JP4661772B2 - Humidity conditioning air-conditioning adsorbent, humidity conditioning air conditioner and operation method thereof - Google Patents

Description

  The present invention relates to a specific adsorbent, a humidity control air conditioner using the same, and an operation method thereof.

  Adsorption heat pump is one of the most excellent exhaust heat recovery and regeneration methods that can operate using low-quality thermal energy as a heat source without using auxiliary power, and is considered as a promising candidate for introduction into an environmentally symbiotic thermal energy utilization system. In this process of operation, to regenerate the adsorbate, eg, the adsorbent that has adsorbed water, the adsorbent is heated to desorb the adsorbate, and the dried adsorbent is cooled to the temperature used for adsorbate adsorption. And again used for adsorbate adsorption.

So far, absorption heat pumps that use exhaust heat and heat at relatively high temperatures (over 120 ° C) as regeneration heat sources for adsorbents have already been introduced as part of a combined heat and power plant (cogeneration system). It has been put into practical use. However, in general, in cogeneration equipment and fuel cells, the exhaust heat / heat temperature is a relatively low temperature of 100 ° C or less, and practically 80 ° C or less. Cannot be used. In addition, this low-temperature thermal energy has a low energy density, so that the cost of collection and use is high, so most of it is discarded to the environment at present, but the total amount of low-temperature thermal energy discarded is Since it occupies 90% or more of the total exhaust heat, and this hinders the improvement of the overall energy utilization rate, effective use of low temperature exhaust heat of 100 ° C. or lower, and further 60 ° C. to 80 ° C. has been demanded. .
On the other hand, humidity control air conditioners such as dehumidification air conditioners and humidification air conditioners are also promising as one of the exhaust heat recovery and regeneration methods, similar to adsorption heat pumps, but examples using low-temperature thermal energy as a driving heat source are known. Absent.

  In the adsorption heat pump and the humidity control air conditioner, the adsorption characteristics required for the adsorbent differ depending on the available heat source temperature even if the operation principle is the same. For example, the exhaust heat temperature of gas engine cogeneration used as a heat source on the high temperature side or a polymer electrolyte fuel cell is 60 ° C to 80 ° C. The heat source temperature on the cooling side used when using these high-temperature heat sources is determined by the restriction of the place temperature where the apparatus can be installed. For example, in a factory or a house, the outside air temperature of the building is used. That is, the operating temperature range of the adsorption heat pump and the humidity control apparatus is about 30 ° C. to 35 ° C. on the low temperature side and about 60 ° C. to 80 ° C. on the high temperature side when installed in a building or the like. In summer when the demand for cold heat increases, the outside air temperature is expected to rise, and the temperature on the low temperature side is likely to be higher than the above. Therefore, in order to effectively use the exhaust heat, an apparatus that can be driven even when the temperature difference between the low temperature side heat source and the high temperature side heat source in the application field is small, the low temperature side heat source is 30 ° C. or higher, and the high temperature side heat source is 80 ° C. or lower is desired. ing.

  In order to make this possible, a material having the following adsorption characteristics is required. That is, (1) there is a difference in the amount of adsorption within the range where the difference between the relative vapor pressure during adsorption and the relative vapor pressure during desorption is small, and in order to reduce the size of the device, (2) (3) Adsorbent that is easily desorbed at a high relative pressure.

The use of various adsorbents as an adsorbent for use in an adsorption heat pump or a humidity control air conditioner has been studied, but there are various problems, and a solution is desired.
Y-type zeolite, which has been studied as an adsorbent for adsorption heat pumps and humidity control air conditioners, adsorbs adsorbed substances even when the relative vapor pressure is close to zero. A high temperature of 150 ° C. to 200 ° C. or higher is required to make the pressure almost zero. Therefore, Y-type zeolite has a problem that it is difficult to use it in an adsorption heat pump or a humidity control apparatus using the low-temperature waste heat described above.

  Similarly, A-type silica gel, which has been studied, has insufficient adsorption characteristics at a low relative vapor pressure, and mesoporous silica synthesized using a micelle structure of a surfactant as a template (such as FSM-10) (see Patent Document 1). Is not adsorbed at a low relative vapor pressure, so that there is a problem that it is not possible to construct an adsorption heat pump or humidity control air conditioner using heat obtained from cooling water, solar heat or the like of the above-mentioned cogeneration equipment, fuel cell or the like.

  Further, among the conventional adsorbents, mesoporous silica is not only required to improve its adsorption characteristics, but also has a problem that its structure is fragile, and is difficult to manufacture industrially and is expensive. Y-type zeolite and A-type silica gel are low cost and difficult to break, but their performance is insufficient.

JP-A-9-178292

  The present invention relates to an adsorbent suitable for a humidity control air conditioner capable of adsorbing and desorbing an adsorbate in a relatively low relative vapor pressure range that can be driven even when the low temperature side heat source is 30 ° C. or higher and the high temperature side heat source is 80 ° C. or less. An efficient humidity control air conditioner used and an operation method thereof are provided.

As a result of intensive studies to solve the above problems, the present inventors have found an adsorbent suitable for humidity control air conditioning. That is, the gist of the present invention is an operation method of a humidity control air conditioner provided with an adsorbent capable of adsorbing and desorbing adsorbate, an adsorption / desorption portion provided with the adsorbent, and a mechanism for regenerating the adsorbent, as the adsorbent, a zeolite containing aluminum and phosphorus and iron framework structure, the framework density is greater than 16.0T / 1000Å ^3, and at 20.0T / 1000Å ³ or less, and was measured at 25 ° C. In the water vapor adsorption isotherm, when the relative vapor pressure changes by 0.1 when the relative vapor pressure is in the range of 0.1 to 0.25, the water adsorption amount change has a relative vapor pressure range of 0.12 g / g or more. The operation method of the humidity control air conditioner is characterized in that the mechanism for regenerating the adsorbent using zeolite is a heat supply mechanism capable of supplying heat of 80 ° C. or less to the adsorption / desorption part.

Another aspect of the present invention is an adsorbent capable of adsorbing and desorbing an adsorbate, an adsorbing and desorbing material provided with the adsorbing material, and a heat supply mechanism for supplying heat to regenerate the adsorbent to the adsorption and desorption part. And the heat of the heat supply mechanism is 80 ° C. or less, and the heat adsorbing material for the humidity control air conditioner that desorbs and regenerates the moisture adsorbed on the adsorbing material when heated by the heat supply mechanism. Still another subject matter of the present invention resides in a humidity control air conditioner using the adsorbent.

  The humidity control air conditioner using the adsorbent exhibiting a large change in adsorption / desorption amount in the range of relative vapor pressure of 0.10 or more and 0.25 or less of the present invention has a large difference in moisture adsorption amount due to adsorption / desorption of the adsorbent Since the adsorbent can be regenerated (desorbed) at a low temperature, the humidity control air conditioner can be efficiently driven using a heat source having a temperature lower than that of the prior art. That is, according to the adsorbent of the present invention, a humidity control air conditioner that is driven by a relatively low temperature heat source of 80 ° C. or less can be provided.

<Humidity control device and adsorption characteristics>
In the present invention, humidity adjustment is a technique for controlling the humidity of the air-conditioned space, and therefore may be dehumidified or humidified. For example, in the case of indoor air conditioning, it can be used for the purpose of dehumidification in the summer when the humidity is high, and for the purpose of humidification in the winter when the humidity is low. The humidity control air conditioner may be a fixed or movable object as long as it has a dehumidifying or humidifying function. For example, a desiccant air conditioner fixed in a building, a small dehumidifier installed indoors, a humidifier, etc. Is included.
In humidity control air conditioning, the operating vapor pressure range is determined by the following desorption side relative vapor pressure φ ₁ and adsorption side relative vapor pressure φ ₂ .

φ ₁ = Absolute humidity of gas after treatment / Saturated vapor pressure at treatment temperature φ ₂ = Absolute humidity of gas before treatment / Saturated vapor pressure at temperature before treatment However, in the case of humidity control air conditioning, air under atmospheric pressure is generally used Because it becomes operation,
φ ₁ = absolute humidity of air after treatment / saturated vapor pressure at treatment temperature φ ₂ = absolute humidity of air before treatment / saturated vapor pressure at temperature before treatment. That is, the relative humidity of the pre-treatment air and the post-treatment air are directly used as the relative vapor pressure.
As an example of humidity conditioning air conditioning, when considering dehumidifying air conditioning in the summer, the dry bulb temperature is 27 ° C. and the wet bulb temperature is 19 ° C., according to the summer indoor conditions specified in JIS-C9612 and the like. The relative humidity at this time is about 50%. On the other hand, it is also described that the external absolute humidity in summer is 21 g / kg. When this air is heated to 80 ° C., the relative humidity is about 7%. In this operation, air having a relative humidity of 7% to 50% alternately contacts. In this case, the operation relative water vapor pressure range is φ ₁ to φ ₂ = 0.07 to 0.5, and an adsorbent material having a large change in the amount of adsorption within this range is preferable.

  However, it is generally known that the relative humidity temporarily decreases in the dehumidifying air conditioning system due to heat generated by the initial adsorption heat. Therefore, in actual operation, it is required to have adsorption performance even at a relative humidity of 50% or less. Further, the adsorbent is preferably a material having a large change in adsorption amount in a narrow relative vapor pressure range. In consideration of these, a material that adsorbs more water vapor at a relative humidity of 0.1 to 0.25 in the above operating humidity range is preferable.

Further, since the adsorption amount is large in the humidity control apparatus and the weight and volume of the adsorbent are small, the adsorbent change is 0.12 g / g or more, preferably 0.15 g / g or more. Is good. When the change in the amount of adsorption is small, the required volume of the adsorbent becomes large and the apparatus becomes undesirably large. The upper limit of the adsorption amount is not particularly limited, but is usually about 0.3 g / g or less due to material restrictions. The relative vapor pressure is 0.1 on the water vapor adsorption isotherm measured at 25 ° C.
When the relative vapor pressure changes by 0.1 within the range of 0.25 or less, it is necessary to have a relative vapor pressure region in which the change in the amount of adsorption of water is 0.12 g / g or more.

In terms of the change in adsorption performance, the adsorption amount is 0.12 g / g or more, preferably 0.15 g / g or more at a relative vapor pressure of 0.25 in the above operating humidity range, and the upper limit is particularly limited. Although it is usually 0.3 g / g or less, on the other hand, in terms of desorption performance, the adsorption amount is 0.05 g / g or less, preferably 0.03 g / g or less at a relative vapor pressure of 0.1. The lower limit is usually preferably an adsorbent of 0.00001 g / g or more.

Humidity control equipment has a difference in adsorption amount in a range where the difference between the relative vapor pressure during adsorption and the relative vapor pressure during desorption is small, so that humidity can be adjusted not only in summer but also when specific humidity is required. It has the advantage that it can be used. In addition, when the amount of adsorption in a narrow range is large, the adsorption / desorption is performed promptly. Therefore, the adsorption / desorption cycle can be shortened, and there is an advantage that leads to a compact apparatus.
One of the features of the present invention is that an adsorbent having the above characteristics is used as an adsorbent for an adsorption / desorption portion of a humidity control air conditioner.
The humidity control air conditioner uses the ability of the adsorbent to adsorb and desorb the adsorbate as a drive source. In the humidity control air conditioner, the adsorbate is adsorbed on the adsorbent as vapor. As the adsorbate, water, ethanol, acetone, or the like can be used, but water is most preferable from the viewpoint of safety, cost, and latent heat of vaporization.

<Adsorbent>
The adsorbent for a humidity control air conditioner, which is a feature of the present invention, is a zeolite that is a crystalline iron aluminophosphate containing at least aluminum, phosphorus, and iron in a skeleton structure, and has a framework density of 16.0 T / 1,000Å. Greater than ³ , 20.0 T / 1,000 Å ³ or less, preferably 16.2 T / 1,000 Å ³ or more, while 19.0 / 1,000 Å ³ or less, or even 18.0 / 1, Zeolite in the range of 3,000 to ³ or less is preferred.

By selecting such zeolite, the above adsorption performance can be achieved. If the framework density is too small, the adsorption amount difference tends to increase, but adsorption / desorption does not occur in an appropriate relative humidity range, and the structure tends to be unstable, which may cause problems in durability. For this reason, it is inappropriate, and if it is too large, the difference in the amount of adsorption is too small. Here, the framework density means the number of elements constituting a skeleton other than oxygen per 1,000 cm ³ of the zeolite, and this value is determined by the structure of the zeolite. The relationship between framework density and geolite structure is shown in ATLAS OF ZEOLITE FRAMEWARK TYPES Fifth Revised Edition 2001 ELSEVIER.

The structure of such zeolite is International Zeolite Assiciation (IZA)
The codes defined by ABW, AEL, AEN, AET, AFI, AFN, AFO, AHT, ANA, APC, APD, AST, ATN, ATO, ATS, ATT, BPH, BRE, CON, CZP, DFT, EDI , FER, LAU, LTL, MAZ, MEL, MFI, MOR, MWW, OSI, SAT, SOD, STT, TER, VNI, VSV, ZON, preferably AEL, AET, AFI, AST, ATS More preferably, it is AFI.

  Framework density correlates with pore volume, and in general, lower framework density zeolites have greater pore volume and therefore higher adsorption capacity. Those with a low framework density are preferable from the viewpoint of the overall adsorption amount, but are suitable as adsorbents at lower humidity, and from the viewpoint of adsorption performance in the relative vapor pressure range in the present invention at higher humidity. Rather, it is rather unsuitable, and in the present invention, a framework with a higher framework density is more suitable. In view of these balances, the above-mentioned framework density is preferable.

The adsorbent of the present invention is a zeolite which is a crystalline iron aluminophosphate containing at least aluminum, phosphorus and iron in the skeleton structure, and the iron of the crystalline iron aluminophosphate is substituted with aluminum and / or phosphorus in the skeleton. Has been.
The zeolite used as the adsorbent in the present invention is a zeolite containing aluminum, phosphorus and iron in the skeleton structure, and has an abundance ratio of atoms represented by the following formulas (1), (2) and (3) Is preferred.

0.001 ≦ x ≦ 0.3 (1)
(Wherein x represents the molar ratio of iron to the total of aluminum, phosphorus and iron in the skeletal structure)

0.3 ≦ y ≦ 0.6 (2)
(Wherein y represents the molar ratio of aluminum to the total of aluminum, phosphorus and iron in the skeleton structure)

0.3 ≦ z ≦ 0.6 (3)
(In the formula, z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and iron in the skeleton structure)
And among the above-mentioned proportions of atoms, the proportion of iron is represented by the following formula (4).

0.003 ≦ x ≦ 0.2 (4)
(Wherein x is as defined above)
Is preferably represented by the following formula (5):

0.005 ≦ x ≦ 0.1 (5)
(Wherein x is as defined above) is more preferred.

  In the skeleton structure of the crystalline iron aluminophosphate in the present invention, an element other than Fe, Al and P may be contained. Examples of other elements include silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, cobalt, nickel, palladium, copper, zinc, gallium, germanium, arsenic, tin, calcium, and boron. Usually, the molar ratio (M / Fe) of other elements (M) to iron (Fe) is 3 or less, preferably 1.5 or less, more preferably 0.5 or less. When M / Fe is not in this range, the adsorption performance in the present invention does not appear sufficiently.

Each molar ratio of the above atoms is determined by elemental analysis. Usually, elemental analysis can be determined by ICP analysis after heating a sample with a hydrochloric acid aqueous solution.
Furthermore, the adsorbent used in the present invention has a change in the amount of water adsorbed when the relative vapor pressure changes by 0.1 in the range of the relative vapor pressure of 0.1 to 0.25 in the water vapor adsorption isotherm measured at 25 ° C. Is an adsorbent having a relative vapor pressure region of 0.12 g / g or more, preferably 0.15 g / g or more, and preferably has a relative vapor pressure of 0.14 or more and 0.22 or less and a relative vapor pressure of 0.1. The adsorbent has a water adsorption amount change of 0.12 g / g or more, preferably 0.15 g / g or more when changed to 08.
The upper limit of change in the amount of adsorption of water when the relative vapor pressure changes by 0.1 is preferably as high as possible, but is usually 0.3 g / g or less due to material limitations, and the relative vapor pressure changed by 0.08. The upper limit of the change in adsorption amount is usually 0.29 g / g or less.

In addition to the above conditions, the adsorbent used in the present invention has an adsorption amount of 0.05 g / g or less at the lower limit relative vapor pressure 0.1 of the present invention and an upper limit relative vapor pressure of 0 in the water vapor adsorption isotherm. More preferably, it is 0.15 g / g or more at .25.
The adsorbent for the humidity control air conditioner of the present invention is basically composed of the above zeolite, but it is necessary to use it together with other adsorbents or as an adsorbent as long as its performance is not impaired. Other components may be included accordingly.

<Manufacture of iron aluminophosphate>
The production conditions of the crystalline iron aluminophosphate in the present invention are not particularly limited, but it is usually produced by mixing an aluminum source, an iron source, a phosphorus source and a template and then hydrothermally synthesizing. An example will be described below.

First, an aluminum source, an iron source, a phosphorus source, and a template are mixed.
Aluminum source: The aluminum source is not particularly limited, and usually includes pseudoboehmite, aluminum isopropoxide, aluminum alkoxide such as aluminum triethoxide, aluminum hydroxide, alumina sol, sodium aluminate, etc., but pseudoboehmite is easy to handle. From the viewpoint of high reactivity.

  Iron source: The iron source is not particularly limited, and is usually an inorganic acid iron such as iron sulfate, iron nitrate, iron phosphate, iron chloride or iron bromide, or an organic acid iron such as iron acetate, iron oxalate or iron citrate. And iron organometallic compounds such as iron pentacarbonyl and ferrocene. Among these, inorganic acid irons and organic acid irons are preferable because they are easily dissolved in water, and inorganic acid iron compounds such as ferric nitrate and ferrous sulfate are more preferable. In some cases, colloidal iron hydroxide or the like may be used.

Phosphorus source: Phosphoric acid is usually used as the phosphorus source, but aluminum phosphate may be used.
Other elements: The skeleton structure of iron aluminophosphate may contain other elements as long as the adsorption / desorption characteristics described above are not impaired. Examples of other elements include silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, cobalt, nickel, iron, palladium, copper, zinc, gallium, germanium, arsenic, tin, calcium, and boron.

Template: As a template, 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-methylpiperidi , N-methylcyclohexylamine, 3-methylpyridine, 4-methylpyridine, quinuclidine, N, N′-dimethyl-1,4-diazabicyclo- (2,2,2) octane ion, di-n-butylamine, neo Pentylamine, di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, pyrrolidine, 2-imidazolidone, di-isopropyl-ethylamine, dimethylcyclohexylamine, cyclopentylamine, N-methyl-n-butylamine, hexamethyleneimine, Primary amines such as secondary amines, secondary amines, tertiary amines, and polyamines. These may be used as a mixture. 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. These may be used alone or in combination of two or more.

(Preparation of aqueous gel)
An aqueous gel is prepared by mixing the aluminum source, iron source, phosphorus source and template described above. Although the mixing order varies depending on the conditions, usually, a phosphoric acid source and an aluminum source are first mixed, and then an iron source and a template are mixed therewith.
The composition of the aqueous gel relating to iron aluminophosphate is 0.01 ≦ FeO / P ₂ O ₅ ≦ 1.5, expressed in terms of the molar ratio of the oxide, and is 0.00 from the viewpoint of ease of synthesis. 02 ≦ FeO / P ₂ O ₅ ≦ 1.0 is preferable, and 0.05 ≦ FeO / P ₂ O ₅ ≦ 0.5 is more preferable. Further, the ratio of P ₂ O ₅ / Al ₂ O ₃ is 0.6 or more and 1.7 or less, and is preferably 0.7 or more and 1.6 or less from the viewpoint of easy synthesis. More preferably, it is 1.5 or less. The lower limit of the proportion of water, relative to Al ₂ O _3, is 3 or more in molar ratio, preferably 5 or more from the viewpoint of easiness of synthesis, and more preferably 10 or more. The upper limit of the ratio of water is preferably 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.
(Hydrothermal synthesis)
Hydrothermal synthesis is carried out by placing an aqueous gel in a pressure-resistant container and maintaining a predetermined temperature under stirring or standing under self-generated pressure or a pressurized gas that does not inhibit crystallization. The conditions for hydrothermal synthesis are 100 to 300 ° C, preferably 150 to 250 ° C, and more preferably 170 to 220 ° C from the viewpoint of ease of synthesis.

The reaction time is from 3 hours to 30 days, preferably from 5 hours to 15 days, more preferably from 7 hours to 7 days, from the viewpoint of ease of synthesis. After hydrothermal synthesis, the product is separated, washed with water, dried, and part or all of the organic matter contained is removed by calcination using air or the like by a method such as calcination to obtain such crystalline iron aluminophosphate .
One of the characteristics of the present invention is to use an adsorbent having the above characteristics as an adsorbent for an adsorption / desorption portion of a humidity control air conditioner. In other words, since a large amount of adsorption can be obtained with a relatively small change in the relative vapor pressure on the relatively low phase pressure resistance side, it is suitable for humidity control air conditioners, such as factory air conditioners, where the lower temperature limit of the low-temperature heat source is limited. ing.

<Operation of humidity control air conditioner>
Next, the operation of the humidity control air conditioner of the present invention using the above adsorbent will be described.
First, the concept of the humidity control air conditioner will be described with reference to FIG . The humidity control air conditioner shown in FIG. 1 includes an adsorbent capable of adsorbing and desorbing adsorbate, an adsorbing portion 61 that is an adsorbing and desorbing portion including the adsorbent, and a mechanism 63 for regenerating the adsorbent, and if necessary. An air path for circulating the air 62 to be conditioned or a device for forcibly exhausting the conditioned air are provided. The adsorbing portion only needs to have a shape that allows sufficient contact between the adsorbing material and the air for adjusting the humidity, and a rotor shape having a honeycomb structure or the like is used. The mechanism 63 for regenerating the adsorbent may be any heat supply mechanism that can supply heat of about 80 ° C. necessary for the regeneration of the adsorbent to the adsorber in the case of dehumidification. When generating heat by heating, etc., heat source such as a heater, heating coil, etc., a mechanism such as a blower for sufficiently transferring heat to the adsorption part, piping to supply the high temperature gas when obtaining a heat source from outside the device, etc. It becomes the mechanism of. The external heat source is not particularly limited, and examples thereof include cogeneration equipment such as a gas engine and a gas turbine, and a fuel cell. In the case of a humidification application, it may be a route through which high-humidity air for reabsorption is circulated.

Next, although the action (operation method) of humidity control using a dehumidifier will be specifically described, the present invention is not limited to this.
FIG. 2 shows a conceptual diagram of a desiccant air conditioner as an example of a dehumidifier. The desiccant air conditioner includes a processing air path 71, a regeneration air path 72, a desiccant rotor 73 to which an adsorbent is attached, two sensible heat exchangers 74 and 75, a heat supply mechanism 76 from a heating source, and a humidifier. 77 is the main component. The processing air is dehumidified by the desiccant rotor 73 and the temperature is increased by the moisture adsorption heat of the desiccant. Thereafter, the first sensible heat exchanger 74 exchanges heat with the regenerated air and cools it. Then, the humidifier 77 humidifies and supplies the air-conditioned space 78. On the other hand, the regeneration air is taken in from the external space, and heat is exchanged with the processing air in the first sensible heat exchanger 74 to increase the temperature. Then, the regeneration air is heated by the heat supply mechanism 76 to lower the relative humidity, and the desiccant Passing through the rotor 73, the moisture of the desiccant rotor 73 is desorbed and regenerated. The sensible heat of the regenerated air after regeneration is recovered by exchanging heat with the regenerated air before heating by the second sensible heat exchanger 75 and then discharged to the outside 79.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following Examples.
[Example 1]
To a mixture of 38.4 g of water and 17.6 g of 85% phosphoric acid, 9.5 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added and stirred. This was stirred for 3 hours, and an aqueous solution prepared by dissolving 6.78 g of ferrous sulfate heptahydrate in 36.6 g of water was added thereto, and further 10.8 g of triethylamine was mixed and stirred for 3 hours. The starting reactant was obtained.

0.32 FeSO ₄ : 0.92 Al ₂ O ₃ : P ₂ O ₅ : 1.4 Triethylamine: 60H ₂ O
The above starting reaction product was charged into a 200 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and allowed to react at 200 ° C. for 12 hours in a stationary state. After the reaction, the reaction mixture was cooled, the supernatant was removed by decantation, and the precipitate was collected. The precipitate was washed three times with water, filtered off and dried at 120 ° C. A 3 g sample containing the template thus obtained was collected, placed in a vertical quartz fired tube, heated to 550 ° C. at 1 ° C./min in an air stream of 200 ml / min, and kept at 550 ° C. for 6 hours. Firing was performed. When the XRD of the crystalline iron aluminophosphate thus obtained was measured, it was a so-called FAPO-5 of AFI type. (Framework density: 17.3 T / 1,000 cm ³ )
In addition, when elemental analysis was conducted by ICP analysis after heating and dissolving in an aqueous hydrochloric acid solution, the composition ratio (molar ratio) of each component to the total of aluminum, phosphorus and iron in the skeleton structure was 4.0% for iron and aluminum for It was 46.7% and phosphorus was 49.3%.

  FIG. 3 is a water vapor adsorption isotherm at 25 ° C. obtained by measuring this zeolite with an adsorption isotherm measuring apparatus (Belsorb 18: Nippon Bell Co., Ltd.). The measurement of the adsorption isotherm was performed at an air hot bath temperature of 50 ° C., an adsorption temperature of 25 ° C., an initial introduction pressure of 3.0 torr, an introduction pressure set point of 0, a saturated vapor pressure of 23.76 mmHg, and an equilibration time of 500 seconds.

  From FIG. 3, the maximum adsorption amount change when water vapor is adsorbed suddenly at a relative vapor pressure of 0.15 to 0.20 and the relative vapor pressure changes by 0.1 in the relative vapor pressure range of 0.10 to 0.25. It can be seen that the amount is 0.17 g / g, and the change in adsorption amount is 0.17 g / g when the relative vapor pressure range is 0.14 to 0.22. FAPO-5 having such characteristics is one of the most preferable adsorbents used in the present invention.

[Comparative example]
To a mixture of 38.4 g of water and 17.6 g of 85% phosphoric acid, 10.3 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added and stirred. This was stirred for 3 hours, 36.6 g of water was added thereto, 11.6 g of triethylamine was further mixed, and the mixture was stirred for 3 hours to obtain a starting reaction product having the following composition.

Al ₂ O ₃ : P ₂ O ₅ : 1.5 Triethylamine: 60H ₂ O
The above starting reaction product was charged into a 200 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and allowed to react at 200 ° C. for 12 hours in a stationary state. After the reaction, the reaction mixture was cooled, the supernatant was removed by decantation, and the precipitate was collected. The precipitate was washed three times with water, filtered off and dried at 120 ° C. A 3 g sample containing the template thus obtained was collected, placed in a vertical quartz fired tube, heated to 550 ° C. at 1 ° C./min in an air stream of 200 ml / min, and kept at 550 ° C. for 6 hours. Firing was performed. When the XRD of the crystalline aluminophosphate thus obtained was measured, it was an AFI type so-called AlPO-5 (the framework structure contains Al and P).

  FIG. 4 is a water vapor adsorption isotherm at 25 ° C. obtained by measuring this zeolite with an adsorption isotherm measuring apparatus (Belsorb 18: Nippon Bell Co., Ltd.). The measurement of the adsorption isotherm was performed at an air hot bath temperature of 50 ° C., an adsorption temperature of 25 ° C., an initial introduction pressure of 3.0 torr, an introduction pressure set point of 0, a saturated vapor pressure of 23.76 mmHg, and an equilibration time of 500 seconds.

FIG. 4 shows that the amount of change in the adsorption amount in the relative vapor pressure range of 0.10 to 0.25 is only 0.03 g / g. AlPO-5 having such characteristics is not suitable for the adsorbent of the present invention.
As described above, since the adsorbent used in the present invention changes more in the same relative vapor pressure range than the conventional silica gel and zeolite, more dehumidification is achieved by using an adsorbent having substantially the same weight. An effect can be generated.

It is a principle figure of a humidity control apparatus. It is a conceptual diagram of a desiccant air conditioner. It is a water vapor | steam adsorption isotherm of the adsorption material (FAPO-5) of an Example. It is a water vapor | steam adsorption isotherm of the adsorbent (ALPO-5) of a comparative example.

Explanation of symbols

61 Adsorption part 62 Air path 63 Heat supply mechanism 71 Processing air path 72 Regeneration air path 73 Desiccant rotor 74, 75 Sensible heat exchanger 76 Heat supply mechanism 77 Humidifier

Claims (10)

  An operation method of a humidity control air conditioner including an adsorbent capable of adsorbing and desorbing an adsorbate, an adsorption / desorption portion including the adsorbent, and a mechanism for regenerating the adsorbent,
The adsorbent is a zeolite containing aluminum, phosphorus and iron in the skeleton structure, and its framework density is 16.0 T / 1000%. ³ Larger, 20.0T / 1000Å ³ The amount of water adsorbed is 0.12 g when the relative vapor pressure changes 0.1 in the range of the water vapor adsorption isotherm measured at 25 ° C. Using a zeolite having a relative vapor pressure range of at least / g, and
The operation method of a humidity control air conditioner, wherein the mechanism for regenerating the adsorbent is a heat supply mechanism capable of supplying heat of 80 ° C. or less to the adsorption / desorption part. The operation method of the humidity control air conditioner according to claim 1, wherein the adsorption / desorption portion provided with the adsorbent is a desiccant rotor. The operation method of the humidity control air conditioner according to claim 1 or 2, wherein an abundance ratio of atoms of the zeolite satisfies the following formulas (1) to (3).
0.001 ≦ x ≦ 0.3 (1)
(In the formula, x represents the molar ratio of iron to the total of aluminum, phosphorus and iron in the skeleton structure.)
0.3 ≦ y ≦ 0.6 (2)
(In the formula, y represents the molar ratio of aluminum to the total of aluminum, phosphorus and iron in the skeleton structure.)
0.3 ≦ z ≦ 0.6 (3)
(In the formula, z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and iron in the skeleton structure.) In the water vapor adsorption isotherm measured at 25 ° C., the zeolite has an adsorption amount of 0.05 g / g or less at a relative vapor pressure of 0.1 and an adsorption amount of 0.15 g at a relative vapor pressure of 0.25. The operation method of the humidity control air conditioner according to any one of claims 1 to 3, wherein the operation method is equal to or greater than / g . The operation method of the humidity control air conditioner according to any one of claims 1 to 4, wherein the zeolite has a structure of AFI type. An adsorbent capable of adsorbing and desorbing the adsorbate; an adsorption / desorption portion including the adsorbent; and a heat supply mechanism for supplying heat to regenerate the adsorbent to the adsorption / desorption portion, and the heat of the heat supply mechanism Is below 80 ° C
And an adsorbent for a humidity control air conditioner that desorbs and regenerates moisture adsorbed on the adsorbent by heating with the heat supply mechanism,
The adsorbent is a zeolite containing aluminum and phosphorus and iron framework structure, the framework density is greater than 16.0T / 1000Å ^3, and at 20.0T / 1000Å ³ or less, and was measured at 25 ° C. In the water vapor adsorption isotherm, when the relative vapor pressure changes by 0.1 when the relative vapor pressure is in the range of 0.1 to 0.25, the water adsorption amount change has a relative vapor pressure range of 0.12 g / g or more. An adsorbent for a humidity control air conditioner that is zeolite , the zeolite is of AFI type, and the abundance ratio of the zeolite atoms satisfies the following formulas (1) to (3) .
0.001 ≦ x ≦ 0.3 (1)
(In the formula, x represents the molar ratio of iron to the total of aluminum, phosphorus and iron in the skeleton structure.)
0.3 ≦ y ≦ 0.6 (2)
(In the formula, y represents the molar ratio of aluminum to the total of aluminum, phosphorus and iron in the skeleton structure.)
0.3 ≦ z ≦ 0.6 (3)
(In the formula, z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and iron in the skeleton structure.) In the water vapor adsorption isotherm measured at 25 ° C., the zeolite has an adsorption amount of 0.05 g / g or less at a relative vapor pressure of 0.1 and an adsorption amount of 0.15 g at a relative vapor pressure of 0.25. The adsorbent for a humidity control air conditioner according to claim 6, wherein the adsorbent is / g or more . An adsorption / desorption portion comprising the adsorbent according to any one of claims 6 to 7 and a heat supply mechanism for regenerating the adsorbent, wherein the heat supplied to the heat supply mechanism is 80 ° C or lower. A humidity control air conditioner. The humidity control air conditioner according to claim 8, wherein the adsorption / desorption portion is a desiccant rotor. The humidity control air conditioner according to claim 8 or 9, further comprising a processing air path and a regeneration air flow path, wherein heat exchange is possible between the air in the processing air path and the air in the regeneration air flow.

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