JP2015075267A - Desiccant air conditioning system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a desiccant air conditioning system that can more expensively produce air-conditioning air having lower temperature and lower humidity.SOLUTION: A desiccant air conditioning system comprises: a dehumidifier 1 using an adsorbent; and an indirect vaporization cooling device 2 using latent heat of vaporization of water. The dehumidifier 1 is for supplying dehumidified air that is obtained in an adsorption process to the indirect vaporization cooling device 2 and discharging moist air that is obtained in a desorption process to outside of the system. The indirect vaporization cooling device 2 includes: a cooling duct 22 that has a wet wall 24 on the inner side and to which part of the dehumidified air is sent from the dehumidifier 1 as air for operation; and a cooled duct 23 to which the other part of the dehumidified air is sent as cooled air and that sends out air-conditioning low-temperature air. A water passage for supplying water discharged from the wet wall 24 of the cooling duct 22 of the indirect vaporization cooling device 2 to a region in the adsorption process and supplying hot water supplied from a cogeneration device 3 to a region in the desorption process is attached to the dehumidifier 1.

Description

  The present invention relates to a desiccant air conditioning system, and more particularly, to a desiccant air conditioning system in which a dehumidifying device using an adsorbent is combined with an indirect evaporative cooling device using the latent heat of vaporization of water.

  The desiccant air conditioning system is a system that adjusts humidity using the adsorption / desorption function of adsorbents. Various cooling devices that can reduce energy consumption by using low-temperature exhaust heat such as cogeneration systems, air conditioning As a device and dehumidifying / humidifying device, contribution to environmental problems is expected.

  For example, a desiccant air conditioning system configured as a dehumidifying device includes a rotor (adsorbing element) in which an adsorbent is supported on a cylindrical honeycomb structure, and one air passage that allows air to be dehumidified to pass through the semicircular portion of the rotor. And the other air passage that allows the adsorbent regeneration air to pass through the other semicircular part of the rotor, and adsorbs water vapor from the air flowing through one air passage to the adsorbent while rotating the rotor. By generating the dehumidified air, the adsorbent is regenerated by desorbing water vapor from the adsorbent with the heated air flowing through the other air passage (see Patent Documents 1 and 2).

  Recently, an air-conditioning system that saves energy and generates dehumidified low-temperature air by combining an indirect evaporative cooling device that uses the latent heat of vaporization of water with the rotor-type dehumidifying device as described above has also been proposed. Has been. An indirect evaporative cooling device (steam cooling assembly) includes a plurality of cooling ducts (secondary channels of an evaporative cooler tube) having a wet wall to which evaporating water is supplied on the inner surface and air for operation is fed. The cooling duct (primary channel) is provided between the cooling ducts and sends out the low-temperature air by sending the cooling air. And in said air conditioning system, the air dehumidified with the rotor (desiccant wheel) is supplied to an indirect vaporization cooling device (refer patent document 3).

JP 2003-38928 A JP 2003-222354 A Special table 2010-526981 gazette

  By the way, in the air conditioning system using the indirect evaporative cooling device as described above, it is desirable to supply air of lower humidity as the working air in order to obtain a sufficient cooling effect, but activated alumina or silica gel is used. Since the dehumidified amount of the rotor is small, there is a problem that the amount of low-temperature air generated by the indirect evaporative cooling device is smaller than the device scale. In addition, when a general zeolite is used as the adsorbent for the rotor, high temperature air of, for example, 90 ° C. or more is required for desorption and regeneration of the adsorbent, and a heater must be disposed, which causes a problem in operating cost. .

  The present invention has been made in view of the above circumstances, and its purpose is a desiccant air conditioning system that is a combination of a dehumidifying device using an adsorbent and an indirect evaporative cooling device using the latent heat of vaporization of water. Then, it is providing the desiccant air-conditioning system which can produce | generate the air for air-conditioning of lower temperature and low humidity at lower cost.

  In order to solve the above problems, in the present invention, dehumidified air obtained in the adsorption process in the dehumidifying device is supplied to the indirect evaporative cooling device, and part of the dehumidified air is used as working air in the indirect evaporative cooling device. The other part of the dehumidified air is used as air to be cooled to generate low-temperature air for air conditioning. At that time, the water used for cooling in the indirect evaporative cooling device is supplied to the adsorption process area of the dehumidifying device by supplying water that has cooled down, thereby promoting the adsorption action of the adsorbent and supplying it from the cogeneration device. By supplying the heated water to the desorption process area of the dehumidifier, the desorption action of the adsorbent was promoted.

  That is, the gist of the present invention is a desiccant air conditioning system that combines a dehumidifying device that generates dehumidified air using an adsorbent and an indirect evaporative cooling device that generates low-temperature air using the latent heat of vaporization of water. The dehumidifier has an air supply path for supplying dehumidified air obtained in the adsorption process to the indirect evaporative cooling device, and an exhaust path for discharging the humid air obtained in the desorption process out of the system. The cooling device has a wet wall to which evaporation water is supplied, and a cooling duct in which a part of the dehumidified air is supplied as working air from an air supply path of the dehumidifying device, and is in contact with the cooling duct. And a cooling duct that sends out low-temperature air for air conditioning by supplying another part of the dehumidifying air from the air supply passage of the dehumidifying apparatus as cooled air, and the dehumidifying apparatus includes an indirect evaporative cooling device Drain from the wet wall of the cooling duct Is the water supply to the region of the adsorption step lies in desiccant air-conditioning system, characterized in that the cogeneration water passage for supplying the area of the desorption step hot water supplied from the device is attached.

  According to the desiccant air conditioning system according to the present invention, a part of the dehumidified air obtained by the dehumidifying device is used as the operating air of the indirect evaporative cooling device, so that the cooling effect in the indirect evaporative cooling device can be improved. In addition, since the water with a reduced temperature generated by the indirect evaporative cooling device is used for the dehumidification device adsorption process, the adsorption effect of the dehumidification device can be improved, and the hot water supplied from the cogeneration device can be removed from the dehumidification device. Therefore, air-conditioning air having a lower temperature and lower humidity can be generated at lower cost than a system using a cooling device or a heater using a refrigerant such as Freon.

It is a flowchart which shows the component of the desiccant air conditioning system which concerns on this invention. It is a flowchart which shows the state which switched the adsorption | suction process and desorption process of the dehumidifier in the desiccant air conditioning system of FIG. It is a graph of the water vapor | steam adsorption isotherm which shows the adsorption | suction characteristic of the adsorbent (SAPO, FAPO) suitably applied to the system of this invention, and another adsorbent.

  An embodiment of a desiccant air conditioning system (hereinafter abbreviated as “air conditioning system”) according to the present invention will be described with reference to the drawings. In addition, this invention is not limited to the following embodiment, unless the meaning is exceeded.

  As shown in FIGS. 1 and 2, the air conditioning system of the present invention includes a dehumidifying device 1 that generates dehumidified air using an adsorbent, and indirect evaporative cooling that generates low-temperature air using latent heat of water evaporation. It is configured in combination with the device 2 and uses hot water obtained by a cogeneration device or the like. In the figure, devices such as an air supply path, an exhaust path, an airflow switching damper, a blower, and a water flow path pump of the dehumidifier 1 to be described later are omitted.

  The dehumidifying apparatus 1 includes an adsorbing element that carries an adsorbent and is configured to be able to heat and cool the adsorbing element. For example, as shown in FIG. 1, the dehumidifying device 1 includes at least one pair of plate fin type adsorbing elements 1a and 1b, and the adsorbing elements 1a and 1b are each formed in a flat plate shape and A large number of adsorbing sheets having adsorbents coated on the surface are arranged in parallel and in parallel, and each adsorbing sheet is configured to pass through a heat medium passage through which cold water or hot water flows. Since the plate fin type adsorption elements 1a and 1b are excellent in heat exchange efficiency, they are suitable for utilizing low-temperature waste heat such as cogeneration.

  As the adsorbing element of the dehumidifying device 1, in addition to the plate fin type adsorbing elements 1a and 1b, a corrugated fin type or rotor type element can be used, although not shown. The corrugated fin-type adsorbing element has an inlet header supplied with cold water or hot water, an outlet header that discharges cold water or hot water, and a plurality of the heat medium flowing between the headers in parallel and in parallel. It is composed of a straight tubular heat medium flow path and a large number of adsorbing sheets inserted between the heat medium flow paths, and each adsorbing sheet is formed in a band shape that bends zigzag along its length direction; An adsorbent is applied to the surface.

  Further, the rotor-type adsorption element is formed by alternately arranging an adsorption sheet formed in a substantially corrugated plate shape and an adsorption sheet formed in a substantially flat plate shape along a diametrical direction, that is, a honeycomb sheet. Is a cylindrical honeycomb structure (for example, a short-axis columnar) honeycomb structure in which a large number of ventilation cells having a substantially triangular opening are provided by laminating a plurality of layers around an axis, and from one end surface to the other end surface It is configured to absorb and desorb water vapor by being configured to be able to vent. In the case of using a rotor-type adsorption element, means for supplying cold air and hot air to the rotor during the adsorption / desorption operation is disposed. The basic structure of the plate fin type, corrugated fin type, and rotor type elements as described above is disclosed in, for example, Japanese Patent Application Laid-Open No. 2007-144417.

  Although not shown, in the dehumidifying device 1, the adsorption / desorption operations by the adsorption elements 1a and 1b are alternately repeated. However, when performing the adsorption operation by the adsorption element 1a, the air (dehumidified air) that has passed through the adsorption element 1a is indirectly used. The air that has been sent to the gasification cooling device 2 and that has passed through the adsorption element 1b (wet air) is exhausted out of the system, and when the adsorption operation is performed in the adsorption element 1b, the air that has passed through the adsorption element 1b (Dehumidified air) is sent to the indirect evaporative cooling device 2 and air (humid air) that has passed through the adsorption element 1a is exhausted outside the system. The flow of the humid air can be switched.

  That is, the dehumidifier 1 includes an air supply path that supplies dehumidified air obtained in the adsorption process to the indirect evaporative cooling apparatus, and an exhaust path that discharges wet air obtained in the desorption process to the outside of the system. In FIG. 1, an arrow indicated by a solid line on the downstream side of the adsorption element 1a and an arrow indicated by a solid line on the downstream side of the adsorption element 1b in FIG. 2 represent the flow of dehumidified air. An arrow indicated by a chain line on the downstream side of FIG. 2 and an arrow indicated by a chain line on the downstream side of the adsorption element 1b in FIG. FIG. 1 is a diagram showing a state in which the adsorption element 1a is in the adsorption process, and FIG. 2 is a diagram showing a state in which the adsorption element 1b is in the adsorption process. In FIGS. Although the flow is different, the apparatus configuration is the same.

  The indirect evaporative cooling device 2 is a device that generates low-temperature air using the latent heat of vaporization of water. The indirect vaporization cooling device 2 includes a wet wall 24 to which evaporation water is supplied and dehumidifies from the air supply path of the dehumidifier 1. A cooling duct 22 in which a part of the air is supplied as working air, and another part of the dehumidified air that is provided in contact with the cooling duct and supplied from the air supply path of the dehumidifier 1 is supplied as cooled air. And a cooled duct 23 for sending out low-temperature air.

  Specifically, as shown in FIG. 1, the indirect evaporative cooling device 2 includes an intake duct 21 that takes in the working air and an intake duct that is continuous with the intake duct and that has a thermally conductive partition wall. A cooling duct 22 provided adjacent to the cooling duct 22 and a cooling duct 23 provided adjacent to the cooling duct 22 with a thermally conductive partition wall therebetween and to which cooled air is supplied are provided. The inside is configured as a wet wall 24 to which water is supplied.

  The wet wall 24 of the cooling duct 22 is composed of a fiber aggregate mat or a porous molding material, and a presser plate having a large number of holes opened to promote water evaporation is disposed on the surface thereof. Yes. In the drawing, the duct structure is schematically shown. However, in the indirect evaporative cooling device 2, a plurality of combinations of the intake duct 21, the cooling duct 22, and the cooled duct 23 are usually configured. Each duct is arranged in a state where the air blowing direction of the cooling duct 22 is orthogonal to the air blowing direction of the duct 23 to be cooled. Note that water is supplied to the wet wall 24 of the cooling duct 22 through a flow path 64 (water flow path) described later. The structure of the main body of the indirect evaporative cooling device as described above is disclosed in JP-T 2010-526981, JP-A 2010-121920, and the like.

  Further, in the dehumidifier 1, cold water and hot water are used for cooling in the adsorption operation of the adsorption elements 1a and 1b and heating in the desorption operation, respectively. Therefore, in the air conditioning system of the present invention, several flows for circulating water are used. There is a road. That is, the dehumidifier 1 supplies the water discharged from the wet wall 24 of the cooling duct 22 of the indirect evaporative cooler 2 to the adsorption process area, and the hot water supplied from the cogeneration apparatus 3 to the desorption process area. A water flow path for supplying to is attached.

  Specifically, the rear end of the cooling duct 22 of the indirect evaporative cooling apparatus 2 is connected to a flow path 61 for taking out water that has not evaporated on the wet wall 24, and the flow path 61 is connected to the dehumidifying apparatus 1. The flow path 62 connected to one end (lower end in FIG. 1) of the heat medium flow path of one adsorption element 1a (FIG. 1) in the adsorption process, and the other adsorption element 1b (FIG. 2) in the adsorption process. Is connected via a four-way switching valve 4 to a flow channel 66 connected to one end (upper end in FIG. 2) of the hot water flow channel. A flow path 63 for taking out water used for cooling (or heating) the adsorption element is connected to the other end (the upper end in FIG. 1) of the heat medium flow path of the adsorption element 1a. The flow path 64 connected to the wet wall 24 of the cooling duct 22 of the indirect evaporative cooling device 2 and the flow path 68 for returning the hot water to the cogeneration device 3 are connected via the four-way switching valve 5. . In addition, the code | symbol 7 has shown the drainage channel used in a maintenance.

  The cogeneration apparatus 3 (hot water supply apparatus) is connected to a flow path 65 for supplying hot water for desorption, and the flow path 65 is connected to the other adsorption element 1b (in the desorption process of the dehumidifying apparatus 1). 1), a flow path 66 connected to one end of the heat medium flow path (upper end in FIG. 1), and one end of the heat medium flow path of one adsorption element 1a (FIG. 2) in the desorption process (FIG. 2). The lower end) is connected via the aforementioned four-way switching valve 4. A flow path 67 for extracting water used for heating (or cooling) the adsorption element is connected to the other end (lower end in FIG. 1) of the heat medium flow path of the adsorption element 1b. Via the four-way switching valve 5, the flow path 68 for returning the hot water to the cogeneration apparatus 3 and the flow path 64 connected to the wet wall 24 of the cooling duct 22 of the indirect vaporization cooling apparatus 2 are connected. It is connected.

  In addition, as the hot water used in the present invention, solar hot water, hot water generated by heat discharged from an automobile, a factory, or the like can be used, but discharged from the cogeneration apparatus 3 having a stable temperature, flow rate, and the like. Hot water is preferred. As is well known, the cogeneration apparatus 3 is a combined heat and power supply system that takes out heat and cold using exhaust heat from an internal combustion engine, an external combustion engine, and the like, and uses low-temperature waste heat by, for example, hot water at 60 to 70 ° C. by a heat exchanger. Can be taken out as.

  By the way, in order to generate cooler air-conditioning air by the indirect evaporative cooling device 2, the adsorption elements 1a and 1b of the dehumidifying device 1 have excellent adsorption capability in the normal temperature range and rapid desorption in the low temperature range. Ability is required. Therefore, in the air conditioning system of the present invention, an adsorbent having specific adsorption characteristics is used for the dehumidifier 1.

  Examples of the adsorbent include zeolite having the following characteristics. That is, the relative vapor pressure in the water vapor adsorption isotherm at 40 ° C. is 0.05 or more, the adsorption amount is 0.1 g / g or less, and the relative vapor pressure is 0.05 or more and 0.3 or less. Zeolite whose water vapor adsorption amount change when 0.15 changes is 0.15 g / g or more. Alternatively, in the water vapor adsorption isotherm at 55 ° C., when the relative vapor pressure is 0.03, the adsorption amount is 0.1 g / g or less, and when the relative vapor pressure changes by 0.15, the change in water vapor adsorption amount is 0.1. 15 g / g or more of zeolite. Alternatively, a zeolite having an adsorption amount of 0.10 g / g or more when the relative vapor pressure is 0.17 in a 35 ° C. water vapor adsorption isotherm. Alternatively, when the relative vapor pressure in the water vapor adsorption isotherm in the adsorption process at 35 ° C. is 0.17 and the relative vapor pressure in the water vapor adsorption isotherm in the desorption process at 75 ° C. is 0.15 A zeolite having a difference from the water vapor adsorption amount of 0.07 g / g or more. By providing the above characteristics, for example, by supplying outside air having a temperature of 35 ° C. and a relative humidity of 40% to the adsorption region (adsorption element 1a or 1b) of the dehumidifier 1, the temperature is 40 ° C. and the relative humidity is 12 % Dehumidified air can be generated, and the outside air having a temperature of 35 ° C. and a relative humidity of 40% is supplied to the desorption region (adsorption element 1b or 1a) of the dehumidifying device 1 and further heated to about 70 ° C. By doing so, it is possible to easily desorb and regenerate.

  Examples of the zeolite having the above characteristics include aluminophosphates containing Al and P in the skeleton structure. The aluminophosphates are crystalline aluminophosphates defined by IZA (International Zeolite Association).

  In the crystalline aluminophosphate, atoms constituting the skeleton structure are aluminum and phosphorus, and a part thereof may be substituted with another atom (Me). Among them, I) Aluminum is a heteroatom (Me1: where Me1 belongs to the third or fourth period of the periodic table, elements of Group 2A, Group 7A, Group 8, Group 1B, Group 2B, Group 3B (excluding Al) A partially substituted Me-aluminophosphate, II) phosphorus is a heteroatom (Me2: where Me2 is a Group 4B element belonging to the third or fourth period of the periodic table) ) Or Me-aluminophosphate in which both aluminum and phosphorus are substituted with heteroatoms (Me1 and Me2 respectively) are preferred from the standpoint of adsorption properties.

  The constituent ratio (molar ratio) of Me, Al, and P constituting the skeleton structure is usually a molar ratio of the following formulas (1-1) to (3-1), and preferably the formula (1- 2) to (3-2). If the value of x is smaller than the above range, the amount of adsorption in the region where the pressure of adsorbate is low tends to be small or the synthesis tends to be difficult. If it is larger than the above range, impurities are mixed during synthesis. It tends to be easy to do. Further, when the values of y and z are out of the above ranges, synthesis is difficult.

  In Me-aluminophosphate, Me may be contained singly or in combination of two or more, and preferred Me (Me1, Me2) is an element belonging to the third and fourth periods of the periodic table. Me1 preferably has an ionic radius of 3 to 0.8 nm in a divalent state, and more preferably has an ionic radius of 0.4 to 7 nm in a divalent and tetracoordinate state. Among the above, in terms of ease of synthesis and adsorption characteristics, Me1 includes silicon, lithium, magnesium, titanium, zirconium, vanadium, iron, chromium, manganese, cobalt, nickel, palladium, copper, zinc, gallium, germanium. Arsenic, tin, calcium, boron and the like. Me2 is a group 4B element belonging to the third or fourth period of the periodic table, and is preferably silicon.

The framework density (FD) of the aluminophosphates is usually 13 T / nm ³ or more, 20 T / nm ³ or less, preferably 13.5 T / nm ³ or more, and more preferably 14 T / nm ³ or more. Yes, the upper limit is preferably 19 T / nm ³ or less. If it is less than the above range, the structure tends to be unstable, and the durability is lowered. On the other hand, if the above range is exceeded, the adsorption capacity becomes small and tends to be unsuitable for use as an adsorbent. Note that FD (T / nm ³ ) means T atoms (number of elements constituting a skeleton other than oxygen per 1 nm ^{3 of} zeolite) present per unit volume (nm ³ ).

  The structure of aluminophosphates is a code defined by IZA and includes AEI, AEL, AET, AFI, AFN, AFR, AFS, AFT, AFX, ATO, ATS, CHA, ERI, LEV, and VFI. Among these, AFI and CHA are preferable from the viewpoint of adsorption characteristics and durability. The structure of crystalline aluminophosphates can be confirmed by measuring XRD (using Cu—Kα rays). In the present invention, from the viewpoint of adsorption characteristics, AFI type FAPO which is a crystalline aluminophosphate containing Al, P, Fe and Me3 (tin and / or titanium) in the skeleton structure, or Al, P in the skeleton structure. And CHA type SAPO, which is a crystalline aluminophosphate containing Si and Si. In the case of AFI-type FAPO containing Me3 (tin and / or titanium), the molar ratio of Me3 / Fe is 0.25 <Me3 / Fe <1.0, preferably 0.5 <Me3 / Fe <1.0. In particular, Me3 is preferably tin. FAPO and SAPO can be used alone or in combination of two or more.

  Aluminophosphates are usually produced by hydrothermal synthesis after mixing an aluminum source, a phosphorus source, and a Me source such as Si and Fe, if necessary, and a template. Such a manufacturing method is a known method described in JP-A-2007-144417.

  Although it does not specifically limit as an aluminum source, Usually, pseudoboehmite, aluminum alkoxide, such as aluminum isopropoxide, aluminum triethoxide, aluminum hydroxide, alumina sol, sodium aluminate etc. are mentioned, but pseudoboehmite. Is preferable because it is easy to handle and has high reactivity.

  Me means a heteroatom in the aluminophosphates described above, and preferably Si, Fe, Co, Mg, Zn, Ti, Sn, and the like. These Me sources are usually used in the form of inorganic acid salts such as sulfates, nitrates and phosphates, organic acid salts such as acetates and oxalates, or organic metal compounds. In some cases, a colloidal hydroxide or the like may be used.

  As the silicon source, fumed silica, silica sol, colloidal silica, water glass, ethyl silicate, methyl silicate, or the like is used. As the phosphorus source, phosphoric acid is usually used, but aluminum phosphate may be used.

  Examples of AFI templates include quaternary ammonium salts such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, morpholine, di-n-propylamine, tri-n-propylamine, tri-n-isopropylamine, Triethylamine, triethanolamine, piperidine, piperazine, cyclohexylamine, 2-methylpyridine, N, N-dimethylbenzylamine, N, N-diethylethanolamine, dicyclohexylamine, N, N-dimethylethanolamine, choline, N, N '-Dimethylpiperazine, 1,4-diazabicyclo (2,2,2) octane, N-methyldiethanolamine, N-methylethanolamine, N-methylpiperidine, 3-methylpiperidine, -Methylcyclohexylamine, 3-methylpyridine, 4-methylpyridine, quinuclidine, N, N'-dimethyl-1,4-diazabicyclo- (2,2,2) octane ion, di-n-butylamine, neopentylamine, Primary such as di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, pyrrolidine, 2-imidazolidone, di-isopropyl-ethylamine, dimethylcyclohexylamine, cyclopentylamine, N-methyl-n-butylamine, hexamethyleneimine Examples include amines, secondary amines, tertiary amines, and polyamines. These may be used alone or in combination of two or more. Among these, triethylamine, isopropylamine, di-n-isopropylamine, tri-n-propylamine, and tetraethylammonium hydroxide are preferable in terms of reactivity, and industrially cheaper triethylamine is more preferable.

  As a template for CHA, each of two or more groups of (1) an alicyclic heterocyclic compound containing nitrogen as a heteroatom, (2) a cycloalkylamine, and (3) an alkylamine is used. It is preferable to select and use one or more compounds per group.

(1) Alicyclic heterocyclic compound containing nitrogen as a hetero atom:
The heterocyclic ring of the alicyclic heterocyclic compound containing nitrogen as a hetero atom is usually a 5- to 7-membered ring, and preferably a 6-membered ring. The number of heteroatoms contained in the heterocycle is usually 3 or less, preferably 2 or less. The type of heteroatom is not particularly limited except nitrogen, but preferably includes oxygen in addition to nitrogen. The positions of the heteroatoms are not particularly limited, but those where the heteroatoms are not adjacent to each other are preferable. The molecular weight is usually 250 or less, preferably 200 or less, more preferably 150 or less. Examples of the alicyclic heterocyclic compound containing nitrogen as a hetero atom include morpholine, N-methylmorpholine, piperidine, piperazine, N, N′-dimethylpiperazine, 1,4-diazabicyclo (2,2,2) octane, N-methylpiperidine, 3-methylpiperidine, quinuclidine, pyrrolidine, N-methylpyrrolidone, hexamethyleneimine and the like can be mentioned, morpholine, hexamethyleneimine and piperidine are preferable, and morpholine is particularly preferable.

(2) Cycloalkylamine:
The number of cycloalkyl groups of the cycloalkylamine is 2 or less, preferably 1 per amine molecule. Moreover, carbon number of a cycloalkyl group is 5-7 normally, Preferably it is 6. The number of cycloalkyl cyclo rings is not particularly limited, but is usually preferably 1. Moreover, it is preferable that the cycloalkyl group has couple | bonded with the nitrogen atom of the amine compound. The molecular weight is usually 250 or less, preferably 200 or less, more preferably 150 or less. Examples of such cycloalkylamine include cyclohexylamine, dicyclohexylamine, N-methylcyclohexylamine, N, N-dimethylcyclohexylamine, and cyclohexylamine is preferred.

(3) Alkylamine:
The alkyl group of the alkylamine is a chain alkyl group, and any number may be contained in one amine molecule, but three is particularly preferable. The number of carbon atoms in the alkyl group is preferably 4 or less, and the total number of carbon atoms of all alkyl groups in one molecule is more preferably 10 or less. The molecular weight is usually 250 or less, preferably 200 or less, more preferably 150 or less. Examples of such alkylamines include di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, triethanolamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, N- Examples include methyldiethanolamine, N-methylethanolamine, di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, di-isopropyl-ethylamine, N-methyl-n-butylamine. Di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, di-n-butylamine, isopropylamine, t-butylamine, ethylenediamine, diisopropyl-ethyl Amine, N- methyl -n- butylamine are preferred, triethylamine being particularly preferred.

Preferred combinations of templates (1) to (3):
As a preferable combination, two or more kinds from morpholine, triethylamine and cyclohexylamine, more preferably morpholine and triethylamine are included. The mixing ratio of each group of these templates needs to be selected according to conditions. When mixing two templates, the molar ratio of the two templates to be mixed is usually 1:20 to 20: 1, preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1. It is. When mixing three templates, the molar ratio of the third template is usually from 1:20 to 20: 1, preferably from 1:10 to the two templates mixed in the above molar ratio. 10: 1, more preferably 1: 5 to 5: 1.

  As described above, an aqueous gel is prepared by mixing an aluminum source, a phosphorus source, and, if necessary, a Me source and a template. Although the mixing order varies depending on the conditions, usually, the phosphoric acid source and the aluminum source are first mixed, and the Me source and the template are mixed therewith.

The composition of the aqueous gel related to MeAPO is expressed as a molar ratio of oxide, and 0.01 ≦ MeOx (x is 1 when Me is divalent and 1.5 when trivalent) / P ₂ O ₅ ≦ 1.5, and 0.02 ≦ MeO / P ₂ O ₅ ≦ 1.0 is preferable from the viewpoint of ease of synthesis, and 0.05 ≦ MeO / P ₂ O ₅ ≦ 0.8 is more preferable. . The ratio of P ₂ O ₅ / Al ₂ O ₃ is 0.6 or more and 1.7 or less, and 0.7 to 1.6 or less is preferable from the viewpoint of ease of synthesis, and 0.8 More preferably, it is 1.5 or less. The lower limit of the ratio of water is 3 or more in terms of molar ratio with respect to Al ₂ O ₃ , preferably 5 or more, and more preferably 10 or more from the viewpoint of ease of synthesis. The upper limit of the ratio of water is 200 or less, preferably 150 or less, and more preferably 120 or less from the viewpoint of ease of synthesis and high productivity. The pH of the aqueous gel is 4 to 10, preferably 5 to 9 and more preferably 5.5 to 8.5 from the viewpoint of ease of synthesis.

  In addition, in each aqueous gel, you may coexist components other than the above as desired. Examples of such components include hydrophilic organic solvents such as hydroxides and salts of alkali metals and alkaline earth metals, and alcohols.

  In hydrothermal synthesis, an aqueous gel is placed in a pressure resistant container, and a predetermined temperature is maintained under stirring or standing in a self-generated pressure or under pressure of a gas that does not inhibit crystallization. The hydrothermal synthesis conditions are 100 to 300 ° C, and 120 to 250 ° C is preferable and 150 to 220 ° C is more preferable from the viewpoint of ease of synthesis. The reaction time is 3 to 30 days, preferably 5 to 15 days, more preferably 7 to 7 days from the viewpoint of ease of synthesis. After hydrothermal synthesis, crystalline aluminophosphates containing at least Al and P in the skeleton can be obtained by separating the product, washing with water, drying, and removing organic matter by a method such as firing.

  The adsorbing elements 1a and 1b are usually manufactured by applying an aqueous dispersion composed of an adsorbent, a binder, a solvent such as water or the like to the element structure (an assembly carrying the adsorbent). After the adsorbent is applied by a method such as immersing in the above aqueous dispersion, it is manufactured by drying or baking, or similarly applied to the fins (elements) constituting the structure, after drying or baking. It can be manufactured by assembling an element structure. Among them, the method of immersing the element structure or the element in an aqueous dispersion is preferable because it easily generates mesopores.

  Incidentally, the crystalline aluminophosphate suitably used as the adsorbent of the adsorbing elements 1a and 1b of the dehumidifying device 1 is shown in FIG. 3 by a graph of Z01 (-▲-), a graph of Z02 (-■-), It has an adsorption characteristic as shown by a graph (solid line) of Z06. In FIG. 3, Z02 indicates the water vapor adsorption isotherm of CHA type SAPO, and Z01 and Z06 indicate the water vapor adsorption isotherm of AFI type FAPO. In addition, in FIG. 3, in addition to these, each adsorption of Z05 (-x-), Y-type zeolite (-◆-), activated carbon (-*-), and silica gel (-●-), which are aluminophosphates. The characteristics are also shown.

  The operation of generating low-temperature air for air conditioning in the air conditioning system of the present invention is as follows. That is, when outside air having a temperature of 35 ° C. and a relative humidity of 40% is supplied to the dehumidifying device 1, for example, in the adsorption element 1a in the adsorption process, the adsorbent adsorbs water vapor in the air, as shown in FIG. Dehumidified air having a humidity of 20 to 5% is generated. At that time, the air flow path corresponding to the adsorption element 1 a of the dehumidifying device 1 is configured to flow toward the indirect vaporization cooling device 2, and the dehumidified air that has passed through the adsorption element 1 a enters the indirect vaporization cooling device 2. It is aired.

  In the indirect evaporative cooling device 2, a part of the dehumidified air supplied from the dehumidifying device 1 is supplied to the intake duct 21, and the other part of the dehumidified air is supplied to the cooled duct 23. In the cooling duct 22, the water supplied from the flow path 64 penetrates the wet wall 24 and evaporates in the cooling duct 24. Due to the latent heat of vaporization, the dehumidified air passing through the cooled duct is cooled in the cooled duct 23. Cooled, for example, low-temperature air for air conditioning at 10 ° C. is generated. The air sent from the intake duct 21 to the cooling duct 22 becomes wet air and is exhausted from the other end of the cooling duct 22 to the outside of the system.

  Further, while the low temperature air is generated in the indirect evaporative cooling device 2 as described above, the water that has not evaporated on the wet wall 24 is also cooled to, for example, about 10 ° C. by the evaporation of the water in the cooling duct 22. Such water is taken out from the end of the cooling duct 22 through the flow path 61 and introduced into the hot water flow path of the adsorption element 1a of the dehumidifying device 1 through the four-way switching valve 4 and the flow path 62 as cooling water. Thereby, the heat of adsorption generated in the adsorption element 1a can be removed, and the adsorption function of the adsorbent can be further enhanced. Then, the water that has passed through the hot water flow path of the adsorption element 1 a is circulated through the flow path 63, the four-way switching valve 5, and the flow path 64 to the wet wall 24 of the cooling duct 22 of the indirect vaporization cooling device 2. In addition, in order to supplement the water evaporated in the wet wall 24, water is appropriately supplied from the water supply path 8 to the flow path 64.

  On the other hand, in the dehumidifier 1, the adsorption element 1b is in the desorption process while the adsorption element 1a is in the adsorption process. In such an adsorption element 1b, the water vapor adsorbed on the adsorbent by the heating operation of the adsorption element. Detach. At that time, in the cogeneration apparatus 3, for example, hot water of 70 ° C. is manufactured, and such hot water is supplied to the hot water flow path of the adsorption element 1b via the flow path 65, the four-way switching valve 4 and the flow path 66. .

  Moreover, in the dehumidifier 1, when the adsorption function of the adsorption element 1a is lowered, the adsorption process of the adsorption element 1a and the desorption process of the adsorption element 1b are switched. In that case, as shown in FIG. 2, by switching operation of the switching damper, an air flow path corresponding to the adsorption element 1b of the dehumidifying device 1 is formed toward the indirect vaporization cooling apparatus 2 and passes through the adsorption element 1b. The dehumidified air obtained in this way is sent to the indirect evaporative cooling device 2. At the same time, the four-way switching valve 4 and the four-way switching valve 5 in the water flow path are switched.

  In the setting of the flow path shown in FIG. 2, water cooled to about 10 ° C., for example, in the cooling duct 22 of the indirect vaporization cooling device 2 is taken out through the flow path 61 and passed through the four-way switching valve 4 and the flow path 66. It is introduced into the hot water flow path of the adsorption element 1b of the dehumidifier 1 as cooling water. Thereby, the adsorption heat generated in the adsorption element 1b can be removed, and the adsorption function of the adsorbent can be enhanced. Further, the hot water generated by the cogeneration device 3 is supplied to the hot water flow path of the adsorption element 1 a via the flow path 65, the four-way switching valve 4 and the flow path 62. Thereby, the adsorption | suction element 1a can be heated and the desorption function of adsorption material can be accelerated | stimulated.

  As described above, in the air conditioning system according to the present invention, the dehumidified air obtained in the adsorption process is indirectly converted to the evaporative cooling apparatus while the adsorption process and the desorption process are alternately switched between the adsorption element 1a and the adsorption element 1b of the dehumidification apparatus 1. In addition, the indirect evaporative cooling device 2 uses part of the dehumidified air as operating air and uses the other part of the dehumidified air as cooled air to generate low-temperature air for air conditioning. At that time, the water used for cooling in the indirect evaporative cooling device 2 is cooled and supplied to the adsorption process region (for example, the adsorption element 1a) of the dehumidifying device 1 to thereby adsorb the adsorbent. Then, the desorption action of the adsorbent is promoted by supplying the hot water supplied from the cogeneration apparatus 3 to the desorption process region (for example, the adsorption element 1b) of the indirect vaporization cooling apparatus 2.

  That is, in the air conditioning system of the present invention, a part of the dehumidified air obtained by the dehumidifying device 1 is used as the operating air for the indirect evaporative cooling device 2, so that the cooling effect in the indirect evaporative cooling device 2 can be improved. In addition, since the water having a lowered temperature generated in the indirect vaporization cooling device 2 is used in the adsorption process of the dehumidification device 1, the adsorption effect in the dehumidification device 1 can be improved. In addition, since the hot water supplied from the cogeneration device 3 is used for the desorption process of the dehumidifying device 1, the air conditioning has a lower temperature and lower humidity than a system using a cooling device or a heater using a refrigerant such as chlorofluorocarbon. Industrial air can be generated at low cost. In particular, in the dehumidifying apparatus 1, by using zeolite having a specific adsorption characteristic as the adsorbent, the apparatus configuration can be reduced in size and air for air conditioning at a lower temperature can be generated.

DESCRIPTION OF SYMBOLS 1: Dehumidification apparatus 1a: Adsorption element 1b: Adsorption element 2: Indirect vaporization cooling apparatus 21: Intake duct 22: Cooling duct 23: Cooling duct 24: Wet wall 3: Cogeneration apparatus (heat source)
4: Four-way switching valve 5: Four-way switching valve 61-68: Flow path (water flow path)
7: Drainage channel 8: Water supply channel

Claims (6)

  A desiccant air conditioning system that combines a dehumidifying device that generates dehumidified air using an adsorbent and an indirect evaporative cooling device that generates low-temperature air using the latent heat of water evaporation. The indirect evaporative cooling device includes an air supply path for supplying dehumidified air obtained in the process to the indirect evaporative cooling device and an exhaust path for discharging the moist air obtained in the desorption process to the outside of the system. A cooling duct having a moist wall to be supplied inside and a part of the dehumidified air sent from the air supply passage of the dehumidifier as working air, and an air supply of the dehumidifier provided in contact with the cooling duct And a cooled duct that sends out low-temperature air for air conditioning by supplying another part of the dehumidified air from the road as cooled air, and the dehumidifying device discharges from the wet wall of the cooling duct of the indirect evaporative cooling device Water adsorption process area Desiccant air-conditioning system, characterized in that supply and cogeneration water passage for supplying the hot water to be supplied to the region of the desorption step from the device is attached.   The dehumidifying device includes at least one pair of plate fin type adsorbing elements, and each adsorbing element is arranged in parallel and in parallel with a large number of adsorbing sheets formed in a flat plate shape and coated with an adsorbent on the surface. The desiccant air conditioning system according to claim 1, wherein each adsorbing sheet is formed by passing a heat medium passage through which hot water flows.   The adsorbent used in the dehumidifier has a relative vapor pressure of 0.05 or more and an adsorption amount of 0.1 g / g or less in a water vapor adsorption isotherm at 40 ° C. and a relative vapor pressure of 0.05 to 0.3. The desiccant air conditioning system according to claim 1 or 2, wherein the zeolite has a water vapor adsorption amount change of 0.15 g / g or more when the relative vapor pressure changes by 0.15 in the following range.   When the adsorbent used in the dehumidifier is 0.1 g / g or less and the relative vapor pressure changes by 0.15 when the relative vapor pressure is 0.03 in the water vapor adsorption isotherm at 55 ° C. The desiccant air conditioning system according to claim 1 or 2, wherein the zeolite has a water vapor adsorption amount change of 0.15 g / g or more.   The desiccant according to claim 1 or 2, wherein the adsorbent used in the dehumidifier is a zeolite having an adsorption amount of 0.10 g / g or more when the relative vapor pressure is 0.17 in a water vapor adsorption isotherm at 35 ° C. Air conditioning system.   The adsorbent used in the dehumidifier is the amount of water vapor adsorbed when the relative vapor pressure in the water vapor adsorption isotherm in the adsorption process at 35 ° C. is 0.17 and the water vapor adsorption isotherm in the desorption process at 75 ° C. The desiccant air conditioning system according to claim 1 or 2, wherein the zeolite is a zeolite having a difference from a water vapor adsorption amount of 0.07 g / g or more when the vapor pressure is 0.15.

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