ).
Furthermore, the amount of activated carbon and CF contained in the slurry was changed to 30 parts by mass of activated carbon and 70 parts by mass of CF, and the same thermal conductivity was measured as above (CF 18 vol%; packing density of activated carbon 0.19 g / mL) ).
The measurement results are shown in FIG.

[Comparative Example 1]
In Example 2, the same measurement as in Example 2 was performed except that the slurry for producing the adsorbent molded body b did not contain CF and the amount of activated carbon was changed to 100 parts by mass.
The packing density of the activated carbon in the adsorbent molded body of Comparative Example 1 is 0.52 g / mL.
The measurement results are shown in FIGS.
6 and 7, the measurement result of Comparative Example 1 is also described as “without CF” for convenience.

6, in Examples 1 to 3 and Comparative Example 1 is a graph showing the relationship between the reaction time and the NH ₃ desorption rate of desorption reactions NH _3.
The time (sec) on the horizontal axis is the reaction time of the NH ₃ desorption reaction, and specifically, the elapsed time (seconds) from when the valve is opened.
The desorption rate (−) on the vertical axis represents the desorption amount of NH ₃ at a reaction time of 300 sec in Example 1 as 1.0, and the desorption amount of NH ₃ at a reaction time of 0 sec in Example 1 as 0.0. Relative value. Here, the desorption amount of NH ₃ was determined based on the pressure increase in the NH ₃ chamber.

As shown in FIG. 6, Example 1 (CF substantially vertical), Example 2 (CF substantially horizontal), and an adsorbent molded body containing CF whose axial center intersects the heat transfer surface, and In Example 3 (CF random), the desorption rate of NH ₃ was improved as compared with Comparative Example 1 (without CF) using an adsorbent molded body containing no CF.
Among Examples 1 to 3, in Examples 1 and 3 using an adsorbent molded body containing CF whose axis is 45 ° or more with respect to the heat transfer surface, the NH ₃ desorption rate is high. confirmed.
Furthermore, in Examples 1 and 3, in Example 1 in which the direction of the axial center of 95% by number or more of CF contained in the adsorbent molded body is 70 ° or more with respect to the heat transfer surface, NH ₃ It was confirmed that the desorption speed of was extremely high.

FIG. 7 shows the activated carbon packing density in the adsorbent molded bodies and the thermal conductivity (W / (m · K)) in the thickness direction of the adsorbent molded bodies in Examples 1 to 3 and Comparative Example 1. It is a graph which shows a relationship.
The thermal conductivity shown in FIG. 7 corresponds well with the desorption rate of NH ₃ shown in FIG. 6, and the thermal conductivity in Examples 1 to 3 (especially Examples 1 and 3, especially Example 1) is high. It was. Thereby, it was confirmed that the ammonia desorption rate of NH ₃ was improved as the thermal conductivity in the thickness direction (direction perpendicular to the heat transfer surface) was improved.
In particular, in Example 1, it was confirmed that large thermal conductivity was obtained in the thickness direction (direction perpendicular to the heat transfer surface) while maintaining a high packing density (0.32 g / mL) of activated carbon. It was. This is considered to be the reason why the NH ₃ desorption rate is remarkably improved in Example 1.

In the above example, the reaction rate (desorption rate) of the NH ₃ desorption reaction was evaluated, but it goes without saying that the same result as in the above example can be obtained for the reaction rate (adsorption rate) of the NH ₃ adsorption reaction. Nor.

DESCRIPTION OF SYMBOLS 10 Piping 20 Heat exchange type | mold reactor 22 Case 24 Reaction chamber 26 Heat medium flow path 30 Laminate body 32A, 32B Adsorbent molded object 34 Support body 40 Evaporative condenser 100 Adsorption-type heat pump M1 Heat medium S Heat transfer surface

Claims (11)

A reaction chamber in which an adsorbent molded body can be accommodated, and a housing in which heat medium flow paths through which the heat medium flows are alternately arranged;
An adsorbent that is housed in the reaction chamber and has a heat transfer surface that exchanges heat with the heat medium, radiates heat when the adsorbate is adsorbed, and stores heat when the adsorbate is desorbed, and a shaft center An adsorbent molded body containing a fibrous heat conductive material whose direction intersects the heat transfer surface;
A heat exchange reactor equipped with   2. The heat exchange reactor according to claim 1, wherein the fibrous heat conductive material has an axis direction of 45 ° or more with respect to the heat transfer surface.   The axial direction of 80% by number or more of the fibrous heat conductive material contained in the adsorbent molded body has an axis direction of 70 ° or more with respect to the heat transfer surface. A heat exchange reactor according to 1.   The heat exchange type reactor according to any one of claims 1 to 3, wherein the heat conductive material has an aspect ratio of 10 or more. The adsorbent molded body is a flat adsorbent molded body in contact with the wall surface of the reaction chamber;
The heat exchange reactor according to any one of claims 1 to 4, wherein the heat transfer surface is a contact surface with the wall surface.   The heat exchange reactor according to any one of claims 1 to 5, wherein the heat conductive material is an inorganic material.   The heat exchange reactor according to any one of claims 1 to 6, wherein the heat conductive material is carbon fiber.   The heat exchange reactor according to any one of claims 1 to 7, wherein the adsorbent is at least one selected from the group consisting of activated carbon, mesoporous silica, zeolite, silica gel, and clay mineral.   The heat exchange type reactor according to any one of claims 1 to 8, wherein the heat conductive material has a thermal conductivity in the direction of an axial center of 2 W / (m · K) or more.   The quantity of the said heat conductive material in the said adsorbent molded object is 1 volume%-30 volume% with respect to the whole quantity of the said adsorbent molded object, The any one of Claims 1-9. Heat exchange reactor.   An adsorption heat pump comprising the heat exchange reactor according to any one of claims 1 to 10.