JP4654582B2 - Adsorption heat pump operation method, adsorption heat pump, humidity control air conditioner operation method, and humidity control air conditioner - Google Patents

Description

  The present invention relates to a specific adsorbent and an adsorption heat pump or humidity control air conditioner using the same.

  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 vapor 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.

  Patent Document 2 discloses that a porous aluminum phosphate zeolite called AlPO-n is used as an adsorbent for a dehumidifying air conditioner. As an example, adsorption of AlPO4-5 is disclosed. An isotherm is disclosed. However, it is slightly hydrophobic and cannot sufficiently adsorb water vapor at a relative humidity of 0.25 at 25 ° C. Therefore, the amount of adsorption when the relative humidity changes by 0.1 in the range of the relative humidity of 0.12 to 0.25 at 25 ° C., which is the condition of the present invention to be described later for effectively using the low-temperature exhaust heat. "Change" is about 0.05 g / g, and the adsorption characteristics are inferior.

Patent Document 3 discloses that zeolite having aluminum, phosphorus, and hetero atoms is effective as an adsorbent for an adsorption heat pump. However, the present invention mainly focuses on the case of using a relatively high temperature of about 100 ° C. mainly for automobiles among low-temperature exhaust heat, and the examples specifically shown are “Adsorption amount change when relative humidity is changed by 0.1 in a range of relative humidity of 0.12 to 0.25 at 25 ° C.”, which is a condition of the present invention described later that effectively uses low-temperature exhaust heat. Adsorption performance is insufficient at about 0.02 g / g. That is, since the desorption performance is insufficient, the water vapor adsorption amount with a relative humidity of 0.12 which is an index of the desorption performance of the present invention described later is large, and as a result, the adsorption amount change is insufficient. Further, in this patent document, various atoms including iron are exemplified as heteroatoms, but those described in Examples all use Si as a heteroatom and have a framework density. Is 16 or less.

Patent Document 4 discloses an adsorption isotherm of AlPO-H6 in the examples. This is the condition of the present invention to be described later in terms of the adsorption characteristics indicated by the adsorption isotherm, “when the relative humidity changes by 0.1 within a range of 0.12 to 0.25 relative humidity at 25 ° C. The change in the amount of adsorption "satisfies 0.12 g / g or more, and low-temperature exhaust heat can be used effectively. However, according to the study by the present inventors, there is a problem in terms of durability. found. That is, according to the study by the present inventors, the zeolite whose structure changes between the adsorption state and the desorption state of water vapor has an unstable structure. It becomes unusable due to destruction. AlPO-H6 described in the patent document is in an adsorbed state of water vapor, and when desorbed, the structure changes to AlPO-D. This is described, for example, in P160 of Molecular Sieves Science and Technology Volume 1 (Springer 1998). Therefore, AlPO-H6 described in the patent document is not preferable because of insufficient durability during repeated adsorption and desorption of water vapor.
JP-A-9-178292 JP-A-11-197439 WO 02/066910 JP 2000-61251 A

  The present invention is an adsorption suitable for adsorption heat pumps or humidity control air conditioners that can adsorb and desorb the 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. It was made for the purpose of providing a material and an efficient adsorption heat pump or humidity control air conditioner using the same.

As a result of intensive studies to solve the above problems, the inventors of the present invention include a specific atom in the skeleton structure, a water adsorption amount difference in a specific relative vapor pressure range is in a specific range, and water vapor It has been found that zeolite having substantially no structural change in the adsorption / desorption of is suitable as an adsorbent for an adsorption heat pump or humidity control air conditioner using adsorption / desorption of adsorbate as a drive source of the apparatus.
That is, the gist of the present invention is that an adsorbate, an adsorption / desorption portion having an adsorbent for adsorbing / desorbing the adsorbate, an evaporation portion for evaporating the adsorbate coupled to the adsorption / desorption portion, and the adsorption / desorption portion An operation method of an adsorption heat pump including a condensing unit that condenses connected adsorbates, wherein the adsorbent is made of zeolite containing aluminum, phosphorus, and gallium in a skeleton structure, and the framework density of the zeolite is 16 greater than .0T / 1,000Å ^3, and at 19.0T / 1,000Å ³ or less, and the adsorption state of the position of the peak top of the 2 [Theta] = 15 degrees or less of the maximum peak in the XRD measurement of the desorption state and the adsorption state of the water vapor The difference from the desorption state is 0.2 degrees or less when expressed in 2θ, and the relative vapor pressure is 0 in the range of the water vapor adsorption isotherm measured at 25 ° C. between 0.12 and 0.25. .1 In International Zeolite Association (IZA) is zeolite having the AFI structure in code stipulated, and absorbing the desorption portion of the regeneration step adsorption change in water when made into having a 0.12 g / g or more relative vapor pressure range the heating medium 50 ° C. or higher 80 ° C. or less is supplied to the adsorbent to desorb the adsorbate adsorbed, characterized Rukoto, was adsorbed adsorbate by cooling the adsorption tower of the adsorption step to 30 to 40 ° C. And the operation method of the adsorption heat pump. Another gist is an operation method of a humidity control air conditioner having an adsorption / desorption part having an adsorbent capable of adsorbing and desorbing adsorbate and a heat supply mechanism for regenerating the adsorbent, wherein the adsorbent is a skeleton. structure consists zeolite containing aluminum and phosphorus and gallium, the framework density of the zeolite is greater than 16.0T / 1,000Å ^3, and at 19.0T / 1,000Å ³ or less, desorption state and the adsorption state of the water vapor The difference between the adsorption state and the desorption state at the peak top position of the maximum peak of 2θ = 15 degrees or less in the XRD measurement of this is 0.2 degrees or less when expressed in 2θ, and the water vapor adsorption isotherm measured at 25 ° C. International Zeolite Associati having a relative vapor pressure range where the amount of water adsorbed is 0.12 g / g or more when the relative vapor pressure changes by 0.1 in the range of 0.12 to 0.25 in on (IZA) is a zeolite having an AFI structure , and the adsorbent is regenerated by supplying heat from the heat supply mechanism to the adsorption / desorption portion at 80 ° C. or less to the adsorption portion. The operation method of the air conditioner exists.

  The adsorption heat pump and humidity control air conditioner using the adsorbent exhibiting a large change in the adsorption / desorption amount in the range of the relative vapor pressure of 0.12 or more and 0.25 or less of the present invention is the moisture adsorption amount by adsorption / desorption of the adsorbent. Since the difference is large and the adsorbent can be regenerated (desorbed) at a low temperature, it is possible to efficiently drive the adsorption heat pump and the humidity control air conditioner using a heat source having a temperature lower than that of the prior art. That is, according to the adsorbent of the present invention, it is possible to provide an adsorption heat pump and a humidity control air conditioner that are driven by a relatively low temperature heat source of 80 ° C. or less. In addition, since the adsorption heat pump of the present invention is driven efficiently by low-temperature heat, exhaust heat from a cogeneration system or the like can be effectively used, and further energy saving can be achieved.

Hereinafter, the present invention will be described in more detail.
<Adsorption heat pump and adsorption characteristics>
The operating vapor pressure range of the adsorption heat pump is determined by the desorption side relative vapor pressure φ1 and the adsorption side relative vapor pressure φ2 obtained from the high temperature heat source temperature High, the low temperature heat source temperature Tlow1, the low temperature heat source temperature Tlow2, and the cold heat generation temperature Tcool.

φ1 and φ2 can be calculated by the following equation, and the range between φ1 and φ2 is an operable relative vapor pressure range.
Desorption side relative vapor pressure φ1 = equilibrium vapor pressure (Tlow1) / equilibrium vapor pressure (High)
Adsorption side relative vapor pressure φ2 = equilibrium vapor pressure (Tcool) / equilibrium vapor pressure (Tlow2)
Here, the high temperature heat source temperature High is the temperature of the heat medium heated when desorbing the adsorbate from the adsorbent to regenerate the adsorbent, the low temperature heat source temperature Tlow1 is the temperature of the adsorbate in the condensing part, and the low temperature heat source temperature Tlow2. Means the temperature of the heat medium to be cooled when the adsorbent after regeneration is used for adsorption, and the cold generation temperature Tcool means the temperature of the adsorbate in the evaporation section, that is, the temperature of the generated cold. In the above formula, the equilibrium vapor pressures (Tlow1), (High), (Tcool), and (Tlow2) are the equilibrium vapor pressures at the respective temperatures (Tlow1), (High), (Tcool), and (Tlow2), respectively. The equilibrium vapor pressure can be obtained from the temperature using the equilibrium vapor pressure curve of the adsorbate.

  Hereinafter, the operating vapor pressure range when the adsorbate is water will be exemplified. The adsorption side relative vapor pressure φ2 is 0.22 when the cold heat generation temperature (Tcool) is 10 ° C. and the low temperature heat source temperature (Tlow2) is 35 ° C., the cold heat generation temperature (Tcool) is 8 ° C., and the low temperature heat source temperature (Tlow2). ) Is 0.25 when it is 30 ° C. The desorption side relative vapor pressure φ1 is 0.14 when the low temperature heat source temperature (Tcool) is 30 ° C. and the high temperature heat source temperature (High) is 70 ° C., the low temperature heat source temperature (Tcool) is 35 ° C., and the high temperature heat source temperature (High). ) Is 80 ° C., it is 0.12.

From the above, a gas engine cogeneration, if using a solid polymer electrolyte fuel cell or plant exhaust heat or the like for driving the adsorption heat pump, operating the relative water vapor pressure range φ1~φ2 = 0.12~0.25, preferably 0.13 to 0.25, and further limited to φ1 to φ2 = 0.14 to 0.22. That is, a material having a large change in adsorption amount within this operating humidity range is preferable.

Next, characteristics required for the adsorbent will be described.
Assume that a cooling capacity of 5.0 kW (= 18,000 kJ) is obtained by an adsorption heat pump. Here, 5.0 kW is a cooling capacity of about 16 tatami mats facing the south of the wooden building. The amount of latent heat of vaporization of water is about 2500 kJ / kg, and if the adsorption / desorption switching cycle is 10 minutes (6 times / hour), if the adsorption amount is 0.12 g / g, the adsorbent needs 10.0 kg. Become. Necessary amount of adsorbent Xkg = 18000 kJ / (2500 kJ × 0.12 kg / kg × 6 times / hr) = 10.0 kg. Similarly, if the adsorption amount is 0.15 g / g, 8 kg is required. When the switching cycle is 6 minutes (10 times / hour), it is 6.0 kg when it is 0.12 g / g and 4.8 kg when it is 0.15 g / g. The larger the amount of adsorption, the better, but the smaller the weight and volume of the adsorbent, the better. This is because, in general, there are many restrictions on the place area required for installation, and thus a smaller apparatus and a larger performance apparatus are required. Since it is necessary to increase the amount of adsorption in order to satisfy both conflicting requirements, the amount of adsorption is 0.12 g / g or more, preferably 0.14 g / g or more, more preferably 0.15 g / g. The above adsorbents are 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 change in adsorption amount is not particularly limited, but is usually about 0.3 g / g or less due to material restrictions.

  Further, the adsorbent is preferably a material having a large change in adsorption amount in a narrow relative vapor pressure range. When the change in adsorption amount is large in a narrow relative vapor pressure range, the amount of adsorbent required to obtain the same adsorption amount under the same conditions is reduced, and the adsorption heat pump is driven even if the temperature difference between the cooling heat source and the heating heat source is small. Because it can. From this point, in the water vapor adsorption isotherm measured at 25 ° C., when the relative vapor pressure changes by 0.1 in the range of 0.12 to 0.25, the change in water adsorption amount is 0.12 g / It is necessary to have a relative vapor pressure range of g or more.

  In terms of 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 not particularly limited. However, in terms of desorption performance, the adsorption amount is 0.05 g / g or less, preferably 0.03 g / g or less, and more preferably 0.03 g / g or less at a relative vapor pressure of 0.12. Is 0.02 g / g or less, and the lower limit is preferably as close to 0 as possible, but usually an adsorbent of 0.00001 g / g or more is preferable.

<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.

Also in the case of humidity control air conditioning, it is determined by the desorption side relative vapor pressure φ1 and the adsorption side relative vapor pressure φ2 as in the case of the adsorption heat pump. However, in the case of humidity control air conditioning, since it is generally an operation using air under atmospheric pressure,
φ1 = absolute humidity of air after treatment / saturated vapor pressure at treatment temperature φ2 = 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 operating relative water vapor pressure range is φ1 to φ2 = 0.07 to 0.5, and an adsorbent material having a large change in adsorption amount 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. Furthermore, for the same reason as in the case of the adsorption heat pump, the adsorbent is preferably a material having a large change in adsorption amount in a narrow relative vapor pressure range. Considering these, a material that adsorbs more water vapor at a relative humidity of 0.12 to 0.25 in the above operating humidity range is preferable.

  Similarly to the adsorption heat pump, since the adsorption amount is large in the humidity control apparatus and the weight and volume of the adsorbent are small, the adsorption amount change is 0.12 g / g or more, preferably 0.14 g / g. An adsorbent of g or more, more preferably 0.15 g / g or more is preferable. 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. When the relative vapor pressure is changed by 0.1 in the range of the water vapor adsorption isotherm measured at 25 ° C. within the range of 0.12 to 0.25, the relative change in water adsorption amount is 0.12 g / g or more. Must have a vapor pressure range.

  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 not usually 0.3 g / g or less, on the other hand, in terms of desorption performance, the adsorption amount at a relative vapor pressure of 0.1 is 0.05 g / g or less, preferably 0.03 g / g or less. The adsorbent is preferably 0.02 g / g or less, and the lower limit is preferably 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 to use an adsorbent having the above characteristics as an adsorbent for an adsorbate adsorption / desorption portion of an adsorption heat pump. That is, since a large amount of adsorption can be obtained with a relatively small change in relative vapor pressure on the relatively low relative pressure side, it is suitable for an adsorption heat pump, such as a factory air conditioner, where the temperature lower limit of the low-temperature heat source is limited.
Another feature of the present invention resides in the use of an adsorbent having the above characteristics for the adsorbing portion of the humidity control air conditioner.

  Adsorption heat pumps and humidity control air conditioners use the ability of adsorbents to adsorb and desorb adsorbate as a drive source. In the adsorption heat pump and 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>
An adsorbent for heat pump or an adsorbent for humidity control air conditioner, which is a feature of the present invention, is a zeolite which is a crystalline gallium aluminophosphate containing at least aluminum, phosphorus and gallium in the skeleton structure, and is substantially absorbed and desorbed by water vapor. This zeolite has no structural change. When used as an adsorption heat pump or an adsorbent for a humidity control air conditioner, it is necessary to repeat the adsorption and desorption of water vapor stably. At that time, as described above, the structure of the zeolite whose structure changes between the adsorption state and the desorption state of water vapor increases the distortion of the structure as the adsorption and desorption is repeated, and the structure becomes unstable, so that sufficient performance cannot be obtained. Therefore, in terms of the performance of adsorption heat pumps and humidity control air conditioners, it is important that there is substantially no structural change due to the adsorption and desorption of water vapor in order to have high durability against repeated adsorption and desorption of water vapor. . The fact that there is substantially no change in structure due to the adsorption / desorption of water vapor means that the results of XRD measurement in the adsorption state and the desorption state of water vapor are substantially the same. More quantitatively, when XRD measurement is performed under the conditions described in the examples, the difference between the adsorption state and the desorption state at the peak top position of the maximum peak (peak height is maximum) of 2θ = 15 degrees or less is When expressed in 2θ, it is 0.2 degrees or less. It becomes a highly durable zeolite by substantially no structural change due to the adsorption and desorption of water vapor. The high durability is, for example, the adsorption and desorption 1,000 under the conditions of the durability test shown in the Examples. The adsorption amount at a relative humidity of 0.25 of the adsorption isotherm at 25 ° C. after the rotation is 70% or more, preferably 80% or more, more preferably 90% or more before the test.

Further, the framework density is greater than 16.0T / 1,000Å ^3, good 19.0T / 1,000Å ³ or less, preferably 16.2T / 1,000Å ³ or more, whereas, 19.0T / 1,000 Å ³ or less, more 18.0T / 1,000Å ³ or less in the range of zeolites are preferred. Further, the structure of at least one pore of the zeolite is preferably an oxygen 8-membered ring or more, more preferably a 10-membered ring or more, and most preferably a 12-membered ring or more. In the case of pores with an oxygen seven-membered ring or less, the diffusion of water vapor into and out of the pores may be insufficient, and even if the adsorption / desorption rate is slow or the adsorption / desorption hysteresis is large, desorption is possible. Problems such as difficulty in peeling may occur.

By selecting such zeolite, the above adsorption performance can be achieved. If the framework density is too small, the difference in adsorption amount tends to increase, but there is a risk that adsorption / desorption will not occur in an appropriate relative humidity range, or the structure will be unstable, resulting in durability problems. If the amount is too large, the difference in the amount of adsorption is too small, so that the performance of the present invention may not be satisfied. 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 zeolite structure is shown in ATLAS OF ZEOLITE FRAMEWARK TYPES Fifth Revised Edition 2001 ELSEVIER.

  The structure of such a zeolite is represented by a code defined by the International Zeolite Association (IZA). AET, AFI, AFN, ANA, AST, ATN, ATS, ATT, BPH, BRE, CON, CZP, DFT, EDI, FER, LAU, LTL, MAZ, MEL, MFI, MOR, MWW, OSI, SAT, TER, VNI, VSV, ZON are mentioned, preferably AET, AFI, AST, ATS, more preferably 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 gallium aluminophosphate containing at least aluminum, phosphorus and gallium in the skeleton structure, and the gallium of the crystalline gallium 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 gallium 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 gallium to the total of aluminum, phosphorus and gallium 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 gallium in the skeleton structure)

0.3 ≦ z ≦ 0.6 (3)
(Wherein z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and gallium in the skeleton structure)
And among the above-mentioned proportions of atoms, the proportion of gallium 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.

  The skeletal structure of the crystalline gallium aluminophosphate in the present invention may contain elements other than Ga, Al and P. Examples of other elements include silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, cobalt, nickel, palladium, copper, zinc, germanium, arsenic, tin, calcium, and boron. Usually, the molar ratio (M / Ga) of other elements (M) and gallium (Ga) is 3 or less, preferably 1.5 or less, more preferably 0.5 or less. When M / Ga 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.
Further, 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 0.12 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 0.14 g / g or more, more preferably 0.15 g / g or more, and preferably a relative vapor pressure of 0.14 or more and 0.22. When the relative vapor pressure is changed by 0.08 in the following range, the adsorption amount change of water is 0.12 g / g or more, preferably 0.14 g / g or more, more preferably 0.15 g / g or more. is there. By having such adsorption characteristics, as described above, the adsorption heat pump can be driven by a low temperature side heat source of 30 ° C. or higher and a high temperature side heat source of 80 ° C. or less, and the adsorption amount difference is large, thereby making the adsorption heat pump compact. Can be.
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 adsorption heat pump or humidity control air conditioner of the present invention is basically composed of the above zeolite, but is used in combination with other adsorbents or as an adsorbent as long as the performance is not impaired. Other components may be included as needed.

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

First, an aluminum source, a gallium 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.

  Gallium source: The gallium source is not particularly limited, and usually includes gallium sulfate, gallium nitrate, gallium phosphate, gallium chloride, gallium bromide, gallium hydroxide, and the like. Of these, gallium nitrate and gallium chloride are preferable.

Phosphorus source: Phosphoric acid is usually used as the phosphorus source, but aluminum phosphate may be used.
Other elements: The gallium aluminophosphate skeleton structure 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, 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-methylpiperi , 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 above-mentioned aluminum source, gallium source, phosphorus source and template. The mixing order varies depending on conditions, but usually, a phosphoric acid source and an aluminum source are first mixed, and a gallium source and a template are mixed therewith.
The composition of the aqueous gel according to gallium aluminophosphate is 0.01 ≦ GaO _1.5 / P ₂ O ₅ ≦ 1.5 in terms of the molar ratio of the oxide, and is 0 from the viewpoint of ease of synthesis. 0.02 ≦ GaO _1.5 / P ₂ O ₅ ≦ 1.0 is preferable, and 0.05 ≦ GaO _1.5 / 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 firing using air or the like by a method such as firing to obtain such crystalline gallium aluminophosphate. .
One of the features of the present invention is to use an adsorbent having the above characteristics as an adsorbent for an adsorbate adsorption / desorption part of an adsorption heat pump or as an adsorbent for an adsorption / desorption part of a humidity control air conditioner. That is, since a large amount of adsorption can be obtained with a relatively small change in relative vapor pressure on the relatively low relative pressure side, an adsorption heat pump or humidity control air conditioner with a lower temperature limit of the low-temperature heat source, such as a factory air conditioner, etc. Suitable for

<Adsorption heat pump action>
Hereinafter, although the action of the adsorption heat pump of the present invention using the above-described adsorbent will be specifically described with the adsorption heat pump having the apparatus configuration shown in FIG. 1, the adsorption heat pump of the present invention is not limited to this.
The conceptual diagram of an example of the adsorption heat pump of this invention is shown in FIG. The adsorption heat pump shown in FIG. 1 includes an adsorbent capable of adsorbing and desorbing adsorbate, and adsorption towers 1 and 2 serving as adsorbing and desorbing portions that are filled with the adsorbent and transmit heat generated by adsorption and desorption of the adsorbate to a heat medium. The evaporator 4 takes out the cold heat obtained by the evaporation of the adsorbate and the condenser 5 discharges the hot heat obtained by the condensation of the adsorbate to the outside. When operating the adsorption heat pump, the operation conditions are obtained from the adsorption isotherm at the ambient temperature so that the adsorption / desorption amount necessary for the operation can be obtained, and the maximum adsorption / desorption amount is usually obtained when the apparatus is operated. To be determined.

As shown in FIG. 1, the adsorption towers 1 and 2 filled with the adsorbent are connected to each other by an adsorbate pipe 30, and the adsorbate pipe 30 is provided with control valves 31 to 34. Here, the adsorbate exists as an adsorbate vapor or a mixture of adsorbate liquid and vapor in the adsorbate pipe.
The evaporator 4 and the condenser 5 are connected to the adsorbate pipe 30. The adsorption towers 1 and 2 are connected in parallel between the evaporator 4 and the condenser 5, and between the condenser 5 and the evaporator 4, the adsorbate condensed in the condenser is returned to the evaporator 4. The return pipe 3 is provided. Reference numeral 41 denotes an inlet of cold water that serves as a cooling output from the evaporator 4, and reference numeral 51 denotes an inlet of cooling water to the condenser 5. Reference numerals 42 and 52 denote outlets of cold water and cooling water, respectively. The cold water pipes 41 and 42 are connected to an indoor unit 300 for exchanging heat with the indoor space (air-conditioned space) and a pump 301 for circulating cold water.

  A heat medium pipe 11 is connected to the adsorption tower 1, and a heat medium pipe 21 is connected to the adsorption tower 2. The heat medium pipes 11 and 21 are provided with switching valves 115 and 116, and 215 and 216, respectively. is there. The heat medium pipes 11 and 21 flow a heat medium serving as a heating source or a cooling source for heating or cooling the adsorbents in the adsorption towers 1 and 2, respectively. The heat medium is not particularly limited as long as the adsorbent in the adsorption tower can be effectively heated and cooled.

  The 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 towers 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 / closing similar switching valves 115, 116, 215, and 216, passes through the respective adsorbers 1 and / or 2, and is led out from the outlets 112 and / or 212. The Moreover, although not shown in figure, the outdoor unit arrange | positioned so that heat exchange with external air, the heat source which produces | generates warm water, and the pump which circulates a heat medium are connected to the heat medium piping 11 and / or 21. It does not specifically limit as a heat source, For example, cogeneration apparatuses, such as a gas engine and a gas turbine, and a fuel cell are mentioned.

  The operation method of the adsorption heat pump will be described with reference to FIG. In the first stroke, the control valves 31 and 34 are closed, the control valves 32 and 33 are released, and the regeneration process is performed in the adsorption tower 1 and the adsorption process is performed in the adsorption tower 2. Further, the switching valves 115, 116, 215, and 216 are operated, and hot water is circulated through the heat medium pipe 11 and cooling water is circulated through the heat medium pipe 21.

  When the adsorption tower 2 is cooled, cooling water cooled by a heat exchanger such as a cooling tower is introduced through the heat medium pipe 21 and is usually cooled to about 30 to 40 ° C. Moreover, the water in the evaporator 4 evaporates by opening operation of the control valve 32, flows into the adsorption tower 2 as water vapor, and is adsorbed by the adsorbent. 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 temperature of the cooling water in the adsorption tower and the temperature of the cold water generated by the evaporator, the relative vapor pressure φ2 on the adsorption side (where φ2 is the equilibrium vapor pressure of the adsorbate at the cold water temperature generated by the evaporator, Calculated by dividing by the equilibrium vapor pressure of the adsorbate at the water temperature), but φ2 can be operated so that the adsorbent specified in the present invention is larger than the relative vapor pressure at which water vapor is adsorbed to the maximum. preferable. This is because when the adsorbent specified in the present invention is smaller than the relative vapor pressure at which water vapor is adsorbed at the maximum, the adsorbing capacity of the adsorbent cannot be used effectively and the operating efficiency is deteriorated. φ2 can be appropriately set according to the environmental temperature or the like, but the adsorption heat pump is operated under a temperature condition in which the adsorption amount at φ2 is usually 0.12 or more, preferably 0.15 or more.

  The adsorption tower 1 in the regeneration step is usually heated with hot water of 40 to 100 ° C., preferably 50 to 80 ° C., more preferably 60 to 70 ° C., and has an equilibrium vapor pressure corresponding to the temperature range. It is condensed with a saturated vapor pressure at a condensation temperature of 30-40 ° C. (this is equal to the temperature of the cooling water cooling the condenser). Water vapor moves from the adsorption tower 1 to the condenser 5 and is condensed to become water. Water is returned to the evaporator 4 by the return pipe 3. From the relationship between the condenser cooling water temperature and the hot water temperature, the desorption side relative vapor pressure φ1 (where φ1 is the equilibrium vapor pressure of the adsorbate at the temperature of the condenser cooling water, and the equilibrium of the adsorbate at the temperature of the hot water) It is preferable to operate so that φ1 becomes smaller than the relative vapor pressure at which the adsorbent rapidly adsorbs water vapor. If φ1 is larger than the relative vapor pressure at which the adsorbent rapidly adsorbs water vapor, the excellent adsorption amount of the adsorbent cannot be used effectively. φ1 can be appropriately set depending on the environmental temperature or the like, but the adsorption heat pump is operated under a temperature condition in which the adsorption amount at φ1 is usually 0.14 or less, preferably 0.10 or less. The difference between the adsorbate adsorption amount at φ1 and the adsorbate adsorption amount at φ2 is usually 0.12 g / g or more, preferably 0.14 g / g or more, more preferably 0.15 g / g or more. To drive. The above is the first step.

  In the next second step, the evaporators are similarly switched by switching the control valves 31 to 34 and the switching valves 115, 116, 215, and 216 so that the adsorption tower 1 is an adsorption process and the adsorption tower 2 is a regeneration process. From 4, it is possible to obtain cold heat, that is, cooling output. The adsorption heat pump is continuously operated by sequentially switching the first and second strokes.

Here, the operation method in the case where two adsorption towers are installed has been described. However, by properly desorbing the adsorbate adsorbed by the adsorbent, one of the adsorption towers can maintain a state in which the adsorbate can be adsorbed. If possible, any number of adsorption towers may be installed.
<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. 2 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 as in the case of the adsorption heat pump, 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. 3 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 47 g of water and 23 g of 85% phosphoric acid, 12.6 g of pseudoboehmite (containing 25% water, manufactured by Condea) was added and stirred. This was stirred for 3 hours, and an aqueous solution obtained by dissolving 8 g of gallium nitrate octahydrate in 51 g of water was added thereto, and further 14.2 g of triethylamine was mixed and stirred for 3 hours. The obtained reaction raw material mixture was charged into a 200 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and reacted at 200 ° C. for 3 hours in a stationary state. After the reaction, the reaction mixture was cooled, the supernatant was removed by decantation, and the precipitate was recovered. The precipitate was washed three times with water, filtered off and dried at 120 ° C. Thereafter, 3 g of the sample containing the template thus obtained was collected, put into 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. After baking for 6 hours and measuring the XRD of the crystalline gallium aluminophosphate thus obtained, it was an AFI type GAPO-5. In addition, when the elemental analysis was performed by ICP analysis after heating and dissolving in an aqueous hydrochloric acid solution, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus and gallium in the skeleton structure was 3.7% for gallium and aluminum. It was 45.5% and phosphorus was 50.8%.

  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.

  From FIG. 4, water vapor is adsorbed suddenly in the vicinity of the relative vapor pressure of 0.20, and the maximum amount of adsorption change when the relative vapor pressure changes by 0.1 in the relative vapor pressure range of 0.12 to 0.25 is 0. It can be seen that the change in adsorption amount is 0.15 g / g when the relative vapor pressure range is 0.14 to 0.22 in the range of 0.16 g / g. GAPO-5 having such characteristics is one of the most preferable adsorbents used in the present invention.

In addition, in-situ XRD measurement was performed in order to examine the structural change during the adsorption and desorption of water vapor. XRD measurement was performed under the following conditions.
Zeolite was set in the following apparatus, and the temperature was raised from room temperature (25 ° C.) to 150 ° C. at a heating rate of 5 ° C./min in a nitrogen atmosphere with a humidity of 0% to desorb water adsorbed on the zeolite. Thereafter, the temperature was decreased from 150 ° C. to 45 ° C. at a temperature decrease rate of 5 ° C./min in a nitrogen atmosphere with a humidity of 0%, and the XRD in a desorbed state was measured at 45 ° C. Thereafter, nitrogen containing water vapor was introduced into the apparatus, and XRD in a water vapor adsorption state at a relative humidity of 70% at 45 ° C. was measured. The result is shown in FIG.

XRD measurement conditions Equipment:
RINT2000
Ultimate + series (Rigaku)
Goniometer Ultimate + Horizontal goniometer Attachment X-ray DSC
Monochromator Fixed Monochromator Scanning Mode 2 Theta / Theta
Scanning Type Continuos Scanning
X-Ray 40kV / 50mA
Divergence slit 1/2 °
Divergence length restriction slit 10mm
Scattering slit 1 °
Receiving slit 0.3mm
Monochrome light receiving slit None

From this, it can be seen that the structure has hardly changed due to the adsorption and desorption of water. The peak position of the maximum peak at 2θ = 15 degrees or less was a change of 0.08 degrees in adsorption / desorption.
In addition, a durability test was performed on the zeolite by the following method.
(Durability test)
The operation of placing the zeolite in a vacuum vessel maintained at 90 ° C. and exposing it to a saturated steam atmosphere at 80 ° C. and a saturated steam atmosphere at 5 ° C. for 90 seconds was repeated. By being exposed to a saturated water vapor atmosphere at 80 ° C., water is adsorbed on the zeolite, and most of the adsorbed in the saturated water vapor atmosphere at 5 ° C. is desorbed and moves to a water reservoir maintained at 5 ° C. This was repeated 1,000 times.
Before and after this durability test, the adsorption isotherm at 25 ° C. was measured under the above conditions to examine the change. As a result, the adsorption amount at a relative humidity of 0.25 was 75% after the durability test and before the durability test, and the change was small.

[Comparative Example 1]
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. The mixture was stirred for 3 hours, 36.6 g of water was added thereto, 11.6 g of triethylamine was further mixed and stirred for 3 hours, and a reaction raw material mixture having the following composition was obtained.

Al ₂ O ₃ : P ₂ O ₅ : 1.5 Triethylamine: 60H ₂ O
The reaction raw material mixture 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. 5 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. 5 shows that the amount of change in the adsorption amount in the relative vapor pressure range of 0.12 to 0.25 is only 0.03 g / g. AlPO-5 having such characteristics is not suitable for the adsorbent of the present invention.

[Comparative Example 2]
While a solution obtained by adding 20 g of water to 8.16 g of pseudoboehmite was added dropwise, a solution obtained by adding 20 g of water to 13.8 g of 85% phosphoric acid was added dropwise, and stirring was continued for 2 hours. To this, 6.6 g of DPA (dipropylamine) was added dropwise and stirred for 2 hours. Half of this starting mixture was charged into 100 ml AC lined with Teflon (registered trademark) and subjected to hydrothermal synthesis at 110 ° C. for 4 days. When this was filtered, washed with water, dried and XRD was measured, it was an AlPO-C (APC) structure.
When this was calcined at 260 ° C. for 6 hours under an air stream and then XRD was measured, it was AlPO-D (APD).
In order to examine the structural change in the water vapor adsorption and desorption, the measurement was performed under the same conditions as in Example 1. The results are shown in FIG. From this, it can be seen that the XRD peak position is changed by adsorption / desorption, and the structure is AlPO-H6 in the adsorbed state and AlPO-D in the desorbed state. The peak position of the maximum peak at 2θ = 15 degrees or less changed by 0.34 degrees during adsorption / desorption.

  Next, a durability test was performed in the same manner as in Example 1. Similarly, when the adsorption amount at a relative humidity of 0.25 before and after the durability test is compared with an adsorption isotherm of 25 ° C., it greatly decreased to 28% after the durability test. That is, it can be seen that the structure is greatly broken by repeated adsorption and desorption, and there is a problem in stability. From this, it was confirmed that the structure that changes in structure due to adsorption / desorption has a problem in durability and is inappropriate.

  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 expressed.

It is a conceptual diagram of an adsorption heat pump. 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 adsorption isotherm of the adsorbent (GAPO-5) of Example 1. It is a water vapor adsorption isotherm of the adsorbent (ALPO-5) of Comparative Example 1. 2 is an XRD diagram of water vapor adsorption / desorption of the adsorbent (GAPO-5) of Example 1. FIG. It is a XRD figure of water vapor adsorption-desorption of the adsorbent (ALPO-D) of the comparative example 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Adsorption tower 2 Adsorption tower 3 Adsorbate piping 4 Evaporator 5 Condenser 11 Heating medium piping 111 Cooling water inlet 112 Cooling water outlet 113 Hot water inlet 114 Hot water outlet 115 Switching valve 116 Switching valve 21 Heating medium piping 211 Cooling water inlet 212 Cooling Water outlet 213 Hot water inlet 214 Hot water outlet 215 Switching valve 216 Switching valve 30 Adsorbate piping 31 Control valve 32 Control valve 33 Control valve 34 Control valve 300 Indoor unit 301 Pump 41 Cold water piping (inlet)
42 Cold water piping (exit)
51 Cooling water piping (inlet)
52 Cooling water piping (exit)
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 (12)

An adsorption / desorption part having an adsorbent for adsorbing and desorbing the adsorbate, an evaporation part for evaporating the adsorbate connected to the adsorption / desorption part, and a condensing part for condensing the adsorbate connected to the adsorption / desorption part An operation method of an adsorption heat pump comprising:
The adsorbent consists of a zeolite containing aluminum and phosphorus and gallium in the skeleton structure, the framework density of the zeolite is greater than 16.0T / 1,000Å ^3, and at 19.0T / 1,000Å ³ or less, the water vapor The difference between the adsorption state and the desorption state at the peak top position of the maximum peak of 2θ = 15 degrees or less in XRD measurement of the adsorption state and the desorption state is 0.2 degrees or less when expressed in 2θ, and at 25 ° C. In the measured water vapor adsorption isotherm, when the relative vapor pressure changes by 0.1 in the range of 0.12 or more and 0.25 or less, the change in the amount of adsorption of water is 0.12 g / g or more. to have a, International zeolite Association (IZA) is zeolite having the AFI structure in code stipulated, and 50 ° C. or higher 80 ° C. or less of the heat medium in the regeneration step of the adsorption-desorption unit Supplied to desorb the adsorbate adsorbed on the adsorbent, the method of operating the adsorption heat pump according to claim, be adsorbed adsorbate by cooling the adsorption tower of the adsorption step to 30 to 40 ° C.. Zeolite containing aluminum, phosphorus and gallium in the skeleton structure is represented by the following formulas (1), (2) and (3)
0.001 ≦ x ≦ 0.3 (1)
(Wherein x represents the molar ratio of gallium to the total of aluminum, phosphorus and gallium 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 gallium in the skeleton structure)
0.3 ≦ z ≦ 0.6 (3)
(Wherein z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and gallium in the skeleton structure)
The operation method of the adsorption heat pump according to claim 1, which has an abundance ratio of atoms represented by: The adsorbent has an adsorption amount at a relative vapor pressure of 0.1 or less in a water vapor adsorption isotherm measured at 25 ° C. of 0.05 g / g or less, and an adsorption amount at a relative vapor pressure of 0.25 of 0.15 g. The operation method of the adsorption heat pump according to claim 1 or 2 , wherein the operating method is at least / g. An adsorption / desorption part having an adsorbent for adsorbing and desorbing the adsorbate, an evaporation part for evaporating the adsorbate connected to the adsorption / desorption part, and a condensing part for condensing the adsorbate connected to the adsorption / desorption part a suction pump having bets, the temperature of the heat medium to be heated when reproducing the adsorbent to desorb the adsorbate from the adsorbent and 50 ° C. or higher 80 ° C. or less, the adsorbent skeleton structure to consist zeolite containing aluminum and phosphorus and gallium, the framework density of greater 19.0T / 1,000Å ³ the range from 16.0T / 1,000Å ^3, water vapor adsorption isotherm measured at 25 ° C. The line has a region where the relative vapor pressure is 0.12 or more and 0.25 or less, and when the relative vapor pressure is changed by 0.1, the water adsorption amount change is 0.12 g / g or more, and Aluminum contained in the skeletal structure An adsorption heat pump characterized in that, and phosphorus and gallium are zeolites having an AFI structure in a code defined by the International Zeolite Association (IZA) satisfying the following formulas (4), (5) and (6):
0.001 ≦ x ≦ 0.3 (4)
0.3 ≦ y ≦ 0.6 (5)
0.3 ≦ z ≦ 0.6 (6)
(Wherein, x, y, and z represent the ratio of aluminum, phosphorus, and gallium atoms to the total of aluminum, phosphorus, and gallium atoms contained in the skeleton structure, respectively) Zeolite containing aluminum, phosphorus and gallium in the skeletal structure has an adsorption amount of 0.05 g / g or less at a relative vapor pressure of 0.1 on a water vapor adsorption isotherm measured at 25 ° C., and a relative vapor pressure. The adsorption heat pump according to claim 4 , wherein the adsorption amount at 0.25 is 0.15 g / g or more. An operation method of a humidity control air conditioner having an adsorption / desorption part having an adsorbent capable of adsorbing and desorbing adsorbate, and a heat supply mechanism for regenerating the adsorbent,
The adsorbent is made of zeolite containing aluminum, phosphorus and gallium in a skeleton structure,
Framework density of the zeolite is greater than 16.0T / 1,000Å ^3, 19.0T / 1,000Å ³ or less, a peak of 2 [Theta] = 15 degrees or less of the maximum peak in the XRD measurement of the desorption state and the adsorption state of the water vapor The difference between the adsorption state and the desorption state at the top position is 0.2 degrees or less when expressed in 2θ, and the relative vapor pressure is 0.12 or more and 0.25 or less in the water vapor adsorption isotherm measured at 25 ° C. A zeolite having an AFI structure in a code defined by the International Zeolite Association (IZA) having a relative vapor pressure range of 0.12 g / g or more when the relative vapor pressure changes by 0.1 in the range; And the operation | movement method of a humidity control air conditioner which regenerates an adsorbent by supplying the heat | fever below 80 degreeC to a adsorption | suction part to the adsorption / desorption part from a heat supply mechanism. The operation method of the humidity control air conditioner according to claim 6 , wherein the adsorption / desorption portion is a desiccant rotor. Zeolite containing aluminum, phosphorus and gallium in the skeleton structure is represented by the following formulas (1), (2) and (3)
0.001 ≦ x ≦ 0.3 (1)
(Wherein x represents the molar ratio of gallium to the total of aluminum, phosphorus and gallium 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 gallium in the skeleton structure)
0.3 ≦ z ≦ 0.6 (3)
(Wherein z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and gallium in the skeleton structure)
The operation method of the humidity control air conditioner according to claim 6 or 7 , wherein the operation ratio of the humidity control air conditioner is represented by: The adsorbent has an adsorption amount at a relative vapor pressure of 0.1 or less in a water vapor adsorption isotherm measured at 25 ° C. of 0.05 g / g or less, and an adsorption amount at a relative vapor pressure of 0.25 of 0.15 g. The operation method of the humidity control air conditioner according to any one of claims 6 to 8 , which is equal to or more than / g. A humidity control air conditioner having an adsorption / desorption portion provided with an adsorbent, and a heat supply mechanism to the adsorption / desorption portion,
In order to regenerate the adsorbent, the temperature of heat supplied from the heat supply mechanism to the adsorption / desorption part is 80 ° C. or less,
The adsorbent is made of zeolite containing aluminum, phosphorus and gallium in a skeleton structure, and the zeolite has a framework density of more than 16.0T / 1,000Å3 and less than 19.0T / 1,000Å3 , The difference between the adsorption state and the desorption state at the peak top position of the maximum peak of 2θ = 15 degrees or less in XRD measurement in the adsorption state and the desorption state is 0.2 degrees or less when expressed in 2θ, and measured at 25 ° C. In the water vapor adsorption isotherm, when the relative vapor pressure changes by 0.1 in the range of 0.12 to 0.25, the change in the amount of water adsorption is 0.12 g / g or more. Defined by the International Zeolite Association (IZA) in which aluminum, phosphorus, and gallium included in the skeleton structure satisfy the following formulas (4), (5), and (6) A humidity control air conditioner characterized in that the cord is a theolite having an AFI structure .
0.001 ≦ x ≦ 0.3 (4)
0.3 ≦ y ≦ 0.6 (5)
0.3 ≦ z ≦ 0.6 (6)
(Wherein, x, y, and z represent the ratio of aluminum, phosphorus, and gallium atoms to the total of aluminum, phosphorus, and gallium atoms contained in the skeleton structure, respectively) The humidity control air conditioner according to claim 10 , wherein the adsorption / desorption portion is a desiccant rotor. The adsorbent has an adsorption amount at a relative vapor pressure of 0.1 or less in a water vapor adsorption isotherm measured at 25 ° C. of 0.05 g / g or less, and an adsorption amount at a relative vapor pressure of 0.25 of 0.15 g. The humidity control air conditioner according to claim 10 or 11 , which is at least / g. "

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