JP5966745B2 - Adsorption heat pump - Google Patents

Description

  The present invention is an adsorptive heat pump using zeolite as an adsorbing material, which suppresses the deterioration of zeolite of the adsorbing material and the occurrence of corrosion of the adsorbing elements and devices used in the adsorptive heat pump. The present invention relates to an adsorption heat pump excellent in stability.

  Adsorption elements in which adsorbents such as silica gel and zeolite are coated or filled on a substrate are known, and heat exchangers using such adsorption elements are used for desiccant air conditioning and adsorption heat pumps.

  In order to adhere the adsorbent to the base sheet or the heat exchanger fin, a binder is used. This binder is roughly classified into inorganic binders such as water glass, silicate, and aluminum phosphate, and organic binders such as acrylic resin, vinyl acetate resin, polyvinyl alcohol, and epoxy resin.

  By using the organic binder, the adsorbent is firmly bonded to the sheet or fin. In Patent Document 1, heat exchange of an adsorption-type refrigerator in which an adhesive acrylic binder is applied to an aluminum fin and 20 to 35 mesh (particle size is about 450 to 850 μm) of powdered silica gel is adhered to the surface. Members are described.

  In Patent Documents 2 and 3, ALPO-based zeolite is attached using a resin binder having a glass transition temperature (Tg) of 35 ° C. or higher, specifically, a binder such as bisphenol A type epoxy resin or vinyl acetate resin. Adsorption sheets and elements are described. An adsorption heat pump and a desiccant air conditioner having a heat exchanger using this element are also described.

  In the adsorption heat pump with the built-in adsorption element using the organic binder described in Patent Documents 1 to 3, as described in Patent Document 4, it is included in the thermal decomposition product of the organic binder and the organic binder. The low molecular weight substances that are released may be released as gas, and the function of the heat pump may be impaired.

  Adsorption type heat pumps with built-in adsorption elements using inorganic binders are prone to hydrogen release due to corrosion of metal materials such as aluminum and carbon dioxide from alkali carbonates. May decrease.

  Patent Document 5 describes an epoxy resin binder with improved heat resistance and less outgas. By using this organic binder, a decrease in internal pressure due to gas release from the organic binder is prevented. However, some organic components are gradually hydrolyzed over a long period of time to generate an acid, and the inside of the apparatus is corroded.

  Since the adsorption elements described in Patent Documents 1 to 3 have a low thermal conductivity of an adsorption layer made of a coating film formed of an adsorbent and an organic binder, the heat transfer performance of a heat exchanger using the adsorption layer is low. .

JP-A-7-301469 JP 2007-190546 A JP 2009-106799 A WO2010 / 040335 JP 2011-240330 A

  The present invention has been made in view of the above circumstances, and is an adsorption heat pump using a heat exchanger using an adsorption element provided with a coating film containing zeolite and an organic binder, and is generated in the apparatus. It is an object of the present invention to provide an adsorption heat pump having an acid neutralizing means. Moreover, this invention is providing the adsorption type heat pump with which the heat-transfer performance was improved in the one aspect | mode.

  As a result of intensive studies, the present inventors have found that at least part of the portion where water vapor is present in the casing of an adsorption heat pump using a heat exchanger using an adsorption element provided with a coating film containing zeolite and an organic binder. It has been found that the acid derived from the organic binder is neutralized by the presence of specific hydroxide particles or particles capable of forming this hydroxide by a hydration reaction. Moreover, when this particle | grain was made to exist in a coating film, it discovered that the heat conductivity of this coating film could be improved.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] An adsorption heat pump having an adsorption / desorption device, a condenser, and an evaporator, the adsorption / desorption device having a heat exchanger and an adsorption element that can be heated or cooled by the heat exchanger. The adsorbing element has a substrate and a coating film containing zeolite and an organic binder provided on the substrate, and has a solubility of 20 ° C. in at least a part of the portion where water vapor as an adsorbate exists. Is an adsorption heat pump in which there is a hydroxide that is 20 mg / 100 cm ³ -H ₂ O or less and / or particles that can form the hydroxide by a hydration reaction.

[2] The adsorption heat pump according to [1], wherein the particles contain a dehydration product of the hydroxide.

[3] The adsorption heat pump according to [2], wherein the hydroxide dehydrate is an oxide.

[4] The adsorption heat pump according to any one of [1] to [3], wherein the hydroxide is at least one selected from magnesium hydroxide, aluminum hydroxide, and zinc hydroxide.

[5] The adsorption heat pump according to any one of [1] to [4], wherein at least some of the particles are magnesium oxide.

[6] The adsorption heat pump according to any one of [1] to [5], wherein the condenser and the evaporator are integrated.

[7] The particles of [1] to [6], wherein the hydroxide particles and / or particles capable of forming the hydroxide by a hydration reaction are present in the coating film of the heat exchanger. An adsorption heat pump according to any one of the above.

[8] The amount of the hydroxide particles in the coating film of the heat exchanger and / or the particles capable of forming the hydroxide by a hydration reaction is 10 wt% or more and 30 wt% or less [7]. The adsorption heat pump described in 1.

[9] The hydroxide particles and / or the particles capable of forming the hydroxide by a hydration reaction are present in a place other than the coating film and in at least a part of a water vapor flow path as an adsorbate. The adsorption heat pump according to any one of [1] to [6].

[10] The heat exchanger includes a first coating film that does not include the hydroxide particles and / or particles that can form the hydroxide by a hydration reaction, the hydroxide particles, and The adsorption heat pump according to any one of [1] to [6], comprising: a second coating film containing particles capable of forming the hydroxide by a hydration reaction.

[11] The adsorption type according to any one of [1] to [10], wherein a container containing the hydroxide particles and / or particles capable of forming the hydroxide by a hydration reaction is installed. heat pump.

[12] The adsorption according to any one of [1] to [11], wherein the hydroxide particles and / or the particles capable of forming the hydroxide by a hydration reaction are arranged in a steam circulation pipe. Type heat pump.

[13] The hydroxide particles and / or the particles capable of forming the hydroxide by a hydration reaction are present in an amount of 0.1 wt% or more with respect to the adsorbate. [12] The adsorption heat pump according to any one of [12].

  In the adsorption heat pump of the present invention, the acid generated by hydrolysis of the organic binder is neutralized by the hydroxide or particles that form a hydroxide by a hydration reaction. Corrosion of the device is suppressed. Thereby, while maintaining the adsorption | suction performance of a zeolite for a long term, the environment in an apparatus can be maintained in the optimal state.

  The coating film containing the particles, zeolite, and organic binder has high thermal conductivity of the particles, so that the thermal conductivity of the coating film can be improved, and the adsorption heat pump can be downsized and improved in performance.

It is a systematic diagram showing a configuration example of a general adsorption heat pump. It is a block diagram of the adsorption | suction element in the adsorption / desorption device of the adsorption | suction type heat pump which concerns on embodiment. It is a cross-sectional perspective view of a part of the adsorption element of FIG. It is sectional drawing of an acid trap device. It is sectional drawing which shows the example of installation of an acid trap device. It is sectional drawing which shows the example of installation of another acid trap device. It is sectional drawing which shows an example of an adsorption | suction type heat pump. It is sectional drawing which shows an example of an adsorption | suction type heat pump. It is sectional drawing which shows an example of an adsorption | suction type heat pump. It is sectional drawing which shows an example of an adsorption | suction type heat pump. It is sectional drawing which shows an example of an adsorption | suction type heat pump. It is sectional drawing which shows an example of an adsorption | suction type heat pump. It is typical sectional drawing which shows the experimental apparatus used in the Example. It is a schematic diagram which shows the experimental apparatus used in the Example.

  Examples of embodiments of the present invention will be described below, but the present invention is not limited to the embodiments described below.

The adsorption heat pump of the present invention (hereinafter sometimes simply referred to as “heat pump”) uses heat as a drive source and water (water vapor) as a heat medium (refrigerant or heat medium). The adsorption heat pump of the present invention has an adsorption / desorption device, a condenser, and an evaporator. The condenser and the evaporator may be used together (integrated). The adsorption / desorption device includes a heat exchanger and an adsorption element heated or cooled by the heat exchanger. This adsorbing element has a base and a coating film containing zeolite and an organic binder provided on the base. At least part of the portion where water vapor is present in the casing of the adsorption heat pump, a hydroxide having a solubility at 20 ° C. of 20 mg / 100 cm ³ —H ₂ O or less and / or the hydroxide by a hydration reaction. There are particles that can be formed (hereinafter sometimes referred to as “acid trapping particles”).

<Acid trap particles>
In the present invention, the acid trapping particles are responsible for the acid neutralization function. Acid trap particles can neutralize carboxylic acids such as acetic acid and formic acid generated by hydrolysis of organic binders, and no gas other than water is generated in the neutralization reaction. The degree of vacuum inside is not reduced.

  However, hydroxides with high water solubility are strongly basic, causing destruction of surrounding zeolites and corrosion of heat exchanger fins. Many of such hydroxides are deliquescent, and there is a concern that the particles lose their shape, fill the voids in the coating film, and hinder diffusion of water vapor in the coating film. A hydroxide having a high solubility in water has a problem that it cannot maintain the shape of particles in an aqueous slurry for forming a coating film and cannot exhibit a neutralizing function.

Therefore, in the present invention, as acid trap particles, particles having a solubility in water at 20 ° C. of 20 mg / 100 cm ³ —H ₂ O or less and poorly water-soluble hydroxide and / or particles capable of forming the hydroxide by a hydration reaction Is used. The solubility may be 20 mg / 100 cm ³ —H ₂ O or less, more preferably 15 mg / 100 cm ³ —H ₂ O or less, and particularly preferably 10 mg / 100 cm ³ —H ₂ O or less. However, those having an excessively low solubility in water are usually 0.5 mg / 100 cm ³ —H ₂ O or more because the acid neutralization effect is also low.

  Among the hydroxides satisfying the above-mentioned solubility conditions, hydroxide particles such as magnesium hydroxide, aluminum hydroxide, and zinc hydroxide are preferred as the hydroxide particles because they are easily available as particles. These acid trap particles may be used alone or in combination of two or more.

  Moreover, it is preferable that the acid trap particle | grains used by this invention contain the oxide which is the dehydration thing of the hydroxide. This is because the oxide, which is a dehydrated product, generally has a higher thermal conductivity than the hydroxide, and the acid trap particles contain the dehydrated product, so that the thermal conductivity of the coating can be efficiently increased. By being able to increase. Therefore, for example, when the acid trap particles are magnesium hydroxide particles, it is preferable to use magnesium oxide particles, and at least a portion thereof is magnesium hydroxide. Examples of such magnesium hydroxide include those intentionally added to magnesium oxide or those obtained by changing magnesium oxide by a hydration reaction. Similarly, it is preferable that alumina or boehmite is contained if the acid trap particles are aluminum hydroxide, and zinc oxide is contained if the acid trap particles are zinc hydroxide.

  When acid trap particles are installed inside an adsorption heat pump, hydroxides such as magnesium hydroxide may absorb carbon dioxide in the air and form carbonates. This carbonate is contained in the adsorption heat pump. In some cases, carbon dioxide is gradually released, causing a decrease in output. The use of oxide particles as the acid trap particles is preferable because the surface becomes a hydroxide by a hydration reaction under the use environment in the adsorption heat pump and the risk of forming the carbonate is reduced.

  Thus, in the case of acid trap particles containing a dehydrate, from the viewpoint of the acid neutralization reaction rate, the surface layer part in contact with the gas phase is preferably a hydroxide, and from the viewpoint of heat conduction, the core part of the particle Particles in which is a dehydrated product are preferred. Such particles can be obtained by reacting the oxide particles with water and converting the surface into hydroxides. Such particles are preferably those obtained by producing an adsorbing element using oxide particles and then naturally hydroxylating the surface in the use environment.

  The thermal conductivity of the acid trap particles used in the present invention is preferably 5 W / (K · m) or more, and more preferably 10 W / (K · m) or more. Since the thermal conductivity of magnesium oxide and zinc oxide is 45 to 60 W / (K · m), the acid trap particles contain these dehydrates, thereby effectively increasing the thermal conductivity of the coating film. I can do it. In addition, although there is no restriction | limiting in particular in the upper limit of the heat conductivity of acid trap particle | grains, Usually, it is 100 W / (K * m) or less.

  The particle diameter of the acid trap particles is preferably small from the viewpoint of acid neutralization rate, but is preferably large from the viewpoint of heat conduction, and the average particle diameter is preferably 1 to 300 μm, more preferably 5 to 100 μm. The average particle diameter of the acid trap particles is a value obtained by a laser diffraction / scattering method.

[Installation form of acid trap particles]
In the adsorption heat pump of the present invention, such acid trap particles are present in at least a part of a portion where water vapor is present as an adsorbate. The acid trap particles may be present in a coating film formed using a zeolite and an organic binder on the substrate of the adsorption element of the heat exchanger. In this case, if the zeolite and the acid trap particles are in contact with each other for a long time, the zeolite may be deteriorated. Therefore, it is preferable not to contact the zeolite and the acid trap particles.

  The form in which the zeolite and the acid trap particles are not brought into contact includes a form in which a layer of the acid trap particles is formed separately from the layer containing the zeolite and the organic binder. For example, an adsorption element in which an acid trap particle layer and a coating layer containing zeolite and an organic binder are laminated on a base material can be provided. In this case, the order of lamination may be either when the acid trap particle layer is outside (surface layer side) or when the coating layer is outside, but when the acid trap particle layer is outside, the adsorbate water In order not to inhibit (water vapor) from being adsorbed on the zeolite in the coating layer, it is necessary to have a structure in which a through hole is provided so that the acid trap particle layer can transmit water vapor. In this case, the method for forming the acid trap particle layer having through-holes is not particularly limited. For example, the amount ratio of the binder and acid trap particles used to adhere the acid trap particle layer to the coating layer, the acid trap A layer having a through hole can be formed by a known method such as adjusting the particle size of the particles.

  The binder used for forming the acid trap particle layer may be organic or inorganic. For example, an organic binder such as acrylic resin, vinyl acetate resin, polyvinyl alcohol, epoxy resin, water glass, silicate, aluminum phosphate, etc. Inorganic binders can be used. In the case of an organic binder, it is preferable to use the same organic binder as that constituting the coating film containing zeolite.

  The acid trap particles may be present by filling the granulated product of the acid trap particles between the coating film containing the zeolite and the organic binder, and as such, the coating of the zeolite and the organic binder on the substrate. The thing which filled the granulated material of the acid trap particle | grains between the adsorption | suction elements which formed the film | membrane is mentioned.

  In the present invention, acid trap particles may be present in a place other than the coating film of the adsorption element. Examples of the presence form of the acid trap particles in this case include a form in which a coating film containing acid trap particles is formed in a part of the adsorption heat pump and a form in which a packed layer of acid trap particles is provided. The acid generated by hydrolysis of the organic binder is transported through the adsorption heat pump along with the adsorbate water vapor, so the location of the acid trap particles is particularly limited as long as it is an arrangement that can sufficiently contact the water vapor. Not. Examples of the installation location of the acid trap particles include a pressure-resistant vessel (chamber) in which a heat exchanger is accommodated, a condenser and / or an evaporator. In an adsorption heat pump having a configuration in which a condenser and an evaporator are separately provided and connected by a pipe, acid trap particles may be arranged in the pipe.

  When acid trap particles are present in a place other than the coating film of the adsorption element, the upper limit of the abundance is not particularly limited, but the lower limit is relative to the amount of water (steam) that is the adsorbate in the adsorption heat pump. Thus, it is desirable that the amount is 0.1 wt% or more, preferably 1 wt% or more, more preferably 5 wt% or more, and still more preferably 10 wt% or more.

  In the present invention, the acid trap particles are preferably provided in the adsorption heat pump as magnesium oxide particles, and at least partly (mainly the particle surface) undergoes hydrolysis to become magnesium hydroxide when the adsorption heat pump is used. It is preferable to be used as In the following description, “acid trap particles” will be described as “magnesium hydroxide” to describe the installation mode of the acid trap particles of the present invention. In the following, “magnesium hydroxide” will be referred to as magnesium oxide. Including those that become magnesium hydroxide by hydration during use, and such are suitable in the present invention.

  Magnesium hydroxide may be installed as a powder, or may be installed as an aggregate by granulating or forming into a pellet, honeycomb or the like using a binder. Handleability can be improved by using an aggregate.

  When acid trap particles such as magnesium hydroxide are granulated or formed into aggregates, the preferred size range depends on the amount and rate of acid generation in the adsorption heat pump, but corrodes the metal. From the viewpoint of quickly neutralizing the acid before, the larger the aggregate, the better.

The amount (g) of the acid trap particles in the aggregate is sufficient if the amount of the hydroxide of the acid trap particles or the hydroxide generated by the hydration reaction is at least the amount obtained from the following formula.
[(Carbon amount of organic binder in adsorption heat pump (g)) · (average molecular weight of acid trap particles (g / mol) · 0.05) / (atomic weight of carbon (g / mol)] · (acid Average valence of trapped particles)
That is, even when 5% of the carbon atoms of the organic binder in the adsorption heat pump is changed to formic acid, it is sufficient if there is an amount of acid trap particles that can be neutralized.

  The shape of the aggregate is preferably such that the surface area of the aggregate is increased. For example, in the case of a spherical shape, it is better that the particle size is small. The shape of the aggregate and the powder is not limited to a spherical shape, and may be a shape having irregularities on the surface. If there is such surface irregularities, the contact area with the acid-containing vapor can be increased to increase the neutralization efficiency of the acid.

  Since the neutralization reaction efficiency is improved when the acid-containing vapor can diffuse into the aggregate, the aggregate is preferably a porous body having many voids.

  The method for producing the aggregate is not particularly limited, and the acid trap particles are produced by molding or granulating according to a conventional method using the inorganic and organic binders exemplified as the binder used for forming the acid trap particle layer described above. can do.

  Magnesium hydroxide powder and aggregates thereof can be placed in the adsorption heat pump as they are, but are preferably arranged so as not to come into contact with liquid water. This is because when liquid water and acid trap particles are brought into direct contact, basic liquid water may flow to the metal portion in the adsorption heat pump and corrode it. For this reason, the magnesium hydroxide powder and its aggregates may be housed and installed in a suitable container. The container may be hung at an appropriate place in addition to being placed at an appropriate place in the adsorption heat pump.

  This container may be made of resin, but from the viewpoint of suppressing gas generation from the container, it is preferably made of glass or metal, workability and durability against breakage after installation in an adsorption heat pump. From the viewpoint of performance, metal is more preferable, and the same material as the container material such as an adsorption / desorption device, a condenser, and an evaporator is particularly preferable.

  This container may be formed of a porous material such as punching metal or a net, and in this case, water vapor comes into contact with magnesium hydroxide in the container from all directions. This container must be fixed at the installation location so that it does not move inside the adsorption heat pump due to the inclination or impact of transportation or installation of the adsorption heat pump and destroy other members such as adsorption elements and valves. desirable.

  Magnesium hydroxide may be attached to various supports and installed in an adsorption heat pump. This “support” means heat exchanger fins (adsorption element substrate described later), and magnesium hydroxide such as metal or fiber plates, rods, sheets, structures, etc. attached to places other than the heat exchanger. The “adhered object” to be installed is shown.

  There is no restriction | limiting in particular in the shape of a support body, Plate shape (a flat plate shape may be sufficient as it may have a curved surface and a level | step difference), spherical shape, rod shape, and various other irregular shapes are mentioned. For example, a magnesium hydroxide layer can be provided on the surface of a metal support having such a shape.

  Further, a fibrous sheet (nonwoven fabric or woven fabric) made of paper, metal, ceramic, glass, carbon or the like can be impregnated with magnesium hydroxide or provided as a surface layer.

  This support may be a three-dimensional structure. For example, a rectangular sheet may be wound into a cylindrical shape to form a tubular shape. More preferably, the support is made into a honeycomb shape and the surface area of the magnesium hydroxide layer formed on the surface thereof is increased.

  When a magnesium hydroxide layer is provided on a metal support, a part of the support may be exposed, and the exposed part of the support may serve as a heat transfer medium. By doing in this way, dew condensation of a magnesium hydroxide layer can be prevented. In this case, heat can be supplied to the exposed portion of the support from a heat medium required for driving the adsorption heat pump (for example, hot water, for example, a heat medium after the outlet of cooling water). From the same viewpoint, a magnesium hydroxide layer may be formed on the outer surface of the tubular support, and the heat medium may be passed through the tube.

  In the case of these magnesium hydroxide powders, aggregates, or magnesium hydroxide adhered to a support, water vapor (gas) permeates to suppress the dispersion of magnesium hydroxide and the influence of condensed water. Water (condensation water, liquid) can be covered with a material that does not permeate, specifically, a moisture-permeable waterproof film (sheet) or the like. Examples of such a moisture permeable waterproof film (sheet) include “KTF” (product of Mitsubishi Plastics), “Tyvek” (product of DuPont), and the like.

  When magnesium hydroxide is present in the gas phase, it is desirable that liquid water adheres to the magnesium hydroxide and the water does not spill out of the container in which the magnesium hydroxide is present. This is because water in contact with magnesium hydroxide becomes water containing alkali components, and the water may be scattered or vaporized, which may damage the metal or zeolite that is a constituent material of the adsorption heat pump. It is. More preferably, the structure in which liquid water does not touch magnesium hydroxide is good.

  In order to prevent condensation, for example, the container in which magnesium hydroxide is present and the magnesium hydroxide are preferably at the same temperature or higher in the gas phase as the space where water vapor is present. For the installation method of magnesium hydroxide, a structure in which a temperature equivalent to that of the adsorption element is supplied is preferable. A coating-type heat exchanger has been proposed because of its good adsorption / desorption efficiency as an adsorption element. In that case, when it is provided in the adsorption / desorption device, a part of the fin is not an adsorbent layer but a magnesium hydroxide layer. Preferably it consists of.

  The container desirably has a structure in which, when liquid water adheres to magnesium hydroxide, the water stays in the container for containing magnesium hydroxide. Therefore, it is preferable that the container holding magnesium hydroxide has a space in which water accumulates at the bottom of the container.

  In an adsorption heat pump, if the connection between the condenser and the adsorption / desorption device and the connection between the evaporator and the adsorption / desorption device are not only valves but also a fine shape by piping, etc. Magnesium may be installed. In this case, a valve may be attached to both the upstream side and / or the downstream side of the magnesium hydroxide installation part so that only the magnesium hydroxide part can be maintained.

[Adsorption element]
The adsorbing element used in the present invention is formed by providing a coating film containing a zeolite and an organic binder, which serves as an adsorbing layer, on the base material. Can be present inside. However, it is sufficient that the acid trap particles are present in at least a part of the portion where water vapor as the adsorbate is present, and the acid trap particles are not necessarily contained in the coating film.

<Base material>
The shape of the substrate that is the adherend of the coating film of the adsorption element is not particularly limited, and is applied to existing heat exchangers such as a sheet shape, plate shape, plate fin type, erotic fin tube type, corrugated type, etc. Things can be used without any particular restrictions. The material is not particularly limited, and any of metal, ceramics, graphite, resin, and other composite materials such as CFRP can be used.

<Zeolite>
The zeolite used for the coating film of the adsorption element is not particularly limited as long as it can be used for applications such as adsorption heat pumps and desiccant air conditioning, and may be a synthetic zeolite or a natural zeolite.

  As the zeolite, aluminosilicates and aluminophosphates that can be easily adsorbed and easily desorbed at low temperatures are particularly preferable. As such zeolite, there are crystalline aluminophosphates (ALPO-type zeolite) containing at least Al and P in the skeleton structure, and a code indicating the skeleton structure defined by the International Zeolite Association (IZA). CHA type and AFI type For example, there are known methods described in, for example, SAPO-34, FAPO-5, ALPO-5, JP-B-1-57041, JP-A-2003-183020, JP-A-2004-136269, and the like. An ALPO-based zeolite such as silicoaluminophosphate (SAPO) produced according to the synthesis method can be preferably used. One type of zeolite may be used alone, or two or more types may be mixed and used.

  Zeolite increases its specific surface area as its particle size decreases, so that the adsorption rate is improved. However, if it is too small, an increase in the required amount of organic binder for coating film formation and the coating ratio of the zeolite surface Problems such as increase occur. Therefore, the average particle diameter of zeolite is preferably in the range of 1 to 100 μm, and when forming a coating film by applying the slurry, it is in the range of 1 to 20 μm from the viewpoint of preventing sedimentation of zeolite in the slurry. It is particularly preferred.

  Here, the average particle diameter of zeolite is a value obtained by a laser diffraction / scattering method.

<Organic binder>
The organic binder used for the coating film of the adsorbing element is not particularly limited as long as it satisfies the heat resistance and adhesiveness necessary for practical use. Organic binders include epoxy resin, phenol resin, polyimide resin, polyester, polyethersulfone, urethane resin, melamine resin, fluorine resin, polycarbonate resin, (meth) acrylic resin, polyvinyl alcohol, silicone resin, vinyl acetate resin, Examples include polyolefin, polystyrene, latex, cellulose, maleimide compound and the like. An organic binder may be used individually by 1 type, and may mix and use 2 or more types.

  The optimum organic binder varies depending on the form of the adsorbing element and the type of adherend, but in general, from the viewpoint of maintaining the strength of the coating film, a thermosetting resin capable of increasing the cohesive force by curing is preferable. For example, when the adherend is a metal such as copper or aluminum, the organic binder is preferably an epoxy resin, a phenol resin, a urethane resin, a silicone resin, or a derivative thereof.

  These organic binders may be used after diluted in a solvent or the like, but are preferably used as an aqueous emulsion (aqueous slurry) from the viewpoint of exposing the surface of zeolite and obtaining a coating film with little adsorption inhibition. .

<Other additives>
The coating film of the adsorption element can contain various additives other than hydroxide particles, zeolite, and an organic binder. For example, various additives such as rheology additives, surfactants, antifoaming agents, curing agents, antioxidants, pH adjusters, rust inhibitors, etc. for the purpose of improving handling properties and stabilizing performance during coating film formation Can be included.

<Coating composition>
The content of zeolite in the coating film of the adsorption element is preferably 60 wt% or more and 90 wt% or less. If there is too much zeolite content in the coating film, the amount of hydroxide particles and organic binder in the coating film will be relatively small, and sufficient thermal conductivity improvement effect, acid neutralization effect, and coating film strength will be obtained. It's hard to be done. On the other hand, if there is too little zeolite in the coating film, it is difficult to obtain a sufficient amount of adsorption and adsorption rate.

  When the coating film contains acid trap particles, the content of the acid trap particles in the coating film is preferably 10 wt% or more from the viewpoint of the function expression, and from the viewpoint of ensuring the necessary content of zeolite and organic binder, 30 wt. % Or less is preferable.

  As for the content rate of the organic binder in a coating film, 5-30 wt% is preferable. If the content of the organic binder is too low, sufficient coating strength cannot be obtained, and if it is too high, the porosity of the coating decreases and the adsorption / desorption rate decreases, which is not preferable.

<Porosity of coating film>
The coating film is porous, and the porosity is preferably 30% or more, more preferably 40% or more. When the porosity is too small, the ratio of the communication holes in the coating film that becomes the adsorption layer becomes low, causing a problem that the adsorption rate is lowered. Although there is no restriction | limiting in particular about the upper limit of the porosity, If a space | gap is made between the particles in a coating film, it will usually be 60% or less. As a method for measuring the porosity of the coating film, for example, a liquid immersion method in which the coating film is impregnated with silicone oil or the like that does not enter the pores of the zeolite, and the porosity is obtained from the weight change before and after the impregnation. This method is an effective measurement method because the hole becomes a communication hole if the coating film has a certain degree of porosity.

<Thickness of coating film>
In the present invention, if the thickness of the coating film is too thin, the effect of improving the thermal conductivity of the coating film is reduced, and the amount of zeolite supported is also reduced. Moreover, since there exists a problem that it will be easy to generate | occur | produce a crack when too thick, the range of 10 micrometers-1 mm is preferable, and the range of 30 micrometers-800 micrometers is more preferable.

<Method for forming coating film>
The coating film containing zeolite and an organic binder, and further containing acid trap particles as necessary, is a coating composition containing zeolite and an organic binder, and if necessary, acid trap particles in a predetermined ratio, preferably an aqueous slurry. It can be formed by applying to a substrate, drying and curing. This coating composition may contain the other additives described above.

  Examples of the coating method include known methods such as dipping (impregnation, immersion), knife, spray, roll coating, rolling granulation, screen printing, pad printing, offset printing, and the like.

  In the adsorption heat pump of the present invention, the heat exchanger using the adsorbing element as described above is manufactured by previously assembling as a heat exchanger and then applying the coating composition described above to form a coating film. It may have been made, or it may be assembled in a heat exchanger after the coating film is formed in advance.

[Specific example of configuration of adsorption heat pump]
Hereinafter, an example of the adsorption heat pump of the present invention will be specifically described with reference to FIGS. 1 to 3, and FIGS. 1 to 3 are diagrams showing an example of the configuration of the adsorption heat pump of the present invention. The adsorption heat pump of the invention is not limited to that shown in FIGS.

  The adsorption heat pump shown in FIG. 1 repeats the operation of adsorbing the adsorbate (water vapor in this embodiment) to the adsorbent and the operation of desorbing the adsorbate from the adsorbent by the heat from the heat exchanger. The adsorption / desorption units 1 and 2 for transferring the heat generated by the adsorption operation to the heat medium and the cold heat obtained by the evaporation of the adsorbate are taken out to the outside, and the generated adsorbate vapor is absorbed by the adsorption / desorption units 1 and 2. The evaporator 4 and the adsorbate vapor desorbed by the adsorption / desorption units 1 and 2 are condensed by external cold heat, and the condensed adsorbate is supplied to the evaporator 4 and obtained by condensation of the adsorbate. And a condenser 5 for discharging the generated heat to the outside.

  The adsorption / desorption units 1 and 2 include an adsorption element and a heat exchanger capable of heating and cooling the adsorption element.

  This adsorption element has a substrate and a zeolite-containing coating film formed on the surface of the substrate. This coating film is formed by attaching zeolite to the surface of the substrate using an organic binder. When operating an adsorption heat pump, the operating conditions are determined from the adsorption isotherm at ambient temperature so that the adsorption and desorption amount required for operation can be obtained, and the maximum adsorption and desorption amount is usually obtained when operating the device. The condition is set to be

  The adsorption / desorption units 1 and 2 each have a pressure-resistant vessel (chamber) constituting the outer shell of the apparatus, and an adsorption / desorption device 10 shown in FIG. 2 arranged in the vessel. The adsorption / desorption device 10 includes a heat exchanger 11 made of a heat transfer tube and fins 12 attached to the heat exchanger 11. In this embodiment, the tubes constituting the heat exchanger 11 are arranged in a zigzag manner and penetrate the fins 12 as shown in FIG.

  The fin 12 includes a plate-like substrate 12a and a coating film 12b formed on the surface of the substrate 12a. The substrate 12a contacts the tube constituting the heat exchanger 11 or is welded or brazed. It is fixed. A large number of fins 12 are arranged with a space between them.

  In one form of the present invention, many of the fins 12 have the coating film 12b made of zeolite and a binder to constitute an adsorbing element, and the other of the fins 12 has an acid trap on the substrate 12a. A coating film 12b containing particles and not containing acid trap particles is formed.

  The coating film containing the acid trap particles and not containing the acid trap particles is formed by applying the acid trap particles to the substrate 12a with an organic binder.

  The number of fins 12 having the acid trap particle-containing coating film is less than the number of fins 12 constituting the adsorption element. For example, the fins 12 having the acid trap particle-containing coating film are arranged at a ratio of one sheet to the fins 12 constituting 10 to 1000 adsorbing elements.

  In another embodiment of the present invention, all of the fins 12 or the coating film 12b of some of the fins 12 contain zeolite, acid trap particles, and an organic binder.

  The adsorption / desorption device 10 configured as described above is installed in the adsorption / desorption units 1 and 2 shown in FIG. 1, and the heat medium pipes 1a and 2a for flowing a heat medium or a cold medium in the heat exchanger. Is connected.

  The heating medium pipes 1a and 2a are provided with switching valves 115 and 116, and 215 and 216, respectively. The heat medium pipes 1a and 2a are pipes for flowing a heat medium serving as a heating source or a cooling source for heating or cooling the adsorption elements in the adsorption / desorption units 1 and 2, respectively. The heat medium is not particularly limited, but water (hot water or cooling water) is preferably used because it is safe and simple.

  Hot water is introduced from the inlets 113 and / or 213 by opening and closing the switching valves 115, 116, 215, and 216, passes through the adsorption / desorption units 1 and / or 2, and is led out from the outlets 114 and / or 214. . The cooling water is also introduced from the inlets 111 and / or 211 by opening and closing the switching valves 115, 116, 215, and 216, and passes through the heat exchanger 11 of each adsorption / desorption unit 1 and / or 2. And / or 212. The heat source for the hot water is not particularly limited, and examples thereof include cogeneration equipment such as a gas engine and a gas turbine, and a fuel cell.

  The pressure-resistant vessels of the adsorption / desorption units 1 and 2 have an inlet port and an outlet port for water vapor, and the inlet port is connected to the evaporator 4 by pipes 3A and 3B. The water vapor outlet port is connected to the condenser 5 by pipes 3C and 3D. Control piping 3a-3d is provided in each piping 3A-3D.

  Between the condenser 5 and the evaporator 4, a return pipe 6 for returning the adsorbate condensed in the condenser 5 to the evaporator 4 is provided.

  The cold water generated by cooling in the evaporator 4 is circulated through the indoor unit 300 by the circulation pipes 4 a and 4 b and the pump 301. The indoor unit 300 exchanges heat with the air in the indoor space (air-conditioned space).

  The condenser 5 is connected to a cooling water inflow pipe 5 a and an outflow pipe 5 b.

  The operation method of the adsorption heat pump shown in FIG. 1 will be described below.

  In the first step, the control valves 3 a and 3 d are closed, the control valves 3 b and 3 c are opened, the regeneration (desorption) step is performed in the adsorption / desorption unit 1, and the adsorption step is performed in the adsorption / desorption unit 2. Further, the switching valves 115, 116, 215, and 216 are operated, and hot water is circulated through the heat medium pipe 1a and cooling water is circulated through the heat medium pipe 2a. Cooling water cooled by a heat exchanger such as a cooling tower is introduced through the heat medium pipe 2a and is circulated through the heat exchanger 11 of the adsorption / desorption unit 2 so that the adsorption element is usually cooled to about 30 to 40 ° C. By opening the control valve 3b, water vapor from the evaporator 4 flows into the adsorption / desorption unit 2 and is adsorbed by the adsorption element in the unit 2.

  Water vapor movement occurs due to the difference between the saturated vapor pressure at the evaporation temperature and the adsorption equilibrium pressure corresponding to the adsorbent temperature (generally 20 to 50 ° C., preferably 20 to 45 ° C., more preferably 30 to 40 ° C.). In the evaporator 4, cold heat corresponding to the heat of vaporization of evaporation, that is, cooling output is obtained. From the relationship between the cooling water temperature of the adsorption / desorption unit 2 and the cold water temperature generated by the evaporator 4, the adsorption side relative vapor pressure φ 2 (where φ 2 is the equilibrium vapor pressure of the adsorbate at the cold water temperature generated by the evaporator 4. Is determined by dividing by the equilibrium vapor pressure of the adsorbate at the temperature of the cooling water of the adsorption / desorption unit 2), φ2 is the relative vapor that adsorbs water vapor most by the adsorbent in the adsorption / desorption unit 2. It is preferable to operate so as to exceed the pressure. If φ2 is smaller than the relative vapor pressure at which the adsorbent adsorbs the most water vapor, the adsorbing capacity of the adsorbent cannot be used effectively, resulting in poor operating efficiency. φ2 can be set as appropriate depending on the environmental temperature, etc., but the adsorption heat pump is used under a temperature condition in which the adsorption amount at φ2 is usually 0.12 g / g-adsorbent or more, preferably 0.15 g / g-adsorbent or more. drive.

  The adsorption element of the adsorption / desorption unit 1 in the regeneration process is usually heated by hot water of 40 to 90 ° C., preferably 50 to 80 ° C., more preferably 60 to 70 ° C., and has an equilibrium vapor pressure corresponding to the temperature range. The condenser 5 is condensed with a saturated vapor pressure at a condensation temperature of 30 to 40 ° C. (which is equal to the temperature of the cooling water cooling the condenser 5). Water vapor moves from the adsorption / desorption unit 1 to the condenser 5 and is condensed to become water. The condensed water is returned to the evaporator 4 through the return pipe 6. From the relationship between the temperature of the cooling water in the condenser 5 and the temperature of the hot water, the desorption side relative vapor pressure φ1 (where φ1 is the equilibrium vapor pressure of the adsorbate at the temperature of the cooling water in the condenser 5 and the adsorption at the temperature of the hot water) It is preferable to operate so that the adsorbent of the adsorption / desorption unit 1 becomes smaller than the relative vapor pressure at which the water vapor is adsorbed abruptly. If φ1 is larger than the relative vapor pressure at which the adsorbent adsorbs water vapor rapidly, the excellent adsorption amount of the adsorbent cannot be used effectively. φ1 can be set as appropriate according to the environmental temperature, etc., but the adsorption heat pump under the temperature condition that the adsorption amount in φ1 is usually 0.14 g / g-adsorbent or less, preferably 0.10 g / g-adsorbent or less To drive.

  The adsorption heat pump has a difference between the adsorbate adsorption amount at φ1 and the adsorbate adsorption amount at φ2 of usually 0.12 g / g-adsorbent or more, preferably 0.15 g / g-adsorbent. It is preferable to operate so as to achieve the above.

  The above is the first step.

  In the next second step, similarly, the control valves 3a to 3d and the switching valves 115, 116, 215, and 216 are switched so that the adsorption / desorption unit 1 becomes the adsorption step and the adsorption / desorption unit 2 becomes the regeneration step. Cooling heat, that is, cooling output can be obtained from the evaporator 4. In the second step, the valves 3 a and 3 d are opened, the valves 3 b and 3 c are closed, and the vapor from the evaporator 4 is introduced into the adsorption / desorption unit 1. The water vapor desorbed by the adsorption / desorption unit 2 is introduced into the condenser 5. Cooling water is passed through the heat exchanger of the adsorption / desorption unit 1, and warm water is passed through the heat exchanger of the adsorption / desorption unit 2.

  The continuous operation of the adsorption heat pump can be performed by sequentially switching the first and second steps.

  When this operation is continued, the organic binder in the coating film 12b is gradually decomposed to generate an acid. This acid volatilizes and becomes gaseous. This gaseous acid is sorbed by the acid trap particles in the coating film 12b. For this reason, the acid concentration in a heat pump becomes low, and deterioration of a zeolite and corrosion of an apparatus are prevented.

  In FIG. 1, two adsorption / desorption units are installed, but one or more units may be installed.

  In the above-described embodiment, the acid trap particles are present in the fins 12, but the acid trap particles may be disposed in places other than the fins 12.

  For example, as shown in FIG. 4, the acid trap device 14 in which the acid trap particles 14 c are arranged on the upper portion of the container 14 a may be installed in the adsorption / desorption units 1 and 2.

  A water-permeable support member 14b made of a punching metal, mesh, screen, or the like is provided in the middle or higher position of the container 14a of the acid trap device 14, and the acid trap particles 14c are filled on the upper side. Water is collected at the bottom of the container 14a when it falls after contacting the acid trap particles 14c.

  Since this water is alkaline containing a hydroxide, it is stored in the container 14a so as not to flow out of the container 14a. The water accumulated at the bottom of the container 14a evaporates during maintenance of the adsorption / desorption unit or during a vacuuming operation incorporated in the operation program. Further, the water may be drained at an appropriate timing, for example, by connecting a drain pipe with a valve to the container 14a in advance during maintenance of the adsorption / desorption unit. As illustrated, the container 14a may have a shape with a large diameter on the upper side, or may have an equal diameter in the vertical direction, and the shape is not limited.

  The acid trap device 14 may be fixedly installed in the adsorption / desorption units 1 and 2 or may be installed in a suspended manner. In order to install in a suspended manner, a wire or handle (handle) for suspension may be provided on the container 14a.

  As shown in FIG. 5, an opening 15e may be provided at the bottom of a vessel 15 such as an adsorption / desorption unit of an adsorption heat pump, and the acid trap unit 14 may be installed so as to face the opening 15e.

  In the present invention, a packed bed of acid trap particles may be formed in the middle of a pipe through which water vapor passes.

  FIG. 6 shows an example thereof, and an acid trap device 16 is provided in the middle of at least one of the pipes 3A to 3D (the pipe 3A in FIG. 6). The acid trap unit 16 includes a canister 16a whose vertical direction is the cylinder axis direction, a water permeable support member 16b made of a punching metal, a mesh, a screen or the like provided in the middle of the canister 16a, and an upper side thereof. And acid trap particles 16c filled in the. One pipe is connected to the upper side of the acid trap particles 16c on the support member 16b, and the other pipe is connected to the lower side of the support member 16b, so that water containing acid gas is filled with the acid trap particles 16c. Passes through the layers and the acid is absorbed.

  The canister 16a extends further downward than the pipe 3A connected to the lower side of the support member 16b, so that the alkaline water generated in contact with the acid trap particles 16c is accumulated at the bottom of the canister 16a. It is configured.

  A drain pipe with a valve for extracting water accumulated at the bottom of the canister 16a may be connected to the bottom of the canister 16a.

  Although illustration is omitted, as the acid trapping device, a plate-like substrate made of a plate-like substrate made of metal, ceramic or the like and a coating film containing acid trap particles formed on the surface of the substrate may be used. This plate-shaped acid trap device is suspended or fixedly installed in a vessel or pipe, for example. The installation form is not particularly limited.

  In FIG. 1, the condenser and the evaporator are provided separately, but it is also possible to use an adsorption heat pump having a configuration in which an evaporator, an adsorption / desorption device, and a condenser are installed in one vessel.

  An example of such an adsorption heat pump will be described with reference to FIGS.

  The adsorption heat pump 20 of FIG. 7 divides the inside of the pressure-resistant vessel 21 into three chambers: a condensation chamber 24, an adsorption / desorption chamber 25, and an evaporation chamber 26 by partition plates 22 and 23.

  The partition plates 22 and 23 are provided with on-off valves 22a and 23a.

  A condenser 27 is installed in the uppermost condensation chamber 24, the adsorption / desorption device 10 is installed in the middle adsorption / desorption chamber 25, and an evaporator 29 is installed in the lowermost evaporation chamber 26.

  The condenser 27 includes a heat transfer tube 27a through which cooling water is passed, and a water collection tray 27b installed below the heat transfer tube 27a.

  The evaporator 29 has a heat transfer tube 29a through which hot water is passed, and a water sprinkler 29b that pours water into the heat transfer tube 29a.

  The water accumulated at the bottom of the evaporation chamber 26 is supplied to the sprinkler 29b by the pump 30.

  The water in the tray 27 b of the condenser 27 is introduced into the evaporation chamber 26 through a pipe 31.

  The adsorption heat pump 20 alternately performs an adsorption process and a desorption process. In the adsorption step, as shown in the figure, the valve 22a is closed and the valve 23a is opened, and cooling water is allowed to flow through the heat exchanger 11 of the adsorption / desorption device 10. Further, water is passed through the heat transfer tube 29a of the evaporator 29 and water is sprinkled from the sprinkler 29b. The generated water vapor enters the adsorption / desorption chamber 25 and is adsorbed by the adsorption / desorption device 10. The water flowing through the heat transfer tube 29a is cooled by latent heat of evaporation.

  In the desorption process, the valve 22 a is opened, the valve 23 a is closed, and hot water is allowed to flow through the heat exchanger 11 of the adsorption / desorption device 10. Further, cooling water is passed through the heat transfer tube 27 a of the condenser 27. The water vapor generated from the adsorption / desorption device 10 is condensed in the condensation chamber 24, collected in the tray 27 b, and returned to the evaporation chamber 26 through the pipe 31.

  It is preferable to provide an acid trap device such as the acid trap device 14 shown in FIG. 4 in at least one of the chambers 24 to 26 of the adsorption heat pump 20.

  The adsorption heat pump 20 </ b> A in FIG. 8 partitions the chambers 24, 25, and 26 by providing a recess 21 a that is recessed inward on the side surface of the vessel 21. In the adsorption heat pump 20A provided with the recess 21a, the acid trap device 14 can be installed on the bottom surface of the condensation chamber 24 and / or the adsorption / desorption chamber 25 as shown in FIG. You may install the acid trap apparatus of FIG. 4 etc. in at least one of the chambers 24-26. The other configurations in FIG. 8 are the same as those in FIG. 7, and the same reference numerals indicate the same parts.

  The adsorption heat pump 20B of FIG. 9 has the same configuration as the adsorption heat pump 20 of FIG. 7 except that the partition plates 22 and 23 are omitted, and the same reference numerals denote the same parts. Also in this case, it is preferable to provide an acid trap device as shown in FIG.

  The adsorption heat pump 20C in FIG. 10 is a condenser / evaporator integrated adsorption heat pump in which one heat transfer tube 29a is used not only as an evaporator but also as a condenser. 27a and water collection tray 27b are omitted. The other structure is the same as that of FIG. 9, and the same code | symbol has shown the identical part. It is preferable to install an acid trap device shown in FIG.

  In the evaporation step, water is passed through the heat transfer tube 29a and water is sprinkled from the sprinkler 29b. In the condensation step, cooling water is passed through the heat transfer tube 29a to condense the water vapor in the vessel 21.

  11 and 12 show adsorption heat pumps 20D and 20E having a structure in which a plurality of (two in this case) adsorption / desorption chambers are arranged in a single vessel.

  11 and 12, by providing a vertical partition plate 33 in the vessel 21, two adsorption / desorption chambers 25A and 25B are provided, valves 22a and 22b are provided at the ceiling of each chamber 25A and 25B, and valves are provided at the bottom. 23a and 23b are provided.

  While continuously passing water through the heat transfer tubes 27a and 29a, the valve 22a is closed in the adsorption / desorption chamber 25A, the valve 23a is opened, the adsorption process is performed, and the valve 22b is opened in the other adsorption / desorption chamber 25B. The valve 23b is closed and the desorption process is performed.

  By opening and closing the valves 22a and 23a and the valves 22b and 23b in reverse to FIG. 9, the desorption process is performed in the adsorption / desorption chamber 25A, and the adsorption process is performed in the adsorption / desorption chamber 25B. Therefore, the adsorption heat pump 20D continuously obtains cold water from the heat transfer tube 29a by switching between opening and closing of the valves 22a and 23a and the valves 22b and 23b.

  The adsorption heat pump 20E of FIG. 12 has the same structure as FIG. 11 except that a recess 21a is provided in the vessel 21 to partition the condensation chamber 24, the adsorption / desorption chambers 25A and 25B, and the evaporation chamber 26. Thus, it is possible to continuously supply cold water as in the adsorption heat pump 20D of FIG.

  11 and 12 are the same as those in FIGS. 7 and 8, and the same reference numerals denote the same parts. 11 and 12, it is preferable to install the acid trap shown in FIG. In the case of FIG. 12, an acid trap device can also be installed in the form shown in FIG.

  In the above embodiment, the adsorption / desorption device 10 has the structure shown in FIGS. 2 and 3, and some of the fins have a coating film containing acid trap particles, and the other fins have a coating film containing zeolite. It has become. However, acid trap particles may be included in some or all zeolite-containing coatings.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited at all by the following examples.

<Example 1>
[Preparation of slurry]
As zeolite, 8 g of AQSOA (registered trademark: omitted hereinafter) -Z02 (Mitsubishi Resin Co., Ltd., product name, average particle size: 3 μm) which is ALPO-based zeolite, Magnesium oxide RF-98 (Ube Materials Co., Ltd., trade name) Magnesium oxide purity 97.5%, thermal conductivity of about 50 W / (K · m), average particle size 58 μm, magnesium hydroxide solubility at 20 ° C. of 9.6 mg / 100 cm ³ —H ₂ O), 2 g, ion-exchanged water 12 g was mixed. At this time, the temperature rises due to the heat of adsorption, but after cooling sufficiently, an aqueous emulsion of jER1256 (trade name of Mitsubishi Chemical Corporation, bisphenol A type epoxy resin) as an organic binder (average particle size 0.5 μm, solid content 45 wt. %) Was added in terms of solid content (actual addition amount 2.2 g) and mixed uniformly. Further, 0.1 g of adipic acid dihydrazide (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing agent was added to this mixed solution, and TAFIGEL PUR61 (manufactured by MUNZING CHEMIE, nonvolatile content: 25 wt%, urethane type for preventing sedimentation of magnesium oxide particles. A slurry was prepared by adding 0.2 g of an aqueous solution obtained by diluting the thickener) twice.

[Formation of coating film]
The slurry was applied on an aluminum plate to a thickness of 1 mm by a casting method, and then cured by heating at 160 ° C. for 1 hour. The formed coating film has a thickness of 1 mm, the zeolite content is 72 wt%, the magnesium oxide particles (the surface layer is magnesium hydroxide) content is 18 wt%, and the organic binder content is 10 wt%. The porosity determined by the immersion method using silicone oil is 50.2 wt%.

[Measurement of thermal conductivity over the coating film]
The coating film was peeled off from the aluminum plate, and a disk-shaped coating film test piece having a diameter of 10 mm and a thickness of 1 mm was cut out. Using the obtained coating film test piece, the thermal conductivity was measured only on the coating film.

  The apparent thermal conductivity of the coating film was determined by specific heat determined by DSC (Differential Scanning Calorimeter DSC-7 type manufactured by Perkin Elmer) and laser flash method (thermal constant measuring device TC-9000 type manufactured by ULVAC-RIKO). Calculated as the product of thermal diffusivity and density. All measurements were performed in an absolutely dry state. The measurement temperature was room temperature (about 20 ° C.).

  As a result, the apparent thermal conductivity of the coating film was 0.171 W / (m · K).

[Confirmation of acid neutralization function of coating film]
The coating film was peeled off from the above aluminum plate and ground with a mortar to make a powder. As shown in FIG. 13, 5 g of this coating powder 61 is taken and placed in a 20 ml glass bottle 62, and this glass bottle 62 is further placed in a 250 ml glass bottle 63, and a formic acid aqueous solution (ion exchange) is placed outside the 20 ml glass bottle 62. 10 ml of 64) in which 30 mg of 90% formic acid was added to 100 ml of water was injected. The upper part of the 20 ml glass bottle 62 is open, the 250 ml glass bottle 63 is covered, and the whole is placed in a constant temperature bath (“SH-241” manufactured by Espec) and the pH and electrical conductivity of the formic acid aqueous solution. Was recorded over time. The results are shown in Table 1.

  The pH and electrical conductivity are measured by removing the aqueous formic acid solution and cooling it with water so that the temperature is 21 ° C. or higher and 25 ° C. or lower, and then a pH meter D-54 manufactured by Horiba, Ltd. -10D), and the liquid was returned again after the measurement.

  In Table 1, for comparison purposes, the results when the coating powder was not placed in the glass bottle 62 and the results of the same measurement with 1 g of magnesium oxide contained in the glass bottle 2 were also shown.

<Comparative Example 1>
Except that the magnesium oxide particles were replaced with AQSOA-Z02, a slurry was prepared in the same procedure as in Example 1, and a coating film was formed and various measurements were performed. 131 W / (m · K). The acid neutralizing function was as shown in Table 1.

  The following can be understood from the above results.

  The apparent thermal conductivity of the coating film of Example 1 was 1.3 times that of the comparative example, and the effect of improving the thermal conductivity was recognized.

  In Example 1, since the pH of the formic acid aqueous solution changed to the neutral side with time and the electrical conductivity also decreased, the formic acid in the aqueous solution was converted into magnesium oxide particles in the coating film (the surface layer was hydroxylated). It turns out to be neutralized by reacting with magnesium.

<Example 2>
An experiment was conducted in the same manner as in Example 1 except that 5 g of the following magnesium oxide powder was used instead of the coating powder, and 50 g of the following formic acid aqueous solution was used, and the thermostat was kept at 90 ° C. The pH and electrical conductivity of the formic acid aqueous solution after the measurement were measured, and the results are shown in Table 2.

Magnesium oxide powder: Wako Pure Chemical Industries, Ltd. Purity 99.9%, average particle size 10μm
Formic acid aqueous solution: A mixture of ion-exchanged water and 99% purity formic acid so that the formic acid concentration is 110 mg / l. pH value 3.3, electrical conductivity 23.2 mS / m

<Example 3>
The experiment was performed in the same manner as in Example 2 except that the amount of magnesium oxide was 1 g, and the results are shown in Table 2.

<Comparative example 2>
Experiments were performed in the same manner as in Example 2 except that magnesium oxide was not used and the glass bottle 62 was left empty in the glass bottle 63. The results are shown in Table 2.

  Table 2 shows the formic acid aqueous solution using an approximate expression (pH = −0.02828 Ln (concentration mg / l) +4.6291) obtained from the relationship between the formic acid concentration and the pH value of the formic acid aqueous solution measured in advance by experiments. The formic acid concentration of the formic acid aqueous solution calculated from the pH value is also shown.

<Example 4>
An experiment was conducted using the same magnesium oxide 5 g used in Example 2 and 40 g of the same formic acid aqueous solution used in Example 2 with the experimental apparatus shown in FIG.

  In a 1000 ml glass four-necked separable flask 70, the magnesium oxide 70 and the formic acid aqueous solution 72 are allowed to coexist so that they do not come into contact with each other, and the aqueous formic acid aqueous solution is refluxed at 80 ° C. The time change was measured.

  5 g of magnesium oxide 71 was put into a glass beaker 73 having a capacity of 50 ml, and the beaker 73 was put into a net 74, and a wire 75 was attached to the net 74 and fixed to one mouth 70 a of the separable flask 70. A rubber plug 70b was installed at the mouth 70a to shut off the outside air.

  A thermometer 76 for measuring the temperature of the formic acid aqueous solution 72 and a cooling pipe 77 for cooling the steam were provided at the mouths 70c and 70d of the other separable flask 70, respectively, and the system was sealed.

  These were placed in an oil bath 79, and a stirrer 80a and a stirrer 80 for stirring the formic acid aqueous solution were installed, and refluxed while maintaining the formic acid aqueous solution at 80 ° C. When a predetermined time had elapsed, the aqueous formic acid solution was extracted with a pipette, water-cooled to 21 ° C. or higher and 30 ° C. or lower, and then the pH and electrical conductivity were measured using the same measuring apparatus as in Example 1. Table 3 shows the formic acid concentration calculated from the pH value in the same manner as in Example 2.

  As a result, as shown in Table 3, the pH value increased with the passage of time, and reached pH 4.0 in 10 hours.

  From Examples 2 to 4, formic acid in the formic acid aqueous solution volatilizes and reacts with magnesium oxide in the system. In Example 2, the formic acid concentration is reduced by about 40%, and in Example 4, about 90% after 10 hours. % Can be seen.

  From the above results, it can be seen that according to the present invention, acids such as formic acid generated in the adsorption heat pump are neutralized and removed by the magnesium oxide installed in the adsorption heat pump.

1, 2 Adsorption / desorption unit 1a, 2a Heat medium piping 3A, 3B, 3C, 3D Adsorbate piping 3a, 3b, 3c, 3d Control valve 6 Return piping 10 Adsorption / desorption device 11 Heat transfer tube 12 Fin 12a Substrate 12b Coating film 14 , 16 Acid trap device 14c, 16c Acid trap particle 20, 20A, 20B, 20C, 20D, 20E Adsorption heat pump 21 Pressure vessel 22, 23 Partition plate 22a, 22b, 23a, 23b Open / close valve 24 Condensing chamber 25, 25A, 25B Adsorption / desorption chamber 26 Evaporation chamber 27 Condenser 29 Evaporator 61 Coating powder 62, 63 Glass bottle 64 Formic acid aqueous solution 70 Separable flask 71 Magnesium oxide powder 72 Formic acid aqueous solution 76 Thermometer 77 Cooling pipe 79 Oil bath 80 Stirrer 115 Switching valve 116 Switching Valve 215 Switching valve 216 Replacement valve 300 indoor unit 301 pump

Claims (13)

An adsorption heat pump having an adsorption / desorption device, a condenser, and an evaporator,
The adsorption / desorption device includes a heat exchanger and an adsorption element that can be heated or cooled by the heat exchanger,
The adsorbing element has a base and a coating film containing a zeolite and an organic binder provided on the base,
A hydroxide having a solubility at 20 ° C. of 20 mg / 100 cm ³ -H ₂ O or less and / or the hydroxide can be formed by a hydration reaction in at least a part of the portion where water vapor is adsorbed. Adsorption heat pump with particles.   The adsorption heat pump according to claim 1, wherein the hydroxide particles contain a dehydrated product of the hydroxide.   The adsorption heat pump according to claim 2, wherein the hydroxide dehydrate is an oxide.   The adsorption heat pump according to any one of claims 1 to 3, wherein the hydroxide is at least one selected from magnesium hydroxide, aluminum hydroxide, and zinc hydroxide.   The adsorption heat pump according to claim 1, wherein at least a part of the particles is magnesium oxide.   The adsorption heat pump according to any one of claims 1 to 5, wherein the condenser and the evaporator are integrated.   7. The hydroxide according to any one of claims 1 to 6, wherein the hydroxide particles and / or particles capable of forming the hydroxide by a hydration reaction are present in the coating film of the heat exchanger. The adsorption heat pump described.   The amount of the hydroxide particles in the coating film of the heat exchanger and / or the particles capable of forming the hydroxide by a hydration reaction is 10 wt% or more and 30 wt% or less. Adsorption heat pump.   The hydroxide particles and / or the particles capable of forming the hydroxide by a hydration reaction are present in a place other than the coating film and in at least a part of the water vapor flow path as an adsorbate. The adsorption heat pump according to any one of claims 1 to 6.   The heat exchanger includes a first coating film that does not include the hydroxide particles and / or particles that can form the hydroxide by a hydration reaction, the hydroxide particles, and / or water. The adsorption heat pump according to any one of claims 1 to 6, further comprising a second coating film containing particles capable of forming the hydroxide by a sum reaction.   The adsorption heat pump according to any one of claims 1 to 10, wherein a container containing the hydroxide particles and / or particles capable of forming the hydroxide by a hydration reaction is installed.   The adsorption heat pump according to any one of claims 1 to 11, wherein the hydroxide particles and / or particles capable of forming the hydroxide by a hydration reaction are disposed in a water vapor circulation pipe.   The hydroxide particle and / or the particle capable of forming the hydroxide by a hydration reaction is present in an amount of 0.1 wt% or more with respect to the adsorbate. The adsorption heat pump according to Item 1.

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