JP2007190546A - Adsorbing sheet, adsorbing element, method for manufacturing the element and use of them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adsorbing sheet which constitutes an adsorbing element of an adsorption unit to be used in an adsorption heat pump or a desiccant system and is excellent in heat-resistant performance and more excellent in adsorption/desorption capacity, to provide the adsorbing element which comprises the adsorbing sheet as a constituent element, is more excellent in heat-resistant performance and adsorption/desorption capacity and is made compact and to provide a method for manufacturing the adsorbing element. <P>SOLUTION: The adsorbing sheet (1) is obtained by depositing an adsorbing material on a base material sheet (12) by using a binder and used for the adsorbing element. The adhesive strength of the adsorbing sheet is ≥0.04 MPa after such a durability test is repeated fifty times that the adsorbing sheet is heated to 120°C, the heated adsorbing sheet is immersed in the water of normal temperature and the immersed adsorbing sheet is cooled to -15°C. The adsorbing element of a plate fin type being one embodiment is provided with: a plurality of adsorbing sheets (1) each of which is formed into a plate-like shape and which are arrayed in parallel and side by side; and one heating medium flow passage penetrating each of adsorbing sheets (1). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an adsorbing sheet, an adsorbing element, and a manufacturing method thereof, and more specifically, an adsorbing sheet that adsorbs adsorbate and moisture by an adsorbent, and an adsorbing material that includes the adsorbing sheet as a component and performs heat transfer The present invention relates to an adsorption element used in a desiccant system that performs humidity control such as a heat pump and dehumidification / humidification, and a method of manufacturing the adsorption element.

  Adsorption heat pumps and desiccant systems are systems that use adsorption and desorption functions of adsorbents to control heat transfer and humidity. For example, various cooling devices that use low-temperature exhaust heat from cogeneration systems, air conditioning units, humidity control Applied to the device. An apparatus using an adsorption heat pump generates heat by adsorption heat on the adsorbent side, generates cold heat by evaporating latent heat of water, for example, on the evaporation side, and an apparatus using a desiccant system is used during periods of high humidity. Dehumidification is performed, and humidification is performed at a time when the humidity is low, and both devices are useful for constructing a comfortable space.

Recently, for the adsorption elements used in the adsorption devices of the adsorption heat pump and desiccant system described above, a technique for directly applying an adsorbent to heat exchange fins, etc. has been studied in order to increase the adsorption capacity and reduce the size of the apparatus. ing. For example, an adsorption element having a structure in which an adsorbent is directly applied to a heat exchange fin is an element used in a heat exchanger of an adsorption refrigeration machine, and an adhesive acrylic binder is attached to a large number of aluminum fins. An adsorbing element has been proposed in which a powdered silica gel having a surface of 20 to 35 mesh (particle size of about 450 to 850 μm) is applied to the surface.
JP-A-7-301469

Furthermore, a slurry-like or paste-like adsorbent in which silica gel, graphite and an organic binder are mixed and water is added and dispersed has been proposed as an adsorbent for an adsorption refrigerator. Then, as a heat exchanger (adsorption element), a large number of heat transfer fins are attached to the heat transfer pipe, and the element itself is immersed in the slurry adsorbent and air-dried. A heat exchanger having a heat-dried monolithic structure has been proposed. Note that silica gel having a particle size of 42 mesh or less (particle size of about 350 μm or more) is added to the slurry adsorbent.
Japanese Patent Laid-Open No. 10-286460

Further, as an adsorption element mainly applied to a desiccant system, a rotor-type element configured into a honeycomb structure by supporting zeolite on a fibrous sheet and forming the fibrous sheet with a honeycomb molding machine. Has been proposed. The honeycomb-structured adsorbing element has a large surface area with respect to the entire volume and is excellent in adsorbing ability.
JP 2002-95964 A

  By the way, in the adsorbing element as described above, adaptability in a wider temperature range is desired on both the low temperature side and the high temperature side due to the expansion of applications of adsorption heat pumps and desiccant systems and the diversification of heat sources. As the performance, heat resistance, that is, the adhesiveness of the adsorbent that is not affected by temperature change is important. However, a conventionally known adsorbent slurry for producing an adsorbing element, in other words, an aqueous dispersion as described above containing an adsorbent and an organic binder, can be obtained by adhering the adsorbents to each other in the resulting adsorbing element. The actual situation is that the adhesive strength between the material and the base material is not so strong and sufficient heat resistance performance cannot be exhibited.

  In addition, in an adsorption element using a heat exchange fin structure, a sufficient ventilation space for exposing the surface of a large number of fins to air or adsorbate vapor is necessary, but the unit volume of the element including such a ventilation space is required. It is important to increase the amount of adsorption / desorption and the adsorption / desorption speed of each fin as much as possible in order to increase the performance and reduce the size of the apparatus. Therefore, in the adsorbing element described above, silica gel having a relatively large particle size of 350 μm or more or about 450 μm or more is selected and applied to the fin surface from the viewpoint of enhancing adsorption / desorption ability.

  However, when the particle size of the adsorbent particles is increased, the diffusion rate of water vapor and adsorbate vapor inside each particle decreases, so the problem is that it cannot exert much capacity compared to the particle size. There is. On the other hand, it is desirable to reduce the particle size of the adsorbent particles as much as possible from the viewpoint of further increasing the adsorption / desorption ability of each adsorbent particle. Since the amount of adsorbing material that can be adhered is reduced and the adsorption / desorption ability of each fin is extremely low, it is not suitable for practical use. Therefore, in the adsorbing element, an improved means capable of supporting a larger amount of adsorbent with a smaller particle diameter is desired.

  The present invention has been made in view of the above circumstances, and its purpose is an adsorption sheet that constitutes an adsorption element of an adsorption device used in an adsorption heat pump or a desiccant system, and has excellent heat resistance performance. An object of the present invention is to provide an adsorbing sheet with further excellent desorption capability. Still another object of the present invention is to provide an adsorbing element including the adsorbing sheet described above as a component, further excellent in heat resistance performance, adsorbing / desorbing ability, and capable of being further reduced in size, and a manufacturing method thereof. is there.

  In order to solve the above problems, in the present invention, a binder having a glass transition temperature after curing of a predetermined temperature or a binder having a specific structure or a binder having a specific structure is used as a binder for supporting the adsorbent on the substrate of the adsorbent sheet. Thus, the adhesive strength between the adsorbents and the adhesive strength between the adsorbent and the base material is increased in a wide temperature range, and a larger amount of the adsorbent having a smaller particle diameter is supported. A so-called plate fin type adsorbing element having a structure in which a plurality of plate-like adsorbing sheets are arranged at regular intervals, and a band-like adsorbing sheet bent in a zigzag manner, has a large number of bridges between the inlet header and outlet header of the heat medium. In the so-called corrugated fin type adsorbing element having a passed structure and the so-called rotor type adsorbing element configured in a cylindrical or columnar honeycomb structure having a large number of cells, the above-described configuration of the adsorbing sheet is applied. As a result, the heat resistance performance and adsorption / desorption capability of the element were improved, and the element was downsized.

  That is, the present invention consists of eleven aspects, and the first aspect is an adsorption sheet for an adsorption element in which an adsorbent is supported on a base material sheet by a binder, which is heated to 120 ° C. under normal temperature water. The adhesive sheet has an adhesive strength of 0.04 MPa or more after a durability test in which the operation of cooling to −15 ° C. after 50 times of immersion is repeated. A preferable embodiment of such an adsorbent sheet is that the amount of water vapor adsorption after performing a durability test in which the operation of heating to 120 ° C. and immersing in normal temperature water and then cooling to −15 ° C. is repeated 50 times is the initial water vapor adsorption. 80% or more based on the amount. And in such an adsorption sheet, as an adsorption sheet constituting the plate fin type and corrugated fin type adsorption elements, in order to increase the heat exchange efficiency between the heat medium and the adsorbent in the heat medium flow path in the adsorption element, The base sheet is preferably a metal sheet, and the adsorbent sheet constituting the adsorbing element of the rotor is preferably a fibrous sheet in order to hold a larger amount of adsorbent.

  The second gist of the present invention is an adsorbing element comprising a plurality of adsorbing sheets according to the first gist in which the base sheet is a metal sheet, and each adsorbing sheet is formed in a plate shape, Each adsorbing sheet is arranged through a fixed ventilation space so that the plate surfaces of the adsorbing sheets are parallel and parallel to each other; It exists in the adsorption | suction element characterized by arrange | positioning in the state penetrated and contacting each said adsorption sheet.

  A third gist of the present invention is an adsorbing element comprising a plurality of adsorbing sheets according to the first gist in which the base sheet is a metal sheet, and each adsorbing sheet is formed in a belt shape bent in a zigzag manner. An inlet-side header and an outlet-side header, and a plurality of straight tubular heat medium passages extending in parallel and parallel therebetween, and each adsorbing sheet has its longitudinal direction in the heat medium passage. Are inserted between each adjacent heat medium flow path, and the concave portion of the adsorption sheet is used as a ventilation space, and each heat medium flow path is formed on each convex portion of the adsorption sheet adjacent thereto. It exists in the adsorption | suction element characterized by contacting.

  A fourth aspect of the present invention is an adsorption element comprising a large number of the adsorption sheets according to the first aspect, wherein the base sheet is a fibrous sheet, and constituted by these adsorption sheets into a cylindrical honeycomb structure. The adsorbing sheets formed in a substantially corrugated plate shape are arranged in a laminated state along the circumferential direction, so that a large number of ventilation cells having a substantially hexagonal opening shape are provided on the circumferential surface. It exists in the adsorption element characterized by this.

  The fifth gist of the present invention is an adsorbing element comprising a large number of adsorbing sheets according to the first gist in which the base material sheet is a fibrous sheet, and constituted by these adsorbing sheets into a cylindrical honeycomb structure. In addition, the suction sheet formed in a substantially corrugated plate shape and the suction sheet formed in a substantially flat plate shape are alternately arranged in a stacked state along the axial direction, thereby having a substantially triangular opening shape. The adsorption element is characterized in that a large number of cells are provided on the peripheral surface.

  The sixth aspect of the present invention is an adsorption element comprising a large number of the adsorption sheets according to the first aspect, wherein the base sheet is a fibrous sheet, and constituted by the adsorption sheets into a cylindrical honeycomb structure. The adsorbent sheets formed in a substantially corrugated plate shape are arranged in a laminated state along the circumferential direction, so that a large number of ventilation cells having a substantially hexagonal opening shape are provided on the end surface. It exists in the adsorption element characterized by this.

  The seventh aspect of the present invention is an adsorption element comprising a large number of the adsorption sheets according to the first aspect, wherein the substrate sheet is a fibrous sheet, and comprising the cylindrical honeycomb structure by these adsorption sheets. And the suction sheet formed in a substantially corrugated plate shape and the suction sheet formed in a substantially flat plate shape are alternately arranged in a laminated state along the diameter direction, thereby having a substantially triangular opening shape. In the adsorption element, a large number of cells are provided on the end face.

  An eighth aspect of the present invention is a method for manufacturing an adsorption element according to the second or third aspect, wherein a skeleton structure substrate of the adsorption element is produced using a substrate sheet, and then the adsorption element is produced. After applying an aqueous dispersion in which a material and a binder are dispersed in water to the base material sheet of the skeletal structure base, the base material sheet is heated and dried to attach the adsorbent to the surface of the base material sheet The present invention resides in a method for manufacturing an adsorption element.

  A ninth aspect of the present invention is a method for manufacturing an adsorbing element according to any of the fourth to seventh aspects, wherein a base material sheet is used to produce a skeleton structure substrate of the adsorbing element, Next, after applying an aqueous dispersion liquid in which an adsorbent and a binder are dispersed in water to the base material sheet of the skeleton structure base material, the base material sheet is heated and dried, whereby the surface and the inside of the base material sheet The present invention resides in a method for manufacturing an adsorbing element, characterized in that an adsorbing material is attached to the adsorbent.

  A tenth aspect of the present invention resides in an adsorption heat pump including the adsorption element according to any one of the second to seventh aspects described above, and an eleventh aspect of the present invention includes The humidity control air conditioner includes the adsorption element according to any one of the second to seventh aspects.

  According to the adsorption sheet according to the first aspect of the present invention, the amount of water vapor adsorption after performing a specific durability test on the initial amount of water vapor adsorption is large, excellent in heat resistance performance and anti-peeling function, Since the desorption capability is excellent, an adsorption element having this as a constituent element can exhibit even better adsorption / desorption performance in a wider temperature range.

  According to the adsorbing element according to the second to seventh aspects of the present invention, since the adsorbing sheet described above is provided as a constituent element, it is excellent in heat resistance performance, adsorbing / desorbing ability, and can be further downsized. Moreover, according to the manufacturing method of the adsorption element which concerns on the 8th and 9th summary of this invention, said adsorption element excellent in heat-resistant performance and adsorption | suction / desorption ability can be manufactured efficiently. And according to the adsorption heat pump which concerns on the 10th summary of this invention, and the humidity control air conditioner which concerns on the 11th summary, since it has said adsorption | suction element, it can be reduced more and the cogeneration by which energy saving is calculated | required It can be applied to various systems that adjust humidity using the system and surplus low-quality thermal energy.

  DESCRIPTION OF EMBODIMENTS Embodiments of an adsorption sheet, an adsorption element, and an adsorption element manufacturing method according to the present invention will be described with reference to the drawings. FIG. 1 is a partial perspective view showing a structure of one form of the suction sheet according to the present invention, and FIG. 2 is a partial perspective view showing a structure of another form of the suction sheet according to the present invention. . 3 is a perspective view showing one embodiment of a plate fin type adsorbing element according to the present invention, and FIG. 4 adsorbs the relationship between the adsorbing sheet arrangement interval and the adsorbent layer thickness in the adsorbing element of FIG. It is a fragmentary sectional view fractured | ruptured and shown in the direction orthogonal to the plate surface of a sheet | seat. FIG. 5 is a perspective view showing another embodiment of the corrugated fin-type adsorption element according to the present invention, and FIG. 6 shows the relationship between the bending pitch of the adsorption sheet and the thickness of the adsorbent layer in the adsorption element of FIG. It is a fragmentary sectional view fractured | ruptured and shown in the direction orthogonal to a plate surface along the longitudinal direction of an adsorption sheet.

  FIG. 7 is a perspective view showing one embodiment of a rotor-type adsorption element having a cylindrical honeycomb structure according to the present invention and a partially enlarged view showing a cell shape. 8 to 11 are diagrams showing a method for manufacturing a honeycomb skeleton structure substrate as a base material, and FIG. 8 is a partial view showing a method for joining the sheets in the production of a laminate of base material sheets. It is a perspective view. FIG. 9 is a partial perspective view showing the outer shape of the base material sheet laminate. FIG. 10 is a partial side view of the laminate showing the deformed state of the base sheet and the shape of the cells formed when the laminate of the base sheet is expanded. FIG. 11 is a perspective view showing a method for developing a laminated body in the production of a skeleton structure substrate of a cylindrical honeycomb. FIG. 12 is a perspective view showing another embodiment of a rotor-type adsorption element having a cylindrical honeycomb structure according to the present invention and a partially enlarged view showing a cell shape. FIG. 13 is a perspective view showing an embodiment of a cylindrical rotor-type adsorption element according to the present invention and a partially enlarged view showing the shape of a cell. FIG. 14 is a diagram showing a method for manufacturing a honeycomb skeleton structure substrate as a base material of the adsorption element of FIG. 13, and is a perspective view showing a method for developing a laminate. FIG. 15 is a perspective view showing another embodiment of a cylindrical rotor-type adsorption element according to the present invention and a partially enlarged view showing the shape of a cell.

  FIG. 16 is a process diagram showing a durability test method performed when measuring the adsorption characteristic of the adsorption sheet, and FIG. 17 is an adsorption amount measurement used when measuring the adsorption characteristic of the adsorption sheet. It is a flowchart which shows the structure of an apparatus. The following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.

  Adsorption element (as shown by reference numerals (2A), (2B), (2C), (2D), (2E), (2F) in FIGS. 3, 5, 7, 12, 13, and 15 respectively) Is applied to an adsorption device that performs adsorption / desorption operation of adsorbate in an adsorption heat pump, or an adsorption device that performs adsorption / desorption operation of water vapor in a desiccant system (humidity control system). An adsorption sheet (for example, a sheet indicated by reference numeral (1) in FIGS. 1 and 2) is a component of the adsorption element as described above.

  As is well known, the adsorption heat pump is a system that pumps heat by using the phase change of adsorbate such as water and alcohol accompanying the adsorption / desorption phenomenon of the adsorbent, and it is low quality without using auxiliary power. Since thermal energy can be operated as a heat source, it can be applied to various systems such as cogeneration systems that require energy saving to generate cold or warm heat.

  In addition, the desiccant system includes a desiccant cooling device for cooling in warehouses, etc., a large desiccant air conditioner installed as building equipment, and a dehumidifying air conditioner that includes a small dehumidifier and humidifier installed indoors. It is configured as a humidity control air conditioner such as an air conditioner or a humidifier air conditioner, and uses the adsorption / desorption action of the adsorbent to remove moisture from the indoor air to be humidity-adjusted or the air supplied to the room, and put it outside. It is a system that absorbs moisture from outdoor air or air that is exhausted to the outside and supplies it to indoor air that should be humidity-adjusted or supplied to the room, using surplus low-quality thermal energy To adjust the humidity.

  First, the suction sheet of the present invention will be described. The adsorbing sheet of the present invention indicated by reference numeral (1) in the figure can be formed in various shapes according to the structure of the adsorbing element. For example, a plate-shaped adsorbing sheet (1a) as shown in FIG. Is formed as a belt-like suction sheet (1b) bent in a zigzag manner along the longitudinal direction, and as a corrugated plate-like or belt-like suction sheet (1c) as shown in FIGS. The The adsorbing sheet (1a) shown in FIG. 1 is a component of a so-called plate fin type adsorbing element (2A) as shown in FIG. 3, and the adsorbing sheet (1b) shown in FIG. 2 is as shown in FIG. This is a constituent element of a so-called corrugated fin-type adsorption element (2B). As shown in FIGS. 7, 12, 13 and 15, the adsorption sheet (1c) is a constituent element of so-called rotor-type adsorption elements (2C) to (2F) having a honeycomb structure. Each of the adsorbing sheets (1) as described above is configured by supporting the adsorbing material on the base sheet (12), (14) with a binder.

  The base sheet (12) constituting the suction sheets (1a) and (1b) as shown in FIGS. 1 and 2 is composed of a plate fin type adsorption element (2A) (see FIG. 3) and a corrugated fin type adsorption element. In (2B) (see FIG. 5), it is a member for transferring heat between the heat medium flowing through the heat medium flow paths (3) and (4) and the adsorbent. As long as the base sheet (12) has sufficient rigidity to maintain the shape of the adsorption sheets (1a) and (1b) and efficient heat exchange with the heat medium flow paths (3) and (4) is possible. It can be composed of various materials. Examples of the constituent material of the base sheet (12) include metals, ceramics, resin materials (polypropylene, polycarbonate, polyacetal, polyamide, etc.), carbon materials, etc., but usually in terms of rigidity, thermal conductivity, and manufacturing cost. The base sheet (12) is made of a metal sheet such as aluminum, copper, brass, iron, chromium, nickel, steel, or an alloy thereof. Among these, aluminum or aluminum alloy, copper or copper alloy is preferable.

  In the case of the suction sheet (1a) used in the plate fin type suction element (2A) shown in FIG. 3, the shape (plate surface shape) of the base sheet (12) is circular, elliptical, depending on the structure of the suction device. Although it can be formed in various shapes such as a square, for example, it is formed in a rectangle as shown in FIG. In the case of such a substrate sheet (12), the length of one side is usually about 1 to 100 cm. And since pipe | tube as a heat-medium flow path (3) is penetrated at the time of manufacturing an adsorption | suction element (2A) in the base material sheet (12), the pipe | tube insertion hole (11 of the diameter which the said pipe | tube fits tightly ) Is provided. In addition, when comprising a suction sheet (1a), a base material sheet (12) may be formed in a corrugated sheet in order to enlarge the holding | maintenance amount of an adsorbent.

  Further, in the case of the suction sheet (1b) used for the corrugated suction element (2B) shown in FIG. 5, the base sheet (12) is formed in a narrow strip shape as shown in FIG. 2, for example. In the case of such a base sheet (12), the width is usually about 1 to 100 cm and the length is about 1 to 500 cm.

  The thickness of each substrate sheet (12) is not particularly limited. From the relationship between the thickness and strength of the adsorbent layer (13) on the surface formed by the adsorbent, the adsorbent sheet (1a) shown in FIG. 2), in any case of the suction sheet (1b) shown in FIG. 2, it is usually set to 50 to 300 μm, preferably 100 to 200 μm. In addition, the surface of the base sheet (12) may be coated with a thin resin film such as an epoxy resin, a phenoxy resin, or a fluorine resin in advance in order to prevent corrosion and to easily carry the adsorbent.

  On the other hand, in the rotor-type adsorption element as shown in FIGS. 7, 12, 13 and 15, the adsorbing sheet (1c) constituting the honeycomb skeleton structure substrate described later maintains the shape of the skeleton structure substrate. It is constituted by a fibrous sheet or resin (polycarbonate, polypropylene, polyacetal, polyamide, etc.) sheet having sufficient rigidity, and among these, a fibrous sheet is preferable. In the present invention, the fibrous sheet refers to a sheet made of an aggregate of inorganic or organic fibrous substances, and the fibrous substances may be intertwined with each other. For example, fillers having a large aspect ratio, nonwoven fabrics, and the like are also included in the concept of “fibrous”.

  Specifically, the material of the fibrous sheet is composed of ceramic fibers mainly composed of silica / alumina, glass fibers, carbon fibers manufactured from carbon-containing raw materials such as PAN and tar, and fibrous clay substances. Examples thereof include mineral fibers, organosilicon fibers produced from organosilicon polymers, and metal fibers produced from metals such as Fe, Cu, Al, Cr, and Ni. Examples of the chemical fiber include fibers such as acrylic, polyethylene, polypropylene, polyurethane, polyclar, nylon, rayon, vinylon, vinylidene, polyvinyl chloride, acetate, and polyester. Natural fibers such as cellulose, silk, and cotton can also be used.

  In particular, in consideration of moldability, handleability, and manufacturing cost, the material for the fibrous sheet is preferably a nonwoven fabric. Examples of such a nonwoven fabric include chemical fiber-based nonwoven fabrics such as rayon, nylon, polyester, polyethylene, polypropylene, acrylic, vinylon, cupra, and aromatic polyamide. The chemical fiber nonwoven fabric as described above may be either a single fiber or a laminate of two or more kinds of fibers. As is well known, the nonwoven fabric is manufactured by a manufacturing method such as a wet method, a dry method, a spun bond method, a melt blow method, a chemical bond method, a thermal bond method, or a needle punch method. The normal thickness of the fibrous sheet is usually 40 to 600 μm, preferably 50 to 400 μm. By using the fibrous sheet as described above, rotor-type adsorption elements having various sizes and shapes can be easily manufactured, and vibration resistance can be improved.

  To support the adsorbent on the base sheet, the adsorbing sheet (1a) shown in FIG. 1 and the adsorbing element (2A) shown in FIG. 3, or the adsorbing sheet (1b) shown in FIG. 2 and the adsorbing element shown in FIG. In the case of (2B), that is, in the case of the base sheet (12) made of a metal sheet, the base sheet (12) is applied after applying an aqueous dispersion as a slurry to at least one side of the base sheet (12). Heat to dry. As a result, the adsorbent is supported in a laminated state on at least one surface of the metal sheet by the binder. In addition, the code | symbol (13) in FIG.1, FIG.2, FIG.4 and FIG. 6 shows the adsorbent layer formed by application | coating.

  In the case of the adsorption element (2C) shown in FIG. 7, the adsorption element (2D) shown in FIG. 12, the adsorption element (2E) shown in FIG. 13, and the adsorption element (2F) shown in FIG. In the case of the base sheet (14), after applying the above aqueous dispersion to the base sheet (14) constituting the honeycomb skeleton structure substrate, the substrate sheet (14) (skeleton structure substrate) is dried by heating. To do. Thereby, the adsorbent is supported by the binder in a state where it is intertwined with the fiber on the surface and inside of the fibrous sheet.

  In the present invention, when the adsorbent sheet (1) is manufactured, the adsorbent is adhering to the base material sheets (12) and (14) of the adsorbent sheet (1). In order to increase the adhesive strength with the material sheets (12) and (14) and to increase the adsorption capacity, the above-mentioned aqueous dispersion is a specific aqueous system in which the following adsorbent and binder are dispersed in water. A dispersion is used.

  Examples of the adsorbent include porous materials such as activated carbon, silica, mesoporous silica, alumina, and zeolite. Among these, zeolite that can easily adsorb adsorbate vapor and water vapor and can be easily desorbed in a low temperature range is preferable. In particular, from the viewpoint of easy control of the structure and adsorption characteristics, crystalline aluminophosphates (ALPO-based zeolite) containing at least Al and P in the skeleton structure are preferable. Typically, SAPO-34, FAPO- 5 is mentioned. The above adsorbents can be used alone or in combination of two or more. The ALPO-based zeolite can be produced by using a known synthesis method described in Japanese Patent Publication No. 1-57041, Japanese Patent Application Laid-Open No. 2003-183020, Japanese Patent Application Laid-Open No. 2004-136269, and the like.

The size of the adsorbent particles is supported on the base sheet (12) and (14) from the viewpoint of enhancing the adsorption / desorption capability by promoting the diffusion of adsorbate vapor and water vapor in the individual particles of the adsorbent. From the viewpoint of improving the adhesive strength of the carrier containing the adsorbent, it is desirable to make it as small as possible. Usually, the average particle size is 0.1 to 300 microns, preferably 0.5 to 250 microns, more preferably 1. ˜200 microns, most preferably 2-20 microns. And in order to provide sufficient adsorption | suction and desorption capability to an adsorption sheet (1), the basis weight of an adsorbent shall be 5-400 g / m < ² >.

Moreover, as said binder, from a heat resistant viewpoint, the heat resistant organic binder, ie, the resin whose glass transition temperature is 35 degreeC or more, Preferably resin whose glass transition temperature is 45 degreeC or more is used. Such a resin can be selected from an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a fluororesin, a polycarbonate resin, a (meth) acrylic resin, and the like, and an epoxy resin is particularly preferable. The epoxy resin refers to an epoxy resin having a peak specific to an epoxy structure at 825 cm ⁻¹ in an infrared absorption spectrum. Furthermore, other resins selected from vinyl acetate resin, acrylic resin, olefin resin, styrene resin, silicon resin and the like may be added to the binder in order to impart flexibility to the adsorption sheet.

  From the viewpoint of adhesiveness, modified vinyl acetate resins and modified acrylic resins are also suitable. The modified vinyl acetate resin means a resin that is not a vinyl acetate resin alone, and includes those in which a copolymer or a functional group portion is substituted. Specific examples include ethylene / vinyl acetate copolymer resins, vinyl acetate / acrylic acid ester copolymer resins, vinyl acetate / vinyl chloride resin copolymer resins, (urethane) -modified ethylene / vinyl acetate copolymer resins, and the like. The modified acrylic resin means one that is not an acrylic resin alone, and includes a copolymer and a functional group partially substituted. Specific examples include methacrylic resins, acrylic / styrene copolymer resins, silica-modified acrylic copolymer resins, and silicone-modified acrylic copolymer resins. In the adsorption sheet (1) of the present invention, by selecting the binder as described above, the adhesion between the adsorbents and the adhesion between the adsorbent and the base sheets (12) and (14) in a wider temperature range. Good adhesion can be obtained. When the ratio of the binder for imparting flexibility exceeds 40% in all binders, the glass transition point is lowered and the adhesive strength is lowered. On the other hand, if it is less than 15%, flexibility cannot be obtained. Therefore, the content of the binder is 3 to 30%, preferably 5 to 25%.

  Incidentally, the glass transition temperature of the organic binder can be measured according to JIS standard “K7121 (1987)”. That is, in the measurement of the glass transition temperature, a heat flux differential scanning calorimeter (heat flux DSC) was used, a 10 mg sample was heated at 10 ° C. per minute, and the obtained DSC curve was converted to JIS standard “K7121 ( 1987) ”, Section 9.3, and“ A method for obtaining a glass transition temperature ”described in Section 9.3.

  The above organic binder can be used by dissolving in an organic solvent. However, when the organic binder is dissolved in an organic solvent, the binder covers the surface of the adsorbent, and the adsorption rate decreases, and the organic solvent volatilizes. This causes the problem of causing environmental pollution. Therefore, in the present invention, it is also used as an emulsion from the viewpoint of securing the adsorption performance of the adsorbent and the adhesiveness with the material of the adsorbent sheet (1). The blending ratio of the binder is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the adsorbent. When the binder is less than 5 parts by weight, the adsorbents are not sufficiently fixed to each other and the base sheets (12) and (14). When the binder is more than 40 parts by weight, the adsorbent can be held in the adsorbent sheet. This is disadvantageous because the amount of adsorbent is reduced, the adsorption capacity is reduced, and the adsorption element is enlarged.

  In addition, in the aqueous dispersion described above, in order to increase the stability and adjust the viscosity, a superabsorbent polymer, an organic thickener such as carrageenan, xanthan gum, gum arabic, or the like may be added. Also, in order to improve thermal conductivity, metal materials with good thermal conductivity, fibrous materials such as carbon fibers, metal powders such as aluminum, copper, silver, or graphite, carbon black, carbon nanotubes, aluminum nitride, nitriding Boron or the like may be added. Furthermore, in order to improve the coating film strength, even if kaolin, acicular calcium silicate, acicular zinc oxide, sepiolite, acicular calcium carbonate, calcium titanate, aluminum borate, acicular basic magnesium sulfate or the like is added. Good. The above-described function-imparting additive may be selected as appropriate depending on the target article, since it may sometimes achieve a plurality of effects such as viscosity adjustment, thermal conductivity improvement, and coating film strength improvement depending on one type. .

  The aqueous dispersion is prepared by adding adsorbent particles and a binder to water to which a particle settling inhibitor has been added. And in this invention, as mentioned later, the handling property at the time of apply | coating to a base material sheet (12) and a base material sheet (14), manufacture of an adsorption sheet (1) and adsorption element (2A)-(2F) Considering efficiency, the solid component concentration is usually set to 30 to 50%, preferably around 40%.

  As a method for producing the adsorption sheet (1), there is a method in which the aqueous dispersion is applied to the base sheet (12) by a method such as dip coating, spray coating, roll coating, screen printing, pad printing, or offset printing. Can be mentioned. Then, the obtained suction sheets (1a) and (1b) are assembled into a plate fin type adsorption element (2A) shown in FIG. 3 or a corrugated fin type adsorption element (2B) shown in FIG. ). Further, the adsorption elements (2A) and (2B) shown in FIG. 3 and FIG. 5 are manufactured by applying the above-mentioned aqueous dispersion to the skeleton structure substrate prepared by the base sheet (12), as will be described later. You can also

  That is, the adsorbing sheets (1a) and (1b) for the adsorbing elements (2A) and (2B) shown in FIG. 3 and FIG. The metal sheet is supported in a laminated state on at least one side. In other words, the adsorbent layer (13) is formed on at least one side of the base sheet (12). The adsorbing sheets (1a) and (1b) (part of the elements) as constituent elements of the adsorbing elements (2A) and (2B) shown in FIG. 3 and FIG. A fibrous holding material may be affixed on the surface of a base material sheet (12), or flocking may be performed so that an aqueous dispersion can be apply | coated.

  On the other hand, the rotor-type adsorbing elements (2C) to (2F) shown in FIGS. 7, 12, 13 and 15 have the above-mentioned aqueous dispersion on the honeycomb skeleton structure substrate made of the base sheet (14). It is manufactured by coating and impregnating. That is, in the adsorption sheets (1c) for the adsorption elements (2C) to (2F) shown in FIGS. 7, 12, 13 and 15, the base sheet (14) is a fibrous sheet, and the adsorbent is a binder. Thus, the fiber sheet is supported on the surface and inside of the fibrous sheet in a state of being intertwined with the fiber.

  After the aqueous dispersion is applied to the base sheet (12) and base sheet (14) (skeleton structure base), the binder is usually dried by heating at 120 to 200 ° C. for 20 to 120 minutes. To support the adsorbent. In addition, although application | coating of said aqueous dispersion liquid may be implemented in multiple times, when using a thermosetting resin binder, in order to prevent peeling | exfoliation and dropping | offset of an adsorbent, it is necessary to heat-harden each time of application | coating. is there.

  As described above, the adsorbent sheet (1) of the present invention is produced by using the above aqueous dispersion, whereby the adsorbents are firmly bonded to each other by the binder, and the base sheet (12), (14) The adsorbent is firmly bonded with a binder. Then, due to the strong adhesive structure of the adsorbent, the adsorbent sheet (1) of the present invention was subjected to a durability test in which the operation of heating to 120 ° C. and immersing in normal temperature water and then cooling to −15 ° C. was repeated 50 times. The subsequent water vapor adsorption amount has an adsorption characteristic of 80% or more with respect to the initial water vapor adsorption amount. That is, it is preferable that the adsorptivity maintenance rate after the above durability test with respect to the initial water vapor adsorption amount is 80% or more.

  The above durability test is performed by the following method. That is, in the durability test, as shown in FIG. 16, first, the adsorption sheet (1) as a sample is loaded in a 120 ° C. constant temperature bath (61), and the adsorption sheet (1) is heated for about 2 minutes. The temperature is raised to 120 ° C. (Step I). Next, the adsorption sheet (1) is taken out from the thermostatic bath (61) and immediately immersed in water at 25 ° C. in the water bath (62) (step II). The immersion time is 60 seconds, and the adsorption sheet (1) is cooled to about 25 ° C. with water. Subsequently, after draining, the adsorption sheet (1) is accommodated for 120 seconds in a freezer (63) having an internal temperature of −15 ° C. and cooled to about −15 ° C. (step III). And a series of operation (process I-III) of the above heating, water cooling, and freezer cooling is repeated 50 times.

  The above heating operation (Process I) is performed to evaluate durability against high temperature regeneration and rapid desorption, and the water cooling operation (Process II) evaluates durability against rapid water vapor adsorption and condensation during water absorption. The cooling operation by the freezer (step III) is performed in order to evaluate the durability against expansion when the adhering water changes to ice and the low temperature durability of the adsorbent adsorbed with water vapor. In other words, in the durability test, the adsorption sheet (1) is exposed to temperature conditions that are far harsher than the normal use temperature range (40 to 90 ° C.) of the adsorption elements (2A) to (2F). This causes dropping and deterioration of the adsorbent. The durability performance of the adsorption sheet (1) can be evaluated by comparing the water vapor adsorption capacity (adsorption / desorption amount) of the adsorbent before and after the durability test as described above.

  The water vapor adsorption capacity of the adsorbent can be confirmed by measuring a steady water vapor adsorption amount during repeated changes in vapor pressure. For the steady water vapor adsorption amount measurement, as shown in FIG. A simple adsorption amount measuring device is used. The adsorption amount measuring apparatus shown in FIG. 17 includes a metal sample container (74) charged in the first constant temperature bath (71) and a water container (75) charged in the second constant temperature bath (72). ), The water trapping container (76) charged in the third constant temperature bath (73), the internally degassed water container (75) and the sample container (74), and an on-off valve (84 ), (87), a pipe (81), a pipe (82) connecting the sample container (74) and the water capturing container (76) and having an on-off valve (85) interposed therebetween, It is mainly composed of a pipe (83) branched from the pipe (81) between the on-off valve (84) and the on-off valve (87) and connected to the vacuum pump (88) via the on-off valve (86).

  In the above adsorption amount measuring apparatus, for example, the sample container (74) is constituted by an aluminum disk-shaped container having a diameter of 130 mm, and the water container (75) and the water capturing container (76) are made of glass having an internal volume of 200 ml. Pipes (81), (82) and deaeration pipes (83) that are constituted by containers and that connect between the containers are constituted by stainless steel pipes having an outer diameter (nominal diameter) of 3/8 inch and a wall thickness of 0.5 mm. Is done.

  In the measurement of the water vapor adsorption amount using the above adsorption amount measuring device, the steam in the water container (75), the sample container (74), and the water trapping container (76) is set according to the temperature setting of each of the thermostats (71) to (73). There is a difference in pressure, the connections between the containers are sequentially switched, moisture is sequentially moved from the water container (75) to the water capturing container (76) by the difference in vapor pressure, and the sample container (74) is loaded with the sample. The difference in the amount of water finally accumulated in the water trapping container (76) is measured when a certain adsorbing sheet (1) is accommodated and when it is not accommodated (blank state). Such a difference in the amount of moisture is the amount of moisture desorbed after being once adsorbed by the adsorbent during the movement from the water container (75) to the water trapping container (76), Equivalent to.

  Specifically, the amount of water movement (blank drainage) from the water container (75) to the water capturing container (76) is measured in advance when the sample container (74) is empty. In the measurement of the blank drainage amount, first, for example, 150 ml of water is accommodated in the water container (75). Further, the opening / closing valves (86) and (87) of the pipe (83) leading to the vacuum pump (88) are opened, and the inside of the water container (75) is deaerated by the vacuum pump (88), and then the opening / closing valve (87). Keep closed. Next, after opening the on-off valves (84) and (85) to make the system vacuum, the on-off valves (84) to (86) are closed and the vacuum pump (88) is stopped. Then, the on-off valve (87) is opened immediately before the start of measurement.

  Then, in the state which maintained the 1st thermostat (71) at 90 degreeC, the 2nd thermostat (72) at 80 degreeC, and the 3rd thermostat (73) at 4 degreeC, respectively, a water container (75) Only the open / close valve (84) of the pipe (81) extending from the pipe to the sample container (74) is opened, for example, for 37 seconds to introduce water vapor from the water container (75) to the sample container (74). Thereafter, the on-off valve (84) is closed, and then only the on-off valve (85) of the pipe (82) from the sample container (74) to the water capturing container (76) is opened for 37 seconds, for example. Water vapor is discharged into the capture container (76), and water is captured in the water capture container (76). After a series of operations of moving water vapor from the water container (75) to the sample container (74) and moving water vapor from the sample container (74) to the water capturing container (76) as described above is repeated 80 times. Finally, the amount of water (blank drainage) accumulated in the water capturing container (76) is measured. Note that the switching time of each on-off valve (84), (85) is, for example, 2 seconds each, and the total time of one cycle is set to 78 seconds.

  Subsequently, in a state where the adsorption sheet (1) as a sample is accommodated in the sample container (74), the amount of water transferred from the water container (75) to the water capturing container (76) (water accompanied by adsorption / desorption by the adsorbent). ). In the measurement of the amount of water that accompanies adsorption / desorption, for example, 150 ml of water is accommodated in the water container (75), and the inside of the water container (75) is evacuated by the vacuum pump (88), as in the case of measuring the blank drainage. After deaeration, the on-off valve (86) is closed. The sample container (74) accommodates, for example, an adsorption sheet (1) carrying 0.5 g of an adsorbent. Then, as in the measurement of the amount of blank waste water, a series of operations consisting of the operation of introducing water vapor into the sample container (74) and the operation of discharging water vapor into the water capturing container (76) are repeated 80 times, and finally Measure the amount of water (drainage) accumulated in the water catching vessel (76).

  In the operation of introducing water vapor from the water container (75) to the sample container (74), the adsorption of water vapor in the adsorbent proceeds, and in the operation of discharging water vapor from the sample container (74) to the water capturing container (76). The desorption of water vapor on the adsorbent proceeds. As a result, the amount of water movement (drainage amount) in the state where the adsorption sheet (1) is accommodated in the sample container (74) is larger than the blank drainage amount by the amount of adsorption / desorption. Therefore, by calculating the difference between the amount of water accumulated in the water capture container (76) when using the sample (drainage amount) and the blank drainage amount, steady water vapor as the adsorption performance of the adsorption sheet (1) The amount of adsorption can be determined. And about the steady water vapor adsorption amount (initial adsorption amount) before performing the above-mentioned durability test, and the steady water vapor adsorption amount (post-test adsorption amount) after performing the durability test, respectively. By measuring the above, it is possible to grasp the degree of deterioration of the adsorption characteristics as the adsorptivity maintenance rate. The initial adsorption amount, the post-test adsorption amount, and the adsorptivity maintenance rate can be calculated based on the following equations.

  In the present invention, the initial amount of water vapor adsorption refers to the amount of water vapor adsorption before the durability test after the production of the adsorption sheet (1). In the measurement of the water vapor adsorption amount, the series of operation times (time for one cycle) as described above are set as conditions for easily evaluating the performance deterioration of the adsorbent, and can be set as appropriate. In other words, when the time for one cycle is set to 78 seconds as described above, the adsorption / desorption amount in one cycle is lower than the theoretical adsorption amount because each operation time is short, but the adsorption / desorption rate decreases. It is easy to grasp the performance degradation accompanied by.

  The adhesive strength of the adsorption sheet (1) after the durability test is usually 0.04 MPa or more, preferably 0.1 MPa or more. When the adhesive strength of the adsorption sheet (1) is 0.04 MPa or more, no difference is observed in the sheet shape before and after the durability test, but when it is less than 0.04 MPa, the adsorbent is detached, peeled off, dropped, etc. Will occur and the shape of the suction sheet cannot be maintained. Therefore, it is practically preferable that the adsorption sheet (1) has an adsorption performance maintenance ratio of 80% or more and an adhesive strength after a durability test of 0.04 MPa or more. Furthermore, the adhesive sheet (1) having an adhesive strength after the durability test of 0.1 MPa or more is more practically preferable.

  The adhesive strength of the suction sheet (1) requires a certain value. Rapid desorption at 120 ° C, rapid adsorption by immersion in water at room temperature, and repeated tests of -15 ° C freezing in water-containing conditions are durable enough for the binder to withstand expansion and contraction. It becomes an acceleration test-like determination means for determining whether or not. When the adhesion durability is low, the particles are peeled off from the base sheet (12) or (14) or the adsorbent particles are peeled apart, and the shape as the adsorbent sheet (1) cannot be maintained. Therefore, the value measured after the durability test is important for the adhesive strength of the adsorption sheet (1). The adhesive strength of the adsorbing sheet (1) is measured according to “Testing method of tensile shear adhesive strength of adhesive-rigid adherend” of JIS standard “K6850”. That is, the adhesive strength is measured by a tensile test performed on the adsorbing sheet (1) after measuring the adsorbed amount after the test, which is performed after the durability test in which the heating, water cooling, and freezer cooling described above are repeated 50 times. The

Adsorbent on the adsorption sheet (1) is usually about 250 g / ^{m 2,} it may be in the range of 5~800g / ^{m 2.} In the measurement of the adhesive strength, a cellophane adhesive tape having a tape strength of 0.4 MPa or more was attached to the adsorption sheet (1) with an adhesion area of 1 cm ² (width 1 cm × length 1 cm), and then applied to the adsorption sheet (1). Then, the cellophane adhesive tape is pulled in the direction of 180 degrees at 10 mm / min to measure the strength at which the coating film breaks, and the average value of the three times is adopted. This test is performed in an environment of 23 ± 2 ° C. In addition, in order to examine the adhesive strength of the cellophane adhesive tape itself, when the tape was directly attached to a copper plate of 50 mm × 40 mm × 0.1 mm (thickness), it was confirmed that it had a strength of 0.4 MPa or more. . It can be judged that this test method is effective for measurements in which the strength measurement value is 0.3 MPa or less.

  As described above, in the adsorbing sheet (1) of the present invention, the glass transition temperature after curing is a predetermined value as a binder for supporting the adsorbent on the base sheet (12), (14) of the adsorbing sheet. By using a binder at or above the temperature, the adhesive strength between the adsorbents and the adhesive strength between the adsorbent and the base sheet (12), (14) is increased over a wide temperature range, and the particle size is, for example, 10 μm or less. The adsorbent having a smaller particle diameter is supported in a larger amount. And the amount of water vapor adsorption after carrying out a specific durability test with respect to the initial amount of water vapor adsorption is large, the heat resistance is excellent, and the adsorption / desorption ability is excellent. Therefore, according to the adsorbing sheet (1) of the present invention, the adsorbing elements (2A) to (2F) having this as a constituent element can exhibit more excellent adsorption / desorption performance in a wider temperature range.

  Next, the adsorption elements (2A) to (2F) of the present invention and the manufacturing method thereof will be described. As described above, the adsorption elements (2A) to (2F) are used in an adsorption heat pump or an adsorption device of a humidity control system.

  Among the adsorbing elements (2A) to (2F) exemplified in the present invention, the plate fin type adsorbing element (2A) as shown in FIG. 3 and the corrugated fin type adsorbing element (2B) as shown in FIG. An element having an adsorption sheet (1) made of a metal base sheet (12) as a constituent element. For example, in an adsorption heat pump, it is housed in a casing having an adsorbate vapor inlet and outlet, and constitutes a vacuum closed system. It is arranged as an adsorption device (adsorber) between the condenser and the condenser. Moreover, the cylindrical rotor type adsorption element as shown in FIGS. 7 and 12 and the columnar rotor type adsorption element as shown in FIGS. 13 and 15 are composed of a fibrous base sheet (14). For example, in a humidity control system, the element is housed in an open casing and is disposed as an adsorbing device (desiccant device) in an air flow path.

  First, the plate fin type adsorption element (2A) shown in FIG. 3 will be described. The adsorbing element (2A) shown in FIG. 3 includes a plurality of adsorbing sheets (1a) as shown in FIG. 1, and each adsorbing sheet (1a) is formed in a plate shape. Specifically, the adsorbing element (2A) includes, for example, an adsorbing sheet (1a) formed in a flat plate shape as shown in the drawing and a single heat medium flow path (3) through which a heat medium (a heat medium and a heat medium) flows. ).

  In the adsorbing element (2A), although the adsorbing sheet (1a) depends on the shape, area and ability of the adsorbing device, usually about 5 to 50 sheets are used, and each adsorbing sheet (1a) It arranges via a fixed minute ventilation space (20) (refer FIG. 4) so that a surface may become parallel and parallel. And the heat-medium flow path (3) is arrange | positioned in the state which penetrated each adsorption sheet (1a). Moreover, the heat medium flow path (3) is arranged in contact with each adsorption sheet (1a).

  The heat medium flow path (3) is constituted by a tube having a circular cross section, and the material of the heat medium flow path is generally aluminum, from the viewpoint of rigidity, thermal conductivity, and production cost, similarly to the base sheet (12). Examples include metals such as copper, brass, iron, chromium, nickel, steel, and alloys thereof. Among these, aluminum or aluminum alloy, copper or copper alloy is preferable. Although depending on the capacity of the adsorption device, the outer diameter of the pipe constituting the heat medium flow path (3) is usually about 6 to 20 mm, and the thickness of the pipe is about 0.2 to 1 mm.

  The heat medium flow path (3) is configured as one continuous pipe line, one end of which is an inlet port (31) for the heat medium and the other end is an outlet port (32) for the heat medium. The form of penetration of the heat medium passage (3) with respect to the adsorption sheet (1a), in other words, the form of routing of the heat medium passage (3) is appropriately determined in consideration of the heat exchange efficiency with the adsorption sheet (1a). Although it can be designed, there are various routing patterns such as, for example, the arrangement of the penetrating parts when viewed from the plate surface side of the suction sheet (1a) in a parallel state vertically and horizontally, and a staggered state in which the upper and lower stages are shifted. The pattern can be adopted. That is, one continuous heat medium flow path (3) is arrange | positioned with respect to the array of adsorption sheet (1a) so that the plate | board surface of these adsorption sheets may be penetrated zigzag several times.

  In the adsorbing element (2A) shown in FIG. 3, a plurality of straight pipes are passed through the array of adsorbing sheets (1a), except for the open ends as the inlet port (31) and outlet port (32) of the heat medium. A straight heat medium flow path (3) is configured by sequentially connecting the ends of the adjacent straight pipes with U-shaped pipes. In addition, the distance between adjacent straight pipe parts is normally set to 10-50 mm from a viewpoint of improving heat conduction efficiency.

  Moreover, in order to perform efficient heat exchange, the heat medium flow path (3) needs to be arrange | positioned in the state which contacted each adsorption sheet (1a). Preferably, the heat medium flow path (3) is in contact with the base sheet (12) of each adsorption sheet (1a). Thereby, the heat and cold of the heat medium flowing through the heat medium flow path (3) can be quickly transmitted to the adsorbent layer (13) of each adsorbent sheet (1a).

  Further, in the adsorption element (2A), as shown in FIG. 4, a constant ventilation space (20) is provided between the adsorption sheets (1a). In order to reduce the size of the element and ensure the necessary air permeability, the distance (2L) between the base sheet (12) of the adsorbing sheet (1a) adjacent to the adsorbing sheet (1a) 13) is set to be larger than twice the thickness (t) and not more than 40 times.

  The reason why the distance (2L) between the base sheet (12) is set in the above range is as follows. That is, when the distance (2L) between the base material sheets (12) is not more than twice the thickness (t) of the adsorbent layer (13), the aeration space (20) cannot be secured and is adsorbed / desorbed. The adsorbate vapor and water vapor which should be able to flow cannot be circulated on the surface of the adsorption sheet (1a). On the other hand, when the distance (2L) between the base material sheets (12) exceeds 40 times the thickness (t) of the adsorbent layer (13), the ventilation space (20) becomes larger than necessary, and the adsorption This is not preferable because the element (2A) is enlarged.

  In other words, the distance (2L) between the base sheets (12) of the adsorbing sheets (1a) adjacent to each other is a half distance (the center between one base sheet (12) and the base sheet (12). The size of the ventilation space (20) is determined so that the thickness (t) of the adsorbent layer (13) is 5 to 95% with respect to the distance (L). Although the optimum value of the thickness (t) of the adsorbent layer (13) with respect to the distance (2L) between the base sheets varies depending on the shape of the adsorption element (2A), the use of the adsorption device, etc., it is applied to the adsorption heat pump. In the case, 10 to 95% is preferable, and 15 to 95% is more preferable. Moreover, when applying to a humidity control system, 10 to 90% is preferable and 10 to 85% is more preferable. In practice, the thickness (t) of the adsorbent layer (13) is 50 to 1000 μm, preferably 100 to 700 μm.

  The adsorbing element (2A) press-fits a predetermined number of straight pipes for constituting the heat medium flow path (3) into the pipe insertion hole (11) with respect to the aggregate of the adsorbing sheets (1a) arranged at regular intervals. Thus, a straight pipe for constituting the heat medium flow path (3) is used for the press-fitting method for fixing each adsorption sheet (1a) to the straight pipe, or for the assembly of the adsorption sheets (1a) arranged at regular intervals. After inserting a predetermined number of pipe insertion holes (11), the diameter of the straight pipe can be increased to manufacture by a pipe expanding method in which each adsorption sheet (1a) is fixed to the straight pipe. In addition, the adjacent edge part of each straight pipe is connected by a U-shaped pipe after fixing each adsorption sheet (1a).

  Moreover, as a manufacturing method of said adsorbent element (2A), as mentioned above, in addition to the method of manufacturing by assembling the adsorbing sheet (1a) produced in advance, the base material sheet (12) and the heat medium flow It is also possible to manufacture by using the pipe for the path (3) and pre-assembling the structure having the element skeleton and then applying the aqueous dispersion described above. That is, in the method for producing the adsorbent element (2A), the base material sheet (12) is used to produce the skeleton structure base of the adsorbent element, and then the adsorbent and the binder are dispersed in water. After applying the aqueous dispersion liquid to the base material sheet (12) of the skeleton structure substrate, the base material sheet (12) is heated and dried to adhere the adsorbent to the surface of the base material sheet (12).

  Examples of the method for applying the aqueous dispersion to the skeletal structure substrate include the above-described application method for producing the base sheet (12), and a method of immersing the entire skeleton structure substrate in the aqueous dispersion. According to the dip coating method, the aqueous dispersion can be applied more easily and more efficiently. After applying the aqueous dispersion, the substrate sheet of the skeletal structure substrate is usually heated and dried at a temperature of 120 to 200 ° C. for 20 to 120 minutes in the same manner as in the production of the adsorption sheet (1) described above. The adsorbent is supported on (12). In addition, the application of the aqueous dispersion to the skeletal structure substrate and heat drying may be performed a plurality of times.

  The adsorbing element (2A) of the present invention as described above is excellent in heat resistance and has the above-described adsorbing sheet (1a) excellent in adsorption / desorption ability as a constituent element. Excellent and further downsizing can be achieved. In particular, according to the method for producing an adsorbing element of the present invention in which a skeletal structure substrate is prepared and an aqueous dispersion containing an adsorbent is applied thereto, the adsorbing element having excellent heat resistance and adsorption / desorption capability ( 2A) can be produced efficiently.

  Next, the corrugated fin-type adsorption element (2B) shown in FIG. 5 will be described. The adsorbing element (2B) shown in FIG. 5 has a plurality of adsorbing sheets (1b) as shown in FIG. 2 described above, and each adsorbing sheet (1b) is bent in a zigzag manner along its length. It is formed. Specifically, the adsorption element (2B) includes an inlet side header (41) to which a heat medium (a hot medium and a cold medium) is supplied, an outlet side header (42) that discharges the heat medium, and each of these headers. And a plurality of straight tubular heat medium passages (4) that extend in parallel and parallel to each other and through which the heat medium flows. Each adsorbing sheet (1b) is formed in a long corrugated plate shape as shown in the figure. It is formed and inserted between the heat medium flow paths.

  In the adsorbing element (2B), although the adsorbing sheet (1b) depends on the capacity of the adsorbing device, usually about 5 to 50 sheets are used. 4) and inserted between the adjacent heat medium flow paths (4), and the respective concave portions (valley portions of the bent portions) of the respective adsorption sheets (1b) serve as ventilation spaces (20). . In addition, each heat medium flow path (4) is arranged in contact with each convex portion (mountain portion in the bent portion) of the adsorbing sheet (1b) adjacent thereto.

  Each heat medium flow path (4) is configured by a flat tube having a cross-section formed into a flat, substantially rectangular shape having an arc-shaped short side, and the constituent material thereof is the same as in the adsorption element (2A). Usually, metals such as aluminum, copper, brass, iron, chromium, nickel, steel, and alloys thereof are used, and aluminum or aluminum alloys, copper or copper alloys are particularly preferable. The external dimensions of the cross section orthogonal to the longitudinal direction of the flat tube constituting the heat medium flow path (4) are such that the long side portion is about 10 to 100 mm and the short side portion is about 0.5 to 10 mm. Is about 0.2 to 1 mm.

  Each heat medium channel (4) has one end connected to the inlet side header (41) and the other end connected to the outlet side header (42) so that the short side portion faces the outside of the adsorption element (2B). The The inlet side header (41) is a box-shaped member that distributes the heat medium supplied from the inlet port (43) to each heat medium flow path (4), and the outlet side header (42) It is a box-shaped member that collects the heat medium flowing in the passage (4) and discharges it from the outlet port (44). The arrangement pitch of the heat medium flow paths (4), that is, the distance between the adjacent heat medium flow paths (4) is usually set to 5 to 100 mm from the viewpoint of increasing the heat conduction efficiency.

  Further, the heat medium flow path (4) needs to be arranged in contact with each adsorption sheet (1b) in order to perform efficient heat exchange as in the adsorption element (2A). Preferably, although not shown, the heat medium flow path (4) is in contact with the base sheet (12) of each adsorption sheet (1b). That is, at each convex part of the adsorption sheet (1b), the outer adsorbent layer (13) is removed and the substrate sheet (12) is exposed, so that the substrate sheet (12) is heated by the heat medium channel ( 4) is in contact with the structure. Thereby, the hot and cold heat of the heat medium flowing through the heat medium flow path (4) can be quickly transmitted to the adsorbent layer (13) of each adsorbing sheet (1b).

  Further, in the adsorbing element (2B), as shown in FIG. 6, a portion surrounded by the concave portion of each adsorbing sheet (1a) and the heat medium flow path (4) constitutes a ventilation space (20). However, in order to reduce the size of the element and ensure the necessary air permeability, the space between the base sheet (12) of the convex portions of the adsorbing sheet (1a) adjacent on the side of the one heat medium flow path (4). The distance (2L) is set to be larger than twice the thickness (t) of the adsorbent layer (13) of the adsorbing sheet (1a) and not more than 40 times.

  The reason for setting the distance (2L) between the base sheets to the above range is the same as in the above-described adsorption element (2A). In other words, a distance that is 1/2 of the distance (2L) between the adjacent base material sheets (12) of the suction sheet (1a) (the convex portion adjacent to the base material sheet (12) of one convex portion). The size of the ventilation space (20) is determined so that the thickness (t) of the adsorbent layer (13) with respect to the distance (L) to the center between the base sheet (12) is 5 to 95%. The When applied to the adsorption heat pump, the thickness (t) of the adsorbent layer (13) with respect to the distance (2L) between the substrate sheets is preferably 10 to 95%, and more preferably 15 to 95%. Moreover, when applying to a humidity control system, 10 to 90% is preferable and 10 to 85% is more preferable. In practice, the thickness (t) of the adsorbent layer (13) is 50 to 1000 μm, preferably 100 to 700 μm.

  The adsorbing element (2B) is a flat tube for constituting the heat medium flow path (4), and the adsorbing sheets (1b) are arranged with their respective longitudinal directions aligned so as to sandwich the adsorbing sheet (1b) from both sides. By pressing the flat tubes in a direction approaching each other, the suction sheet (1b) is elastically deformed in a direction that slightly extends the zigzag bend, and then the inner surfaces of the inlet side header (41) and the outlet side header (42) Each flat tube is fixed to the inlet side header (41) and the outlet side header (42) by inserting the end portion of each flat tube into a slit provided in advance in the suction sheet (1b) between the flat tubes. It can manufacture by the method of fixing.

  Moreover, as a manufacturing method of said adsorbent element (2B), the base sheet (12) and the pipe | tube for heat-medium flow path (4) structure are used similarly to the manufacturing method of the above-mentioned adsorbent element, It can also be manufactured by pre-assembling a structure having an element skeleton and then applying the aqueous dispersion described above. That is, in the manufacturing method of each adsorbent element (2B) described above, the base material sheet (12) is used to prepare the skeleton structure base of the adsorbent element, and then the adsorbent and the binder are dispersed in water. After the above aqueous dispersion is applied to the base material sheet (12) of the skeleton structure substrate, the base material sheet (12) is dried by heating, whereby an adsorbent is applied to the surface of the base material sheet (12). Adhere.

  As a method for applying the aqueous dispersion to the skeletal structure substrate, as in the case of the adsorbing element (2A) described above, in addition to the same method as the application method for producing the adsorbing sheet (1b), A method of immersing the entire skeletal structure substrate is exemplified. After applying the aqueous dispersion, as in the case of the adsorption element (2A) described above, the substrate is heated and dried at a temperature of 120 to 200 ° C. for 20 to 120 minutes to form a base material sheet (12) of the skeleton structure substrate. The adsorbent is supported. Moreover, you may implement multiple times of application | coating and heat drying of said aqueous dispersion.

  The adsorbing element (2B) of the present invention as described above is excellent in heat resistance and adsorption / desorption ability, and can be further reduced in size, like the adsorbing element (2A) described above. And according to the manufacturing method of the adsorption element of the present invention in which the above-mentioned aqueous dispersion is applied to the skeleton structure substrate, the adsorption element (2B) having excellent heat resistance and adsorption / desorption ability can be efficiently produced. I can do it.

  Next, the cylindrical rotor type adsorption element (2C) shown in FIG. 7 will be described. The adsorbing element (2C) shown in FIG. 7 is a cylindrical element that adsorbs and desorbs adsorbate vapor and water vapor by being configured to allow ventilation from the outer peripheral surface to the inner peripheral surface or from the inner peripheral surface to the outer peripheral surface. Such an adsorbing element (2C) comprises a large number of the adsorbing sheets (1c) described above, wherein the base sheet (14) is made of a fibrous sheet, and these adsorbing sheets (1c) constitute a cylindrical honeycomb structure. The And the adsorption | suction sheet | seat (1c) is formed in a substantially corrugated plate shape, and is arrange | positioned in the lamination | stacking state along the circumferential direction, The cell (50) for ventilation | gas_flowing which has a substantially hexagonal opening shape is formed in a surrounding surface. Many are provided.

  The adsorbing element (2C) has a substantially corrugated adsorbing sheet (1c) formed in a strip shape and bent in a zigzag manner with respect to its longitudinal direction. The adsorbing element (2C) has its longitudinal direction as an axis of the adsorbing element (honeycomb structure). It has a structure in which a large number of layers are stacked along the circumferential direction so as to be aligned in parallel. In the cell (50) formed on the peripheral surface, adjacent convex portions of the substantially corrugated suction sheet (1c) are joined to each other with a predetermined width (width of a linear joint portion (51) described later). Thus, the opening shape is formed in a substantially hexagonal shape. In the adsorbing element (2C), the arrangement direction (X) of the cells (50) formed by the adjacent substantially corrugated adsorbing sheets (1c) is the direction along the longitudinal direction of the sheet (1c), that is, The direction along the axis of the adsorption element (honeycomb structure).

  The adsorbing element (2C) is configured by adsorbing an adsorbent on a honeycomb skeleton structure substrate made of the above-described fibrous base sheet (14) (adsorption sheet material). The honeycomb skeleton structure substrate is formed by laminating a large number of substrate sheets (53) (molded body of the substrate sheet (14)) formed in a rectangular flat plate shape (for example, a belt shape), and each substrate sheet (53). ) On the front and back sides of each of the base materials adjacent to each other in a large number of linear joints (51) (see FIG. 8) set at a constant pitch and shifted by a 1/2 pitch on the front and back sides. When a laminated body (5b) (see FIG. 9) formed by joining sheets (53) to each other is used and expanded, the two parallel laminated surfaces on the side where the cells (50) open are curved. It is comprised by developing a laminated body (5b).

  The manufacturing method of the skeleton structure substrate of the honeycomb and the adsorbing element (2C) will be described with reference to FIGS. 8 to 11. In order to manufacture the skeleton structure substrate of the honeycomb, first, as shown in FIG. A plate-like base sheet (14) large enough to produce a structural substrate is prepared and laminated, and for example, the adjacent base sheets (14) vertically are joined at predetermined sites. The base sheet (14) finally corresponds to the base sheet (53) of the substantially corrugated adsorbent sheet (1c) described above, and as such a flat base sheet (14), The above-mentioned fibrous sheet is used.

  The flat base sheet (14) shown in FIG. 8 is laminated, for example, about 100 to 1000 sheets depending on the size of the skeleton structure base and the size of the cells (50). And each base material sheet (14) is laminated | stacked with respect to each adjacent base material sheet (14) by joining methods according to materials, such as heat welding, ultrasonic welding, or adhesion | attachment using an adhesive agent, when laminating | stacking. Sequentially joined at a predetermined site. In the base material sheet (14), as a joint part with each adjacent base material sheet (14), the front and back surfaces of each base material sheet (14) are parallel to one side of the base material sheet at a constant pitch and 1 on the front and back surfaces. A large number of linear joints (51) are set in a state shifted by / 2 pitches. When the interval between the linear joint portions (51) on one surface of the base sheet (14) is about 2 to 15 mm, and the linear joint portion (51) is set at the above-described interval, one cell ( 50) can be formed in a cell having a maximum diagonal of about 2 to 20 mm.

  After laminating the base sheet (14), as shown in FIG. 9, the base sheet (in the form of a strip having a length (M) and a width (N) of each end face on the laminating direction side is formed. 14) is cut to produce a rectangular parallelepiped laminate (5b). That is, the laminate (5b) is formed by laminating a large number of strip-shaped base sheets (53) of a predetermined size formed from a flat base sheet (14), and each adjacent base sheet (53) is the above-mentioned Are joined to each other at the straight joint (51). The length (M) of the laminate (5b) corresponds to the axial length of the skeleton structure substrate of the honeycomb, and the width (N) corresponds to the difference between the outer diameter and the inner diameter (cylinder thickness) of the skeleton structure substrate. Although it differs depending on the apparatus to which the adsorption element (2C) is applied, the size of the skeleton structure substrate, that is, the size of the laminate (5b) is usually about 60 to 400 mm in length (M) and width (N ) Is about 10 to 60 mm.

  When the laminate (5b) obtained as described above is expanded in the laminating direction (vertical direction in FIG. 9), as shown in FIG. While deforming into a corrugated plate shape, a large number of cells (50) are opened in two parallel laminated surfaces along the length (M) of the laminated body (5b). In addition, the arrow of the code | symbol (Y) in FIG. 9 has shown the communication direction of the cell (50) formed when a laminated body (5b) is expanded, and FIG. The cell (50) formed is shown, and the arrow (X) in FIG. 10 indicates the cell (50) formed by the extending direction of each base sheet (53) and each adjacent base sheet (53). Indicates the direction of arrangement.

  Therefore, in the present invention, as shown in FIG. 11, the opening of the cell (50) that appears when the laminate (5b) is used and expanded, is formed on the peripheral surface of the cylindrical skeleton structure substrate. By deploying the laminate (5b) in a state where it is located, that is, when the laminate (5b) is expanded, the two parallel laminated surfaces on the side where the cell (50) opens are curved. A skeleton structure substrate of a cylindrical honeycomb is formed. In other words, in developing the laminate (5b), the laminate (5b) is arranged such that one long side of the belt-shaped base sheet (53) is located on the inner periphery and the other long side is located on the outer periphery. ) Is bent into a ring. And base material sheet | seat (53) equivalent to the both end surfaces of the lamination direction of a laminated body (5b) is joined.

  When a honeycomb skeleton structure substrate is manufactured, the laminate (5b) is formed by directly laminating a number of strip-like sheets (53) formed in advance in length (M) and width (N). At this time, they may be produced by joining them at the linear joining part (51) set as described above.

  The skeleton structure substrate obtained as described above has a structure in which only the substantially corrugated adsorbing sheets (1c) are laminated along the circumferential direction, and the opening shape of each cell (50) is substantially hexagonal. Is formed. The adsorbing element (2C) of the present invention is manufactured by applying the above-mentioned aqueous dispersion to the above-described honeycomb skeleton structure substrate and then performing a drying treatment with hot air or the like. That is, in the manufacturing method of the adsorbing element (2C), a fibrous base material sheet (14) is used to produce a skeleton structure substrate of the adsorbing element, and then the adsorbent and the binder are dispersed in water. After coating and impregnating the base material sheet (14) of the skeletal structure substrate with the aqueous dispersion formed as described above, the base material sheet (14) is heated and dried, so that the surface and the inside of the base material sheet (14) are formed. Adsorb the material.

  As in the case of each of the adsorption elements (2A) and (2B) described above, in the heat drying treatment of the base sheet (14), the heat drying is usually performed at a temperature of 120 to 200 ° C. for 20 to 120 minutes. Do. In addition, the application of the aqueous dispersion and the heat drying may be performed a plurality of times. The adsorbing element (2C) of the present invention produced as described above has a structure in which an adsorbent is supported by a binder on each base sheet (53) of a honeycomb skeleton structure base as a base. That is, in the adsorbing element (2C), the adsorbent is supported by the binder in a state where the adsorbent is intertwined with the fiber on the surface and inside of the fibrous sheet which is the base sheet (14) constituting the skeleton structure base.

  The adsorbing element (2C) of the present invention as described above is similar to the adsorbing elements (2A) and (2B) described above, with the adsorbing sheet (1c) having excellent heat resistance and adsorbing / desorbing ability. ) As a component, it has excellent heat resistance and adsorption / desorption ability, and can be further downsized. According to the method for manufacturing an adsorbing element of the present invention in which an aqueous dispersion containing an adsorbent is applied to a honeycomb skeleton structure substrate, the adsorbing element (2C) having excellent heat resistance and adsorption / desorption ability can be efficiently used. Can be manufactured.

  Moreover, according to the adsorption element (2C) of the present invention, it has a laminated structure of only the substantially corrugated adsorbing sheet (1c), and a laminated body (5b) of a large number of rectangular flat plate-like substrate sheets (53). ) (See FIG. 9), a honeycomb skeleton structure substrate can be easily produced, so that the manufacturing cost can be further reduced. And since the opening shape of each cell (50) is formed in the substantially hexagonal shape by said laminated structure, ventilation efficiency can be improved and adsorption | suction and desorption performance can be improved more.

  Next, the cylindrical rotor-type adsorption element (2D) shown in FIG. 12 will be described. The adsorbing element (2D) shown in FIG. 12 is configured to be able to ventilate from the outer peripheral surface to the inner peripheral surface or from the inner peripheral surface to the outer peripheral surface, similarly to the adsorbing element (2C) shown in FIG. And a cylindrical element that adsorbs and desorbs water vapor, and the base sheet (14) includes a large number of the above-described adsorbing sheets (1c) made of a fibrous sheet, and the adsorbing sheets (1c) are substantially cylindrical. Constructed into a honeycomb structure. Then, the suction sheet (1c) formed in a substantially corrugated plate shape and the suction sheet (1c) formed in a substantially flat plate shape are alternately arranged in a stacked state along the axial direction, thereby forming a substantially triangular opening shape. A large number of air-permeable cells (50) having a peripheral surface are provided.

  The adsorbing element (2D) is a honeycomb sheet in which a row of cells (50) is formed by overlapping a corrugated adsorbing sheet (1c) on a flat adsorbing sheet (1c). It has a structure in which a large number of layers are stacked along the axial direction. The cell (50) formed on the peripheral surface has a substantially triangular opening shape by bonding each convex portion of the corrugated suction sheet (1c) to the adjacent flat suction sheet (1c). It is formed. In the adsorbing element (2D), the arrangement direction (X) of the cells (50) formed by the flat adsorbing sheet (1c) and the corrugated adsorbing sheet (1c) is the longitudinal direction of the adsorbing sheet (1c). The direction along the direction, that is, the direction along the circumference of the adsorption element (honeycomb structure).

  The adsorbing element (2D) is configured by supporting an adsorbing material on a honeycomb skeleton structure base made of the above-described fibrous base sheet (14). The manufacturing method of the adsorption element (2D) will be described. The honeycomb skeleton structure substrate is formed by laminating a large number of the above honeycomb sheets in which the corrugated plate sheet (14) is stacked on the flat plate sheet (14). It is manufactured by the laminated body which consists of. Specifically, a large number of honeycomb sheets are stacked and formed so that both end surfaces on the stacking direction side are substantially fan-shaped to produce a columnar stacked body, and then a plurality of the columnar stacked bodies are used. Then, these laminated bodies (eight laminated bodies in FIG. 12) are connected in a ring shape so that the end face thereof is located on the end face of the skeletal structure substrate.

  The laminated body in which the flat base sheet (14) and the corrugated base sheet (14) are laminated as described above is alternately laminated with two types of base sheets (14) having different lengths. In addition, it can be produced by a so-called honeycomb forming machine that joins the longer base sheet (14) at a constant interval while drawing it. At that time, the adjacent flat plate-like substrate sheet (14) and corrugated plate-like substrate sheet (14) are subjected to an opening width of the cell (50) by heat welding, ultrasonic welding, or adhesion using an adhesive. In one cell (50) that is joined and formed at a constant pitch according to the above, for example, the opening width (triangle base length) is about 2 to 15 mm, and the height (triangle height) is 0.5. It is set to about 10 mm. And about 100-1000 honeycomb sheets which consist of a flat base material sheet (14) and a corrugated base material sheet (14) are laminated | stacked, for example.

  The above laminate is molded so that both end faces are substantially trapezoidal or fan-shaped. After the laminated body is manufactured, a plurality of laminated bodies, for example, 8 to 12 are used, and these are connected in a ring shape by bonding with an adhesive or the like, thereby manufacturing a substantially cylindrical honeycomb skeleton structure substrate. In addition, in order to reduce the gap between the casing on the outer peripheral side of the element and reduce the through-path such as air when incorporated in the adsorption device, more of the above laminate is used and the skeleton structure base is more cylindrical. It is preferable to approach. In addition, the manufacturing method of said skeleton structure base | substrate of a honeycomb is well-known, For example, it is disclosed by Unexamined-Japanese-Patent No. 2004-209420.

  After the honeycomb skeleton structure substrate is manufactured, the above-described aqueous dispersion is applied to the skeleton structure substrate, followed by drying treatment with hot air or the like. That is, in the manufacturing method of the adsorbing element (2D), a skeleton structure base of the adsorbing element is prepared using a fibrous base sheet (14), and then the adsorbent and the binder are dispersed in water. After coating and impregnating the base material sheet (14) of the skeletal structure substrate with the aqueous dispersion formed as described above, the base material sheet (14) is heated and dried, so that the surface and the inside of the base material sheet (14) are formed. Adsorb the material.

  As in the case of each of the adsorption elements (2A) to (2C) described above, in the heat drying treatment of the base sheet (14), heat drying is usually performed at a temperature of 120 to 200 ° C. for 20 to 120 minutes. In addition, the application of the aqueous dispersion and the heat drying may be performed a plurality of times. The adsorbing element (2D) of the present invention produced as described above has a structure in which an adsorbent is supported by a binder on each base sheet (14) of a honeycomb skeleton structure base as a base. That is, in the adsorption element (2D), the adsorbent is supported by the binder in a state where the adsorbent is intertwined with the fiber on the surface and inside of the fibrous sheet which is the base sheet (14) constituting the skeleton structure base.

  The adsorbing element (2D) of the present invention as described above is similar to the adsorbing elements (2A) to (2C) described above. The adsorbing sheet (1c) has excellent heat resistance and excellent adsorbing / desorbing ability. ) As a constituent element, it has excellent heat resistance and adsorption / desorption ability, and can be further reduced in size. According to the method for manufacturing an adsorbing element of the present invention in which an aqueous dispersion containing an adsorbent is applied to a honeycomb skeleton structure substrate, the adsorbing element (2D) having excellent heat resistance and adsorption / desorption ability is efficiently used. Can be manufactured

  Next, the columnar rotor-type adsorption element (2E) shown in FIG. 13 will be described. The adsorbing element (2E) shown in FIG. 13 is a columnar element that adsorbs and desorbs solute vapor and water vapor by being configured to allow ventilation from one end face to the other end face. Such an adsorbing element (2E) includes a large number of the above-mentioned adsorbing sheets (1c) in which the base sheet (14) is made of a fibrous sheet, and the adsorbing sheets (1c) form a column (for example, a short-axis columnar) ) Honeycomb structure. Then, the suction sheet (1c) is formed in a substantially corrugated plate shape and arranged in a laminated state along the circumferential direction, whereby a large number of ventilation cells (50) having a substantially hexagonal opening shape are formed on the end face. Provided.

  As shown in FIG. 13, the adsorbing element (2E) is formed in, for example, a short-axis cylindrical shape, and a rotation shaft is mounted at the center. The adsorbing element (2E) has a substantially corrugated adsorbing sheet (1c) formed in a strip shape and bent in a zigzag manner with respect to its longitudinal direction, and the radius of the adsorbing element (honeycomb structure) in the longitudinal direction. A structure in which a large number of layers are stacked along the circumferential direction is provided. In the cell (50) formed on the end face, adjacent convex portions of the substantially corrugated suction sheet (1c) are joined to each other with a predetermined width (width of the linear joint portion (51)). The opening shape is formed in a substantially hexagonal shape. In the adsorption element (2E), the arrangement direction (X) of the cells (50) formed by the adjacent substantially corrugated adsorption sheet (1c) is a direction along the longitudinal direction of the adsorption sheet (1c), That is, the direction is along the radius of the adsorption element (honeycomb structure).

  The adsorbing element (2E) is configured by adsorbing an adsorbent on a honeycomb skeleton structure substrate made of the above-described fibrous base sheet (14) (adsorption sheet material). The honeycomb skeleton structure substrate is formed by laminating the laminated body (5b) shown in FIG. 9, that is, a large number of rectangular flat plate-like base sheets (53) formed in a rectangular flat plate shape (for example, a belt shape). The front and back surfaces of each base sheet (53) are adjacent to each other at a large number of linear joints (51) set at a constant pitch and a half pitch shift on the front and back sides in parallel with one side of the base sheet. When the laminate (5b) formed by joining the base sheet (53) to each other is used and expanded, the other two parallel laminate surfaces adjacent to the laminate surface on the side where the cells (50) are opened are formed. It is comprised by developing a laminated body (5b) in the state made to curve.

  The manufacturing method of the skeleton structure substrate of the honeycomb and the adsorbing element (2E) will be described based on FIGS. 8 to 10 and FIG. 14. First, the skeleton structure substrate of the honeycomb is manufactured. A laminated body (5b) is produced through the same steps as in the cylindrical adsorption element (2C). That is, the skeleton structure substrate uses a flat substrate sheet (14) shown in FIG. 8 made of the same material as described above as the material of the substrate sheet (53) deformed into a substantially corrugated plate. After producing a laminated body (5b) as shown in FIG. 9 by the same method as described above, the laminated body (5b) is developed and manufactured.

  In the present invention, when manufacturing a skeleton structure substrate of a honeycomb having a short-axis columnar shape, as shown in FIG. 14, the above-described laminate (5b) is used, and a cell (50) that is expressed when this is expanded. Other parallel laminated surfaces adjacent to the laminated surface on the side where the cells (50) are opened when the laminated body (5b) is expanded (see FIG. 9 is constructed by developing the laminate (5b) in a state in which the laminate (5b) on the width (N) side of the laminate (5b) in Fig. 9 is curved. In other words, when unfolding the laminate (5b), the laminate (5b) is such that one short side of the belt-like base sheet (53) is located on the inner periphery and the other short side is located on the outer periphery. ) Is bent into a ring. And base material sheet | seat (53) equivalent to the both end surfaces of the lamination direction of a laminated body (5b) is joined.

  In the case of manufacturing the above-described honeycomb skeleton structure substrate, as in the case of the above-described adsorption element (2C), the laminate (5b) is a strip-shaped base sheet (53) formed in advance with a predetermined size. May be produced by directly laminating them at the above-mentioned linear joint (51) when they are laminated.

  The skeleton structure substrate obtained as described above has a structure in which only the substantially corrugated adsorbing sheets (1c) are laminated along the circumferential direction, and the opening shape of each cell (50) is substantially hexagonal. Is formed. Then, the adsorbing element (2E) of the present invention, like the adsorbing element (2C) described above, is coated with the above-mentioned aqueous dispersion on the above-described honeycomb skeleton structure substrate, and then subjected to a drying treatment with hot air or the like. Manufactured by. That is, in the manufacturing method of the adsorbing element (2E), a skeleton structure substrate of the adsorbing element is prepared using the fibrous base sheet (14), and then the adsorbent and the binder are dispersed in water. The base material sheet (14) of the skeletal structure base is coated and impregnated with the aqueous dispersion liquid, and then the base material sheet (14) is heated and dried to attach the adsorbent to the surface and inside of the base material sheet (14). Let

  In addition, as in the case of each of the adsorption elements (2A) to (2D) described above, in the heat drying treatment of the base sheet (14), the heat drying is usually performed at a temperature of 120 to 200 ° C. for 20 to 120 minutes. Do. In addition, the application of the aqueous dispersion and the heat drying may be performed a plurality of times. The adsorbing element (2E) of the present invention produced as described above has a structure in which an adsorbent is supported by a binder on each base sheet (53) of a honeycomb skeleton structure base as a base. That is, in the adsorbing element (2C), the adsorbent is supported by the binder in a state where the adsorbent is intertwined with the fiber on the surface and inside of the base sheet (14) made of the fibrous sheet constituting the skeleton structure substrate.

  The adsorbing element (2E) of the present invention as described above is similar to the adsorbing elements (2A) to (2D) described above, and has the above-described adsorbing sheet (1c) having excellent heat resistance and excellent adsorbing / desorbing ability. ) As a component, it has excellent heat resistance and adsorption / desorption ability, and can be further downsized. According to the method for manufacturing an adsorbing element of the present invention in which an aqueous dispersion containing an adsorbent is applied to a honeycomb skeleton structure substrate, the adsorbing element (2E) having excellent heat resistance and adsorbing / desorbing ability can be efficiently used. Can be manufactured in

  In addition, according to the adsorption element (2E) of the present invention, the laminate (5b) has a laminated structure of only the substantially corrugated adsorption sheet (1c), and a large number of rectangular flat plate-like substrate sheets (53). ) (See FIG. 9), a honeycomb skeleton structure substrate can be easily manufactured, and thus the manufacturing cost can be further reduced. And since the opening shape of each cell (50) is formed in the substantially hexagonal shape by said laminated structure, ventilation efficiency can be improved and adsorption | suction and desorption performance can be improved more.

  Next, the cylindrical rotor-type adsorption element (2F) shown in FIG. 15 will be described. The adsorbing element (2F) shown in FIG. 15 has a cylindrical shape that adsorbs and desorbs solute vapor and water vapor by being configured to be able to vent from one end face to the other end face, similarly to the adsorbing element (2E) shown in FIG. A honeycomb structure in which the base sheet (14) is provided with a large number of the above-mentioned adsorbing sheets (1c) made of a fibrous sheet, and the adsorbing sheets (1c) have a cylindrical shape (for example, a short axis cylindrical shape). Constructed in the body. Then, the suction sheet (1c) formed in a substantially corrugated plate shape and the suction sheet (1c) formed in a substantially flat plate shape are alternately arranged in a stacked state along the diametrical direction, thereby forming a substantially triangular opening shape. A large number of air-permeable cells (50) having an end face are provided on the end face.

  The adsorbing element (2F) is a honeycomb sheet in which a row of cells (50) is formed by overlapping a corrugated adsorbing sheet (1c) on a flat adsorbing sheet (1c). It has a structure in which a large number of layers are stacked around the central axis. That is, it has a structure in which honeycomb sheets are laminated in the radial direction of the adsorption element (honeycomb structure). The cell (50) formed on the end face is formed into a substantially triangular shape by bonding each convex portion of the corrugated suction sheet (1c) to the adjacent flat suction sheet (1c). Is done. In the adsorbing element (2F), the arrangement direction (X) of the cells (50) formed by the flat adsorbing sheet (1c) and the corrugated adsorbing sheet (1c) is the longitudinal direction of the adsorbing sheet (1c). The direction along the direction, that is, the direction along the circumference of the adsorption element (honeycomb structure).

  The adsorbing element (2F) is configured by adsorbing an adsorbent on a honeycomb skeleton structure base made of a fibrous base sheet (14). The manufacturing method of the adsorbing element (2F) will be described. The honeycomb skeleton structure substrate is formed by a long honeycomb sheet in which a corrugated base sheet (14) is stacked on a flat base sheet (14). It is manufactured by spirally winding around a material (center axis) or sequentially laminating around a core material (center axis). Specifically, one continuous honeycomb sheet having a width corresponding to the thickness (length in the axial direction) of the adsorption element (2F) is continuously wound around the core material a number of times. Alternatively, a large number of honeycomb sheets having the same width as described above are sequentially wound around the core material every round.

  Note that the honeycomb sheet can be manufactured by a honeycomb molding machine in the same manner as in the case of the adsorption element (2D) shown in FIG. Thickness) is set to about 2 to 15 mm, and the height (the height of the triangle) is set to about 0.5 to 10 mm. And the lamination | stacking number of honeycomb sheets in a frame | skeleton structure base | substrate is about 100-1000 sheets, for example. Moreover, the manufacturing method of said skeleton structure base | substrate of a honeycomb is well-known, For example, it is disclosed by Unexamined-Japanese-Patent No. 2004-209420.

  After the honeycomb skeleton structure substrate is manufactured, as in the case of the adsorbing element (2D) shown in FIG. 12, the aqueous dispersion is applied to the skeleton structure substrate, followed by drying treatment with hot air or the like. That is, in the manufacturing method of the adsorbing element (2F) described above, a fibrous base sheet (14) is used to prepare the skeleton structure base of the adsorbing element, and then the adsorbent and the binder are dispersed in water. After coating and impregnating the base material sheet (14) of the skeletal structure substrate with the aqueous dispersion formed as described above, the base material sheet (14) is heated and dried, so that the surface and the inside of the base material sheet (14) are formed. Adsorb the material.

  As in the case of each of the adsorption elements (2A) to (2E) described above, in the heat drying treatment of the base sheet (14), heat drying is usually performed at a temperature of 120 to 200 ° C. for 20 to 120 minutes. In addition, the application of the aqueous dispersion and the heat drying may be performed a plurality of times. The adsorbing element (2F) of the present invention produced as described above has a structure in which an adsorbent is supported by a binder on each base sheet (14) of a honeycomb skeleton-structured base body. That is, in the adsorption element (2F), the adsorbent is supported by the binder in a state where the adsorbent is intertwined with the fiber on the surface and inside of the base sheet (14) made of the fibrous sheet constituting the skeleton structure substrate.

  The adsorbing element (2F) of the present invention as described above is the same as the adsorbing elements (2A) to (2E) described above. ) As a constituent element, it has excellent heat resistance and adsorption / desorption ability, and can be further reduced in size. According to the method for manufacturing an adsorbing element of the present invention in which an aqueous dispersion containing an adsorbent is applied to a honeycomb skeleton structure substrate, the adsorbing element (2F) having excellent heat resistance and adsorption / desorption capability can be efficiently used. Can be manufactured.

  Further, as described above, the adsorption elements (2A) to (2F) are excellent in heat resistance performance, adsorption / desorption ability, and can exhibit even better adsorption / desorption performance in a wider temperature range. The adsorption heat pump of the present invention having (2F) can be further reduced in size and is suitable for a cogeneration system or the like that requires energy saving. And the humidity control air conditioner of this invention provided with adsorption | suction element (2A)-(2F) is suitable for the various systems which adjust humidity using excess low-quality heat energy.

Example 1:
An aqueous dispersion containing an adsorbent was prepared and applied to the base sheet (12) to produce an adsorbent sheet (1a). And while performing a durability test, the water vapor | steam adsorption amount (F) and (U) before and behind a durability test was measured, and the adsorptivity maintenance factor (X) of the adsorption sheet (1a) was confirmed. Furthermore, the above-mentioned adhesive strength test (“CT-18S” (trade name) manufactured by Nichiban Co., Ltd. was used as the cellophane adhesive tape) was performed, and the adhesive strength of the coating film was measured.

  In the preparation of the aqueous dispersion, first, 10 g of silica gel (manufactured by GL Sciences; trade name “Unibeads 1S”) having an average particle diameter of 190 μm was added to 12 g of water and stirred. Next, as a binder, a mixed solution of 1.7 g of epoxy emulsion and 0.09 g of a curing agent (manufactured by Japan Epoxy Resin Co., Ltd .; trade name “Epicure IBM 12”) and 3.8 g of water was added and stirred. The epoxy emulsion had a non-volatile content (made by Japan Epoxy Resin; trade name “Epiletz 3540WY55”) of 53.5 wt%. The solid component of the aqueous dispersion was 40 wt%. Further, the binder was individually heated and dried at 120 ° C. for 30 minutes, and the glass transition temperature Tg was measured by DSC. The Tg was 48 ° C. Furthermore, when the peak wavelength was measured by Fourier transform infrared spectroscopy, peaks derived from the following structure were observed.

  The adsorbing sheet (1a) is coated with the above aqueous dispersion on a base sheet (12) made of a copper plate of 50 mm × 40 mm × 0.1 mm (thickness), and then heated and dried at a temperature of 120 ° C. for 30 minutes. Produced by doing. The silica adhering to the adsorption sheet (1a) was 0.5 g, and the epoxy resin was 0.05 g. And when the water vapor adsorption amount (adsorption weight of water with respect to 1 gram of adsorbent) (F) of the adsorption sheet (1a) was measured, the water vapor adsorption amount (F) was 0.063 g / g.

  Next, as a durability test, the adsorption sheet (1a) was heated in a thermostatic bath (61) at 120 ° C. for 2 minutes, immersed in room temperature water in a water bath (62) for 1 minute, and then stored in a freezer (63) at −15 ° C. The operation of cooling for 2 minutes was repeated 50 times. And when the adsorption amount after a test (adsorption weight of water with respect to 1 gram of adsorbents after a durability test) (U) of the adsorption sheet (1a) was measured again, the adsorption amount after the test (U) was 0.062 g / g, and the adsorptive maintenance rate (X) was as good as 99%. Moreover, softening was not recognized by the surface of the adsorption sheet (1a) in the 120 degreeC heating operation in a durability test. About the adsorption sheet (1a) after a durability test, the adhesive strength test was done and the adhesive strength of the coating film was measured. As a result, it broke at 0.052 MPa.

Example 2:
According to the same procedure as in Example 1, an aqueous dispersion was applied to the base sheet (12) to produce an adsorption sheet (1a), and the durability test was performed, and the water vapor adsorption amount before and after the durability test (F) and (U) were measured, and the adsorptive maintenance rate (X) of the adsorbing sheet (1a) was confirmed. Further, an adhesive strength test was performed to measure the adhesive strength of the coating film.

  The aqueous dispersion was added to 0.015 g of a superabsorbent polymer with respect to 15.5 g of water and sufficiently stirred, and then synthesized according to Example 1 described in JP-A No. 2004-136269 and refined by dry pulverization. 10 g of FAPO-5, which is an aluminum phosphate zeolite having an average particle diameter of 4 μm, was added and stirred, and 2.0 g of epoxy emulsion was further added as a binder and stirred. The epoxy emulsion used was an epoxy equivalent of about 8000 as a base resin, a bisphenol A type and a molecular weight of about 50000 (manufactured by Japan Epoxy Resin; trade name “Epicoat 1256”). A surfactant and water were added to this resin and mixed by stirring to obtain an epoxy emulsion having a solid content of 50 wt%. This epoxy emulsion is white opaque and has a BM viscometer No. In the viscosity measurement at 1 rotor, 25 ° C. and 20 rpm, the viscosity was 400 mPa · s. The solid component of the aqueous dispersion was 40 wt%. Further, the binder was individually heated and dried at 120 ° C. for 30 minutes, and the glass transition temperature Tg was measured by DSC. The Tg was 52 ° C.

  The adsorption sheet (1a) was produced by applying the above aqueous dispersion to the same base sheet (12) as in Example 1 and then drying by heating under the same conditions as in Example 1. FAPO-5 adhering to the adsorption sheet (1a) was 0.5 g, and the epoxy resin was 0.05 g. And when the initial water vapor adsorption amount (F) of the adsorption sheet (1a) was measured, the water vapor adsorption amount (F) was 0.111 g / g.

  Subsequently, after performing the durability test similar to Example 1, when the adsorption amount (U) after the test of the adsorption sheet (1a) was measured again, the adsorption amount (U) after the test was 0.101 g / g. Yes, the adsorptive maintenance rate (X) was as good as 91%. Moreover, softening was not recognized by the surface of the adsorption sheet (1a) in the 120 degreeC heating operation in a durability test. About the adsorption sheet (1a) after a durability test, the adhesive strength test was done and the adhesive strength of the coating film was measured. As a result, it broke at 0.162 MPa.

Example 3:
According to the same procedure as in Example 1, an aqueous dispersion was applied to the base sheet (12) to produce an adsorption sheet (1a), and the durability test was performed, and the water vapor adsorption amount before and after the durability test (F) and (U) were measured, and the adsorptive maintenance rate (X) of the adsorbing sheet was confirmed. Further, an adhesive strength test was performed to measure the adhesive strength of the coating film.

  The aqueous dispersion was obtained by adding 0.012 g of carrageenan as a thickener to 15.5 g of water and stirring sufficiently, and then synthesizing according to Example 1 described in JP-A No. 2004-136269. 10 g of FAPO-5, which is an aluminum phosphate zeolite having a diameter of 190 μm, was added and stirred, and 2.0 g of an epoxy emulsion as a binder was further added and stirred. The same epoxy emulsion as in Example 2 was used. The solid component of the aqueous dispersion was 40 wt%.

  The adsorption sheet (1a) was produced by applying the above aqueous dispersion to the same base sheet (12) as in Example 1 and then drying by heating under the same conditions as in Example 1. FAPO-5 adhering to the adsorption sheet (1a) was 0.5 g, and the epoxy resin was 0.05 g. And when the initial water vapor adsorption amount (F) of the adsorption sheet (1a) was measured, the water vapor adsorption amount (F) was 0.100 g / g.

  Subsequently, after performing the durability test similar to Example 1, when the adsorption amount (U) after the test of the adsorption sheet (1a) was measured again, the adsorption amount (U) after the test was 0.085 g / g. Yes, the adsorptive maintenance rate (X) was as good as 85%. Moreover, softening was not recognized by the surface of the adsorption sheet (1a) in the 120 degreeC heating operation in a durability test. About the adsorption sheet (1a) after a durability test, the adhesive strength test was done and the adhesive strength of the coating film was measured. As a result, it broke at 0.065 MPa.

Example 4:
By producing a plate fin type adsorbing element (2A) having the structure shown in FIG. 3 having the adsorbing sheet (1a) as a constituent element, performing a heat resistance test, and measuring a water vapor adsorption amount before and after the heat resistance test, The deterioration of the adsorption characteristics was confirmed.

  In the manufacture of the adsorption element (2A), 51 base sheets (12) made of a copper plate of 130 mm × 40 mm × 0.1 mm (thickness) were prepared as fins, and 9.6φ pipe insertion holes ( After providing 12 pieces of 11), these base sheet (12) was made into the lamination state, and the copper pipe was penetrated to each piping penetration hole (11). Subsequently, these base material sheets (12) were arranged at a pitch of 2 mm, and each of the base material sheets (12) was fixed by expanding 12 copper tubes. And the end part of each copper pipe was connected in order with the U-shaped pipe, the heat-medium flow path (3) was comprised, and the frame structure base | substrate of an element was produced.

  Subsequently, an aqueous dispersion prepared by the same method as in Example 2 and containing 1 kg of FAPO-5 as an adsorbent was applied to the skeleton structure substrate, and the adsorbent was adhered. . In the application of the aqueous dispersion liquid, the liquid application by spraying the aqueous dispersion liquid onto the skeleton structure substrate was repeated 8 times. In addition, in the application of the aqueous dispersion, in order to enhance the adhesion with the previously formed adsorbent layer, each time the aqueous dispersion was applied once, it was heated and dried at 120 ° C. for 30 minutes and then fixed. The same amount of water as the solid content was included. And about the obtained adsorption element (2A), when the adhesion amount of the adsorbent was confirmed, 83g of FAPO-5 adhered to the whole element. In the adsorption element (2A), the distance (2L) between the adsorption sheets (1a) (fins) is 2 mm, and the thickness (t) of the adsorbent layer (13) is 0.2 mm. The ratio of / t was 10 times.

  Next, in order to confirm the initial adsorption characteristics of the adsorbing element (2A), the adsorbing element (2A) was exposed to an air current having a temperature of 23 ° C. and a relative humidity of 70% RH for 20 minutes, and then the water vapor adsorption amount was measured. However, the water vapor adsorption was 15.02 g. Subsequently, the adsorption element (2A) was heated at a temperature of 120 ° C. for 20 minutes to desorb moisture from the adsorption element (2A). After moisture desorption, softening of the surface of each adsorbing sheet (1a) (fin) and scattering of the adsorbent were not observed. After that, again, the adsorption element (2A) was exposed to an air flow at a temperature of 23 ° C. and a relative humidity of 70% RH for 20 minutes, and when the amount of water vapor adsorption was measured, the water vapor adsorption was 15.02 g, and the adsorption performance of the adsorbent deteriorated. It was confirmed that they did not.

Example 5:
According to the same procedure as in Example 2, an aqueous dispersion was applied to the base sheet (12) to produce the adsorption sheet (1), and the durability test was performed, and the water vapor adsorption amount before and after the durability test F and U were measured, and the adsorptive maintenance rate X of the adsorbing sheet was confirmed. Further, an adhesive strength test was performed to measure the adhesive strength of the coating film.

  The aqueous dispersion is an aluminum phosphate-based zeolite having an average particle diameter of 4 μm obtained by synthesizing according to Example 1 described in JP-A No. 2004-136269 with respect to 14.9 g of water and finely pulverizing by dry pulverization. 10 g of FAPO-5 was added and stirred, and then 2.56 g of a modified acrylic emulsion was added as a binder and stirred. As for the composition of the modified acrylic emulsion, the nonvolatile content (manufactured by Chuo Rika Co., Ltd .; trade name “ET-19N”) was 39 wt%, and the solid content of the aqueous dispersion was 40 wt%. The binder was individually heated and dried at 120 ° C. for 30 minutes, and the glass transition temperature Tg was measured by DSC. The Tg was 29 ° C.

  The adsorption sheet (1) was produced by applying the above aqueous dispersion to the base sheet (12) in the same manner as in Example 1 and then drying by heating under the same conditions as in Example 1. The amount of FAPO-5 adhered to the adsorption sheet (1) was 0.5 g, and the binder resin was 0.05 g. And when the initial water vapor adsorption amount (F) of the adsorption sheet (1) was measured, the water vapor adsorption amount (F) was 0.087 g / g.

  Subsequently, after performing the durability test similar to Example 1, when the adsorption amount (U) after the test of the adsorption sheet was measured again, the adsorption amount (U) after the test was 0.068 g / g, and adsorption The maintenance factor (X) was 78%. Furthermore, about the adsorption sheet (1) after a durability test, the adhesive strength test was done and the adhesive strength of the coating film was measured. As a result, it broke at 0.180 MPa.

Example 6:
According to the same procedure as in Example 2, an aqueous dispersion was applied to the base sheet (12) to produce the adsorption sheet (1), and the durability test was performed, and the water vapor adsorption amount before and after the durability test F and U were measured, and the adsorptive maintenance rate X of the adsorbing sheet was confirmed. Further, an adhesive strength test was performed to measure the adhesive strength of the coating film.

  The aqueous dispersion was stirred by adding 10 g of FAPO-5, which is an aluminum phosphate zeolite having an average particle diameter of 4 μm, to 15.7 g of water, and then adding 1.82 g of a modified ethylene vinyl acetate resin emulsion as a binder. It was prepared by doing. As for the composition of the modified ethylene vinyl acetate resin emulsion, the non-volatile content (manufactured by Power Ace; trade name “Quick Dry Clear”) was 55 wt%, and the solid component of the aqueous dispersion was 40 wt%. Moreover, when the binder was individually heated and dried at 120 ° C. for 30 minutes and the glass transition temperature Tg was measured by DSC, the Tg was 6 ° C.

  The adsorption sheet (1) was produced by applying the above aqueous dispersion to the base sheet (12) in the same manner as in Example 1 and then drying by heating under the same conditions as in Example 1. The amount of FAPO-5 adhered to the adsorption sheet (1) was 0.5 g, and the binder resin was 0.05 g. And when the initial water vapor adsorption amount F of the adsorption sheet was measured, the water vapor adsorption amount (F) was 0.106 g / g.

  Subsequently, after performing the durability test similar to Example 1, when the adsorption amount (U) after the test of the adsorption sheet (1) was measured again, the adsorption amount (U) after the test was 0.099 g / g. Yes, the adsorptive maintenance rate (X) was 93%. Moreover, about the adsorption sheet (1) after a durability test, the adhesive strength test was done and the adhesive strength of the coating film was measured. As a result, it broke at 0.182 MPa.

Example 7:
According to the same procedure as in Example 2, an aqueous dispersion was applied to the base sheet (12) to produce an adsorption sheet. Then, a durability test was performed, and the water vapor adsorption amount (F) before and after the durability test. , (U) was measured, and the adsorptive retention rate (X) of the adsorbing sheet was confirmed. Further, an adhesive strength test was performed to measure the adhesive strength of the coating film.

  The aqueous dispersion was stirred after adding 10 g of FAPO-5, which is an aluminum phosphate zeolite having an average particle diameter of 4 μm, to 14.9 g of water, and then adding 2.56 g of an acrylic / styrene copolymer emulsion as a binder. It was prepared by doing. The composition of the acrylic / styrene copolymer emulsion was 39 wt% of non-volatile content (manufactured by Chuo Rika Co., Ltd .; trade name “FK-480N”), and the solid content of the aqueous dispersion was 40 wt%. Moreover, when the binder was individually heated and dried at 120 ° C. for 30 minutes and the glass transition temperature Tg was measured by DSC, the Tg was 8 ° C.

  The adsorption sheet was produced by applying the above aqueous dispersion to the base sheet (12) in the same manner as in Example 1 and then drying by heating under the same conditions as in Example 1. The amount of FAPO-5 attached to the adsorption sheet was 0.5 g, and the binder resin was 0.05 g. And when the water vapor adsorption amount (F) of the initial stage of the adsorption sheet was measured, the water vapor adsorption amount (F) was 0.087 g / g.

  Subsequently, after performing the durability test similar to Example 1, when the adsorption amount (U) after the test of the adsorption sheet was measured again, the adsorption amount (U) after the test was 0.068 g / g, and adsorption The maintenance factor (X) was 78%. In addition, many cracks were observed on the surface of the adsorption sheet after the durability test. About the adsorption sheet after a durability test, the adhesive strength test was done and the adhesive strength of the coating film was measured. As a result, it broke at 0.044 MPa.

Example 8:
According to the same procedure as in Example 1, an aqueous dispersion was applied to the base sheet (12) to produce an adsorption sheet (1a), and the durability test was performed, and the water vapor adsorption amount before and after the durability test (F) and (U) were measured, and the adsorptive maintenance rate (X) of the adsorbing sheet (1a) was confirmed. Further, an adhesive strength test was performed to measure the adhesive strength of the coating film.

  The aqueous dispersion was prepared by adding 10 g of FAPO-5, which is an aluminum phosphate zeolite having an average particle diameter of 4 μm, to 15.5 g of water, stirring the mixture, and further using the same epoxy emulsion as used in Example 2 as a binder. 6 g and urethane-modified ethylene / vinyl acetate emulsion 0.3 g were added and prepared by stirring. The urethane-modified ethylene / vinyl acetate emulsion had a nonvolatile content (made by Chuo Rika Co., Ltd .; trade name “BA-53”) of 57 wt%, and the binder weight ratio in the dry state was 80:20. The solid component of the aqueous dispersion was 40 wt%. The binder “BA-53” was individually heated and dried at 120 ° C. for 30 minutes, and the glass transition temperature Tg was measured by DSC. The Tg was −3 ° C. From the glass transition temperature Tg of both binders, the weighted average Tg was 41 ° C.

  The adsorption sheet (1a) was produced by applying the above aqueous dispersion to the same base sheet (12) as in Example 1 and then drying by heating under the same conditions as in Example 1. The amount of FAPO-5 adhering to the adsorption sheet (1a) was 0.5 g, and the binder resin was 0.05 g. And when the initial water vapor adsorption amount (F) of the adsorption sheet (1a) was measured, the water vapor adsorption amount (F) was 0.107 g / g.

  Subsequently, after performing the durability test similar to Example 1, when the adsorption amount (U) after the test of the adsorption sheet (1a) was measured again, the adsorption amount (U) after the test was 0.098 g / g. Yes, the adsorptivity maintenance rate (X) was as good as 92%. Moreover, softening was not recognized by the surface of the adsorption sheet (1a) in the 120 degreeC heating operation in a durability test. About the adsorption sheet (1a) after a durability test, the adhesive strength test was done and the adhesive strength of the coating film was measured. As a result, it broke at 0.171 MPa.

Example 9:
The adsorbing element shown in FIG. 15 comprising a large number of adsorbing sheets (1c) according to the first aspect, in which the base sheet is a fibrous sheet, and having a cylindrical honeycomb structure formed by these adsorbing sheets (1c) ( 2F) was manufactured, a heat resistance test was performed, and the water vapor adsorption amount before and after the heat resistance test was measured to confirm the deterioration of the adsorption characteristics.

  The adsorption element (2F) was manufactured as follows. Flat and corrugated silica alumina fiber papers were wound while being alternately laminated to obtain a honeycomb structure having substantially triangular cells (50) having a width of 3 mm and a height of 1.6 mm. This was cut to obtain a cylindrical honeycomb having a diameter of 200 mm and a thickness of 18 mm. Subsequently, the cylindrical honeycomb structure was immersed in an aqueous dispersion prepared by the same method as in Example 8 and containing 1 kg of FAPO-5 as an adsorbent. Cutting was performed, followed by heating and drying at 120 ° C. for 30 minutes to obtain a columnar honeycomb adsorbing element (2F) carrying FAPO-5. This columnar honeycomb adsorbing element (2F) was confirmed to have a supported amount of FAPO-5 of 161 g / L by measuring the P element content using a fluorescent X-ray analyzer EDX-700 manufactured by Shimadzu Corporation. .

  Next, in order to confirm the initial adsorption characteristics of the cylindrical honeycomb adsorption element (2F), air at a temperature of 23 ° C. and a relative humidity of 70% RH was passed through the adsorption element (2F) at 3 m / s for 10 minutes. Then, when the water vapor adsorption amount was measured, the water vapor adsorption amount was 30.6 g. Subsequently, the adsorption element (2F) was heated at a temperature of 120 ° C. for 20 minutes to desorb moisture from the adsorption element (2F). After moisture desorption, softening of the surface of each adsorbing sheet (1c) and scattering of the adsorbent were hardly observed. After that, again, the adsorption element (2F) was exposed to an air current at a temperature of 23 ° C. and a relative humidity of 70% RH for 20 minutes, and when the amount of water vapor adsorption was measured, the water vapor adsorption was 30.6 g, and the adsorption performance of the adsorbent deteriorated. It was confirmed that they did not.

Comparative Example 1:
According to the same procedure as in Example 2, a dispersion liquid was applied to the base sheet (12) to produce an adsorption sheet, and the durability test was performed, and the water vapor adsorption amount (F) before and after the durability test, (U) was measured and the adsorption maintenance factor (X) of the adsorption sheet was confirmed. Further, an adhesive strength test was performed to measure the adhesive strength of the coating film.

  The aqueous dispersion was prepared by adding a vinyl acetate resin emulsion as a binder and stirring. As for the composition of the vinyl acetate resin emulsion, the nonvolatile content (manufactured by Konishi Co., Ltd .; trade name “for bond woodworking”) was 41 wt%, and the solid content of the aqueous dispersion was 40 wt%. Moreover, when the binder was individually heated and dried at 120 ° C. for 30 minutes and the glass transition temperature Tg was measured by DSC, the Tg was 31 ° C. When the initial water vapor adsorption amount (F) of the adsorption sheet was measured, the water vapor adsorption amount (F) was 0.093 g / g.

Subsequently, after performing the durability test similar to the comparative example 1, when the adsorption amount (U) after the test of the adsorption sheet was measured again, the adsorption amount (U) after the test was 0.080 g / g. The sex maintenance rate (X) was 86%. In the durability test, peeling started at the 15th time. Further, about 80% of the adsorbing sheet after the durability test was peeled off in a planar shape from the surface, and it was impossible to apply an adhesive tape at 1 cm ² , and an adhesive strength test could not be performed. It was confirmed that the aqueous dispersion using this binder is not suitable for the production of an adsorption sheet.

Comparative Example 2:
According to the same procedure as in Comparative Example 1, a dispersion liquid was applied to the base sheet (12) to produce an adsorption sheet, and the durability test was performed, and the water vapor adsorption amount before and after the durability test (F), (U) was measured and the adsorption maintenance factor (X) of the adsorption sheet was confirmed. Furthermore, the adhesive strength test was performed and the adhesive strength of the coating film was measured.

  10 g of FAPO-5, which is an aluminum phosphate-based zeolite having an average particle diameter of 4 μm, is added to 12.7 g of acetone, and the dispersion is stirred. Further, a solvent-type adhesive (manufactured by KOKUYO; It was prepared by adding 4.76 g of "adhesive" product number TA-650) and stirring. The solvent-type adhesive contains 21 wt% of urethane resin as a non-volatile component, and acetone and butyl acetate as organic solvents. The solid component in the dispersion containing acetone was 40 wt%. The binder was individually heated and dried at 120 ° C. for 30 minutes, and the glass transition temperature Tg was measured by DSC, but a clear transition temperature could not be measured.

  Furthermore, in the durability test, cracks entered the surface at the 20th time and peeling started at the 31st time. The adsorbent sheet after the durability test had severe surface irregularities and many peelings. Therefore, the durability test could not be performed. It was confirmed that the organic solvent dispersion using this binder is not suitable for the production of the adsorption sheet. Further, the adhesion strength test after the durability test could not be performed in the same manner.

It is a partial perspective view which shows the structure of one form of the suction sheet which concerns on this invention. It is a partial perspective view which shows the structure of the other form of the suction sheet which concerns on this invention. It is a perspective view which shows one form of the plate fin type adsorption | suction element based on invention. It is a fragmentary sectional view which fractures | ruptures in the direction orthogonal to the plate | board surface of an adsorption sheet, and shows the relationship between the arrangement | positioning space | interval of the adsorption sheet and the thickness of an adsorbent layer in the adsorption | suction element of FIG. It is a perspective view which shows the other form of the corrugated fin type adsorption | suction element based on this invention. FIG. 6 is a partial cross-sectional view showing the relationship between the bending pitch of the adsorbing sheet and the thickness of the adsorbing material layer in the adsorbing element of FIG. 1 is a perspective view showing one embodiment of a rotor-type adsorption element having a cylindrical honeycomb structure according to the present invention, and a partially enlarged view showing the shape of a cell. It is a figure which shows the manufacturing method of the frame | skeleton structure base | substrate of a honeycomb as a base material, and is a partial perspective view which shows the joining method of each sheet | seat in preparation of the laminated body of a base material sheet. It is a figure which shows the manufacturing method of the skeleton structure base material of the honeycomb as a base material, and is a partial perspective view which shows the external shape of the laminated body of a base material sheet. It is a figure which shows the manufacturing method of the frame | skeleton structure base material of the honeycomb as a base material, and when the laminated body of a base material sheet is expanded, the deformation | transformation state of the base material sheet and the partial form of the laminated body which show the shape of the cell formed It is a side view. It is a figure which shows the manufacturing method of the skeleton structure base | substrate of the honeycomb as a base material, and is a perspective view which shows the expansion | deployment method of the laminated body in preparation of the skeleton structure base | substrate of a cylindrical honeycomb. FIG. 4 is a perspective view showing another embodiment of a rotor-type adsorption element having a cylindrical honeycomb structure according to the present invention and a partially enlarged view showing a cell shape. 1 is a perspective view showing an embodiment of a rotor-type adsorption element having a cylindrical honeycomb structure according to the present invention and a partially enlarged view showing a cell shape. It is a figure which shows the manufacturing method of the skeleton structure base | substrate of a honeycomb as a base material of the adsorption | suction element of FIG. 13, and is a perspective view which shows the expansion | deployment method of a laminated body. FIG. 6 is a perspective view showing another embodiment of a rotor-type adsorption element having a cylindrical honeycomb structure according to the present invention and a partially enlarged view showing a cell shape. It is process drawing which shows the method of the durability test performed when measuring the adsorption | suction characteristic of an adsorption sheet. It is a flowchart which shows the structure of the adsorption amount measuring apparatus used when measuring the adsorption | suction characteristic of an adsorption sheet.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1: Adsorption sheet 1a: Flat adsorption sheet using a metal sheet as a base sheet 1b: Corrugated adsorption sheet using a metal sheet as a base sheet 1c: Adsorption using a fibrous sheet as a base sheet Sheet 12: Substrate sheet made of metal sheet 13: Adsorbent layer 14: Substrate sheet made of fibrous sheet 2A: Adsorption element 2B: Adsorption element 2C: Adsorption element 2D: Adsorption element 2E: Adsorption element 2F: Adsorption element 20 : Ventilation space 3: Heat medium flow path 4: Heat medium flow path 41: Inlet side header 42: Outlet side header 5b: Laminate of base sheet 50: Cell 53: Square flat base sheet 61: Constant temperature bath 62 : Water tank 63: Freezer 71: First thermostat 72: Second thermostat 73: Third thermostat 74: Sample container 75: Water container 76: Water capture container 88: Vacuum pump 2L: Base material sea T: Thickness of adsorbent layer X: Cell arrangement direction Y: Cell ventilation direction

Claims (20)

  An adsorbing sheet for adsorbing elements in which an adsorbing material is supported on a base material sheet by a binder, and the durability test is repeated 50 times by heating to 120 ° C. and immersing in normal temperature water and then cooling to −15 ° C. An adsorbing sheet having an adhesive strength of 0.04 MPa or more after performing.   The water vapor adsorption amount after performing the durability test of repeating the operation of heating to 120 ° C. and immersing in normal temperature water and then cooling to −15 ° C. 50 times is 80% or more with respect to the initial water vapor adsorption amount. The adsorption sheet according to claim 1.   The adsorption sheet according to claim 1 or 2, wherein the binder has a glass transition temperature of 35 ° C or higher.   The adsorption sheet according to any one of claims 1 to 3, wherein the binder is an epoxy resin.   The adsorbent sheet according to any one of claims 1 to 4, wherein the adsorbent is one or more selected from the group consisting of activated carbon, silica, mesoporous silica, alumina, and zeolite.   The adsorbent sheet according to claim 1, wherein the adsorbent has an average particle size of 0.1 to 300 μm.   The adsorbent sheet according to any one of claims 1 to 6, wherein the base sheet is a metal sheet, and the adsorbent is supported in a laminated state on at least one surface of the metal sheet by a binder.   The adsorbent sheet according to any one of claims 1 to 6, wherein the base sheet is a fibrous sheet, and the adsorbent is supported by a binder in a state where the adsorbent is intertwined with the fiber on and inside the fibrous sheet.   An adsorbing element comprising a plurality of adsorbing sheets according to claim 7, wherein each adsorbing sheet is formed in a plate shape, comprising a single heat medium flow path, and each adsorbing sheet is formed on each of these plates. Arranged through a certain ventilation space so that the surfaces are parallel and parallel, and the heat medium flow path is arranged in a state of penetrating each adsorption sheet and is in contact with each adsorption sheet Adsorption element characterized by.   The distance (2L) between each base sheet of the adsorbing sheet adjacent to the adsorbing sheet is set to be larger than twice the thickness (t) of the adsorbing material layer of the adsorbing sheet and not more than 40 times. The adsorption element as described.   An adsorbing element comprising a plurality of adsorbing sheets according to claim 7, wherein each adsorbing sheet is formed in a band shape that bends in a zigzag manner, and includes an inlet-side header and an outlet-side header, parallel and parallel therebetween. A plurality of straight tubular heat medium passages spanned across, each of the adsorbing sheets is inserted between the adjacent heat medium passages along the longitudinal direction of the adsorbing sheet, An adsorbing element, wherein a concave portion of the adsorbing sheet is used as a ventilation space, and each heat medium flow path is in contact with each convex portion of the adsorbing sheet adjacent thereto.   The distance (2L) between the base sheet of the convex portions of the adsorbing sheet adjacent on one heat medium flow path side is larger than twice the thickness (t) of the adsorbent layer of the adsorbing sheet and 40 times The adsorption element according to claim 11 set as follows.   An adsorbing element comprising a large number of the adsorbing sheets according to claim 8 and constituted by these adsorbing sheets into a cylindrical honeycomb structure, wherein the adsorbing sheets formed in a substantially corrugated plate shape are arranged in a circumferential direction. An adsorbing element, wherein a plurality of ventilation cells having a substantially hexagonal opening shape are provided on the peripheral surface by being arranged in a stacked state along the periphery.   An adsorbing element comprising a large number of adsorbing sheets according to claim 8 and constituted by these adsorbing sheets into a cylindrical honeycomb structure, wherein the adsorbing sheet and the substantially flat plate are formed in a substantially corrugated plate shape. The adsorbing element, wherein the formed adsorbing sheets are alternately arranged in a stacked state along the axial direction so that a large number of ventilation cells having a substantially triangular opening shape are provided on the peripheral surface. .   An adsorbing element comprising a large number of the adsorbing sheets according to claim 8 and configured by these adsorbing sheets into a cylindrical honeycomb structure, wherein the adsorbing sheets formed in a substantially corrugated plate shape are arranged in a circumferential direction. An adsorbing element comprising a plurality of venting cells having a substantially hexagonal opening shape on an end face thereof, arranged in a stacked state along the end surface.   An adsorbing element comprising a large number of adsorbing sheets according to claim 8 and constituted by these adsorbing sheets into a cylindrical honeycomb structure, wherein the adsorbing sheet and the substantially flat plate are formed in a substantially corrugated plate shape. An adsorbing element, wherein the adsorbing elements are arranged in a stacked state alternately along the diametrical direction so that a large number of ventilation cells having a substantially triangular opening shape are provided on an end surface.   It is a manufacturing method of the adsorption element in any one of Claims 9-12, Comprising: The base material sheet | seat is produced using the base material sheet | seat, Then, an adsorbent and a binder are disperse | distributed to water. An adsorbent is attached to the surface of the substrate sheet by applying the aqueous dispersion to the substrate sheet of the skeleton structure substrate and then drying the substrate sheet by heating and drying. Production method.   The method for producing an adsorbing element according to any one of claims 13 to 16, wherein a base material sheet is used to produce a skeleton structure substrate of the adsorbing element, and then the adsorbent and the binder are dispersed in water. After the aqueous dispersion liquid is applied to the base material sheet of the skeletal structure substrate, the base material sheet is heated and dried to attach an adsorbent to the surface and the inside of the base material sheet. Device manufacturing method.   An adsorption heat pump comprising the adsorption element according to claim 9.   A humidity control air conditioner comprising the adsorption element according to any one of claims 9 to 16.