JP4354755B2 - Adsorbent for adsorption heat pump and adsorption heat pump using the same - Google Patents

Description

  The present invention relates to an adsorbent for an adsorption heat pump and an adsorption heat pump using the same, and more specifically, an adsorbent for an adsorption heat pump capable of realizing efficient adsorption / desorption using a heat source obtained from an automobile or the like, and the use thereof This is related to the adsorption heat pump.

  Adsorption heat pumps are installed in buildings, factories, etc., and are used to effectively use energy resources using waste heat, heat, etc. discharged from them. Adaptation is also being considered for houses and vehicles. In such an adsorption heat pump, a desorption process in which the adsorbent is heated to desorb an adsorbent such as water from the adsorbent, and an adsorbent that adsorbs the adsorbent to the adsorbent by cooling the adsorbent after desorbing the adsorbent. The process is repeated. In order for such a desorption process and adsorption process to be repeated efficiently, it is necessary that the adsorbent that adsorbs and desorbs the adsorbed material has an adsorption characteristic corresponding to the heat source supplied.

  Generally, the heat obtained by cooling water, solar heat, etc. of cogeneration equipment, fuel cells, automobile engines, etc. is 120 ° C. or less, mostly 105 ° C. or less, more often about 60 to 100 ° C., There is a demand for the development of an adsorbent that can efficiently absorb and desorb such low-temperature waste heat.

In particular, for automobiles that generate a large amount of waste heat and have the problem of further reducing fuel consumption due to the use of air conditioners, there is a strong demand for the practical use of compact adsorption heat pumps equipped with such adsorbents.
JP-A-9-178292

  However, Y-type zeolite, which has been studied as an adsorbent for adsorption heat pumps, adsorbs adsorbed substances even when the relative vapor pressure is close to zero. In order to make it almost 0, a high temperature of 150 ° C. to 200 ° C. or higher is required. Therefore, there is a problem that Y-type zeolite is difficult to use in the adsorption heat pump using the low-temperature waste heat described above.

  Similarly, the A-type silica gel being studied does not have sufficient adsorption characteristics at a low relative vapor pressure, and mesoporous silica (FSM-10 or the like) synthesized using a micelle structure of a surfactant as a template (see Patent Document 1 above). Is not adsorbed at a low relative vapor pressure, so that there is a problem that an adsorption heat pump using heat obtained by cooling water, solar heat, etc. of the above-mentioned cogeneration equipment, fuel cells, automobile engines, etc. cannot be constructed.

  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.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an adsorbent for an adsorption heat pump capable of realizing efficient adsorption / desorption using a heat source obtained from an automobile or the like, and this It is in providing the adsorption heat pump using this.

  As a result of intensive studies to solve the above problems, the present inventors have found that an adsorbent that has a specific relationship between the relative vapor pressure (synonymous with relative humidity; the same shall apply hereinafter) and the amount of adsorption is an adsorption heat pump, particularly The present invention has been found by finding that it is advantageous as an adsorbent used in an adsorption heat pump mounted on a vehicle.

The adsorption heat pump of the present invention that solves the above problems includes an adsorption substance, an adsorption / desorption part having an adsorbent for adsorbing / desorbing the adsorbed substance, and an evaporation part connected to the adsorption / desorption part for evaporating the adsorbed substance And a condensing unit that is coupled to the adsorption / desorption unit and condenses the adsorbent, and the adsorbent is evaporated at a temperature of 30 to 60 ° C. when adsorbed on the adsorbent. An adsorption heat pump,
Adsorbing the adsorbent is the zeolite crystalline iron aluminophosphate or crystalline silicon aluminophosphate zeolite, the framework density is 10T / nm ³ or more 18T / nm ³ or less, measured at 55 ° C. In the isotherm, the adsorption amount of the adsorbent at a relative vapor pressure of 0.02 is greater than 0 and 0.12 g / g or less, and the adsorption amount of the adsorbent at a relative vapor pressure of 0.1 is 0.13 g / g or more. 0.4 g / g or less, and when the relative vapor pressure is changed by 0.05 within the range of relative vapor pressure of 0.02 or more and 0.1 or less, the adsorption amount change of the adsorbed substance is 0.08 g / g or more. It has a relative vapor pressure region.

  According to this adsorption heat pump, since it has the adsorbent having the above-mentioned adsorption / desorption characteristics, the adsorption heat pump is mounted on an automobile or the like that has a problem of effective use of a large amount of waste heat and improvement in fuel consumption reduction based on air-conditioner driving. As a very suitable.

In this adsorption heat pump, (1) the crystalline iron aluminophosphate is at least 9.5 ± 0.3, 10.1 ± in powder X-ray diffraction measurement with Cu-Kα ray having an X-ray wavelength of 1.5418 mm. For diffraction angles (2θ) of 0.3, 12.8 ± 0.3, 19.5 ± 0.3, 20.4 ± 0.3, 24.3 ± 0.3 and 30.7 ± 0.4 (2) the amount of adsorption of the adsorbed substance at a relative vapor pressure of 0.02 is greater than 0 g / g and 0.1 g / g or less, and the amount of adsorbed substance at a relative vapor pressure of 0.1 Is preferably 0.15 g / g or more and 0.4 g / g or less.

The first feature of the adsorbent of the present invention that solves the above problems is that an adsorbent, an adsorbent / desorber comprising an adsorbent that adsorbs / desorbs the adsorbent, and the adsorbent / desorber are connected to the adsorbent. An evaporation unit that performs evaporation; and a condensing unit that is connected to the adsorption / desorption unit and that condenses the adsorbed material, and the temperature of the adsorbent when the adsorbed material is evaporated and adsorbed on the adsorbent It is an adsorbent for use in the adsorption heat pump described above, which is 30 to 60 ° C.
Adsorbing the adsorbent is the zeolite crystalline iron aluminophosphate or crystalline silicon aluminophosphate zeolite, the framework density is 10T / nm ³ or more 18T / nm ³ or less, measured at 55 ° C. In the isotherm, the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.02 is greater than 0 g / g and 0.12 g / g or less, and the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.1 is 0.13 g / g. g or more and 0.4 g / g or less, and when the relative vapor pressure is changed by 0.05 in the range of relative vapor pressure of 0.02 or more and 0.1 or less, the change in the amount of adsorption of the adsorbed substance is 0.08 g / g or more. And having a relative vapor pressure region.

In this adsorbent, (1) the amount of adsorbed material adsorbed at a relative vapor pressure of 0.02 is 0.0 g / g or more and 0.1 g / g or less, and the amount of adsorbed material adsorbed at a relative vapor pressure of 0.1 Is 0.15 g / g or more and 0.4 g / g or less , and (2) the amount of adsorption of the adsorbed substance at a relative vapor pressure of 0.02 is 0.0 g / g or more and 0.05 g / g or less. The adsorption amount of the adsorbed substance at a vapor pressure of 0.1 is 0.2 g / g or more and 0.4 g / g or less , and the relative vapor pressure is changed by 0.05 within the range of the relative vapor pressure of 0.02 or more and 0.1 or less. The change in the amount of adsorption of the adsorbed material is 0.12 g / g or more, and (3) the amount of adsorption of the adsorbed material at a relative vapor pressure of 0.02 is 0.0 g / g or more and 0.1 g / g or less. There, the adsorption amount of adsorbate at a relative vapor pressure 0.07 is not more than 0.15 g / g or more 0.4 g / g, relative vapor pressure of 0.0 It is preferable adsorption change in the adsorbate when the relative vapor pressure is 0.05 varied from 0.1 inclusive to be at 0.08 g / g or more, either.

In this adsorbent,
(I) the crystalline iron aluminophosphate is, contains at least Fe, Al and P in a framework structure, that the framework density of 10T / nm ³ or more 16T / nm ³ or less,
(Ii) The crystalline iron aluminophosphate is at least 9.5 ± 0.3, 10.1 ± 0.3, 12 in powder X-ray diffraction measurement with Cu-Kα rays having an X-ray wavelength of 1.5418 mm. A diffraction peak appears at diffraction angles (2θ) of .8 ± 0.3, 19.5 ± 0.3, 20.4 ± 0.3, 24.3 ± 0.3, and 30.7 ± 0.4. ,
(iii) the Fe, Al, and P constitute a skeletal structure at a molar ratio of the following formulas 1-3;
0.001 ≦ x ≦ 0.3… 1
(X represents the molar ratio of Fe to the total of Fe, Al and P)
0.2 ≦ y ≦ 0.6 2
(Y represents the molar ratio of Al to the total of Fe, Al and P)
0.3 ≦ z ≦ 0.6 3
(Z represents the molar ratio of P to the sum of Fe, Al and P),
(Iv) the crystalline silicon aluminophosphate is, contains at least Si, Al and P in a framework structure, Si, molar ratio of Si to the sum of Al and P is greater than 9 percent, the framework density of 10T / nm ³ or more and 16 T / nm ³ or less,
(V) Si, Al, and P constitute a skeleton structure in a molar ratio of the following formulas 4 to 6,
0.09 <p ≦ 0.30 4
(P represents the molar ratio of Si to the sum of Si, Al and P)
0.30 ≦ q ≦ 0.60… 5
(Q represents the molar ratio of Al to the sum of Si, Al and P)
0.30 ≦ r ≦ 0.60… 6
(R represents the molar ratio of P to the sum of Si, Al and P)
It is preferable that it is either.

According to the adsorbent of the present invention having the characteristics described above, the adsorbent has an adsorption isotherm of 0 g / g at a relative vapor pressure of 0.02 on the adsorption isotherm measured at 55 ° C. Since it is larger than 0.12 g / g, it exhibits excellent desorption performance under such relative vapor pressure conditions. Such a relative vapor pressure condition is brought about by a relatively low heating temperature condition as a desorption temperature. Therefore, for example, a relatively low temperature of about 100 to 120 ° C. using waste heat of a generation device, a fuel cell, an automobile engine, etc. Even under a low heating temperature condition, the adsorbed material can be desorbed from the adsorbent satisfactorily and efficiently. Furthermore, (b) since the adsorption amount of the adsorbed substance at a relative vapor pressure of 0.1 is 0.13 g / g or more and 0.4 g / g or less , excellent adsorption performance is exhibited under such a relative vapor pressure condition. Such a relative vapor pressure condition is brought about by a relatively high temperature condition as the adsorption temperature. Therefore, for example, a relatively high cooling temperature condition using cooling water of about 30 to 60 ° C. obtained by an automobile radiator or the like. Even under the condition, the adsorbed substance can be adsorbed to the adsorbent well and efficiently. Furthermore, (c) the change in the amount of adsorption of the adsorbent when the relative vapor pressure is changed by 0.05 in the range of relative vapor pressure of 0.02 or more and 0.1 or less is as large as 0.08 g / g or more. Even if the difference between the desorption temperature and the cooling temperature is small, a good and efficient adsorption / desorption cycle can be achieved. As a result, it can be applied to an adsorption heat pump system having a slight temperature difference between a heating temperature of about 100 to 120 ° C. and a cooling temperature of about 30 to 60 ° C., such as an automobile. As described above, since the adsorbent of the present invention has such adsorption / desorption characteristics, it is preferably applied to an adsorption heat pump for automobiles that has an object of effective use of a large amount of waste heat and improvement of fuel consumption reduction based on air conditioner driving. Can do.

  The second feature of the adsorbent of the present invention that solves the above problems is a crystalline iron aluminophosphate containing at least Fe, Al, and P in the skeleton structure, and the crystalline iron aluminophosphate is X In powder X-ray diffraction measurement with Cu-Kα ray having a linear wavelength of 1.5418Å, at least 9.5 ± 0.3, 10.1 ± 0.3, 12.8 ± 0.3, 19.5 ± 0.00. The diffraction peak appears at diffraction angles (2θ) of 3, 20.4 ± 0.3, 24.3 ± 0.3, and 30.7 ± 0.4.

  In this adsorbent, the peak intensity appearing at the diffraction angle (2θ) 10.1 ± 0.3 is preferably 10% or more of the peak intensity appearing at the diffraction angle (2θ) 9.5 ± 0.3. More preferably, the peak intensity appearing at the folding angle (2θ) 19.5 ± 0.3 is 10% or more of the peak intensity appearing at the diffraction angle (2θ) 9.5 ± 0.3.

Further, the adsorbent has a framework density of 10 T / nm ³ or more and 18 T / nm ³ or less, and in the adsorption isotherm measured at 55 ° C., the adsorption amount of the adsorbed substance at a relative vapor pressure of 0.02 is 0 g / g is 0.12 g / g or more, the adsorption amount of the adsorbed substance at a relative vapor pressure of 0.1 is 0.13 g / g or more and 0.4 g / g or less , and the relative vapor pressure is 0.02 or more and 0.00. It is preferable to have a relative vapor pressure region in which the change in the amount of adsorption of the adsorbed material when the relative vapor pressure changes by 0.05 in the range of 1 or less is 0.08 g / g or more. The adsorption amount of the adsorbing substance at 02 is 0.0 g / g or more and 0.1 g / g or less, and the adsorption quantity of the adsorbing substance at the relative vapor pressure of 0.1 is 0.15 g / g or more (2 ) adsorption of adsorbate at a relative vapor pressure 0.02 0.0 g / Or 0.05 g / g or less, adsorption of the adsorbate at a relative vapor pressure of 0.1 is below 0.2 g / g or more 0.4 g / g, relative vapor pressure of 0.02 to 0.1 The change in the adsorption amount of the adsorbed material when the relative vapor pressure changes by 0.05 within the range of 0.12 g / g or more in the range of (3), and (3) the adsorption amount of the adsorbed material at the relative vapor pressure of 0.02 is 0.1 . 0 g / g or more and 0.1 g / g or less, the adsorption amount of the adsorbed substance at a relative vapor pressure of 0.07 is 0.15 g / g or more and 0.4 g / g or less , and the relative vapor pressure of 0.02 or more and 0 It is preferable that the change in the amount of adsorption of the adsorbed material when the relative vapor pressure changes by 0.05 in a range of 0.1 or less is 0.08 g / g or more.

  As described above, the adsorbent having the first and second characteristics has excellent adsorption / desorption characteristics under relatively low heating temperature conditions and excellent adsorption performance under relatively high cooling temperature conditions. Furthermore, even if the difference between the heating temperature and the cooling temperature is small, there is a sufficient difference in adsorption amount, so that a good and efficient adsorption / desorption cycle can be achieved. As a result, the present invention can be preferably applied to an adsorption heat pump for automobiles that has an object to effectively reduce waste heat generated in large quantities and to improve fuel consumption reduction based on driving of an air conditioner.

  According to the adsorbent for adsorption heat pump of the present invention, its adsorption / desorption characteristics are excellent in desorption performance under relatively low heating temperature conditions, excellent in adsorption performance under relatively high temperature cooling conditions, Even if the difference between the heating temperature and the cooling temperature is small, there is a sufficient difference in adsorption amount, so that a good and efficient adsorption / desorption cycle can be achieved. As a result, the present invention can be preferably applied to an adsorption heat pump for automobiles that has an object to effectively reduce waste heat generated in large quantities and to improve fuel consumption reduction based on driving of an air conditioner.

  Further, according to the adsorption heat pump of the present invention, since the adsorbent having the above-described adsorption / desorption characteristics is provided, it is mounted on an automobile or the like that has a problem of effective use of a large amount of waste heat and improvement of fuel consumption reduction due to air conditioner driving. It is extremely suitable as an adsorption heat pump.

  Hereinafter, the adsorption material for adsorption heat pump of the present invention and the adsorption heat pump using the same will be described with reference to the drawings.

(Configuration of adsorption heat pump)
First, an adsorption heat pump to which the adsorbent of the present invention is applied will be described. FIG. 1 is a conceptual diagram illustrating an example of an adsorption heat pump.

  The adsorption heat pump includes an adsorbent, an adsorbent that adsorbs and desorbs the adsorbent, and an adsorption / desorption section that is filled with the adsorbent and transmits heat generated by the adsorption and desorption of the adsorbent to a heat medium (also referred to as adsorption towers 1 and 2). ), An evaporating unit (also referred to as an evaporator 4) for taking out the cold heat obtained by the evaporation of the adsorbing substance, and a condensing unit (also referred to as a condenser 5) for releasing the heat obtained by the condensation of the adsorbing substance to the outside. And is composed mainly of.

  The adsorption towers 1 and 2 contain a heat exchanger therein. The adsorbent is adhered to the surface of the heat exchanger and further packed in the packed tower. In the adsorption towers 1 and 2, adsorption / desorption is selectively caused by a heat source (cooling water / cooling water) supplied thereto to cause an exothermic reaction or an endothermic reaction based on heat. The adsorption tower 1 and the adsorption tower 2 are connected to each other by an adsorbent material pipe 30, and control valves 31 to 34 are provided in the middle of the pipe. In the pipe 30, the adsorbed substance vapor or a mixture of vapor and liquid exists.

  The evaporator 4 and the condenser 5 are connected to the adsorption towers 1 and 2 through an adsorbent material pipe 30. As an arrangement | positioning aspect, as shown in FIG. 1, it arrange | positions so that it may become a parallel aspect between the evaporator 4 and the condenser 5. As shown in FIG.

  A gaseous (for example, water vapor) adsorbed substance desorbed from the adsorbent is introduced into the condenser 5 from the adsorption towers 1 and 2. The condenser 5 includes a heat exchanger and condenses the gaseous adsorbed material. The heat exchanger is supplied with a heat medium cooled by outside air or the like (for example, cooling water cooled by a radiator). The adsorbed substance (for example, regenerated condensed water) condensed by the condenser 5 is sent to the evaporator 4 through the return pipe 3.

  The evaporator 4 is a device for evaporating the condensed adsorbed material. A refrigerant (for example, water) is sealed inside the evaporator 4 while being kept in a substantially vacuum, and further includes a heat exchanger. The heat exchanger exchanges heat between the above-described refrigerant and a heat medium (for example, a fluid in which ethylene glycol-based antifreeze is mixed with water) heat-exchanged with air-conditioner air blown indoors in the indoor unit 300, for example. . Reference numeral 41 is an inlet of cold water that serves as a cooling output from the evaporator 4, and reference numeral 51 is an inlet of cooling water to the condenser 5. Reference numerals 42 and 52 are 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.

Further, the heating medium pipe 11 to the adsorption tower 1, the heating medium pipe 21 to the adsorption column 2 is, respectively it connected to its heating medium pipe 11 and 21, the switching valves 115 and 116 and 215 and, respectively therewith 216 is provided. In addition, 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 flows through the heat medium pipes 11 and 21, respectively. The heat medium is not particularly limited as long as the adsorbent in the adsorption tower can be effectively heated and cooled.

  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 each adsorption tower 1 and / or 2, and is led out from the outlets 114 and / or 21, 4. The The cooling water is also introduced from the inlets 111 and / or 211 by passing the opening and closing of the 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 heat medium piping 11 and / or 21 are connected to an outdoor unit disposed so as to be able to exchange heat with the outside air, and a pump for circulating a hot / warm heat medium that generates hot water. The heat source is not particularly limited, and examples thereof include automobile engines, cogeneration equipment such as gas engines and gas turbines, and fuel cells. When used for automobiles, automobile engines and automobile fuel cells are preferable examples of heat sources. As mentioned.

  When operating an adsorption heat pump with such a configuration, the operating conditions are determined from the adsorption isotherm at the ambient temperature so that the adsorption / desorption amount required for operation can be obtained, and usually the maximum adsorption / desorption is required when operating the apparatus. The operating conditions are determined so that a quantity can be obtained.

(Operation method of adsorption heat pump)
Next, an operation method of the adsorption heat pump will be described.

  In the first step, the control valves 31 and 34 are closed, the control valves 32 and 33 are released, the desorption process (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 so that warm water is circulated through the heat medium pipe 11 and cooling water is circulated through the heat medium pipe 21.

  When cooling the adsorption tower 2, cooling water cooled by exchanging heat with outside air, river water, or the like by a heat exchanger such as a cooling tower is introduced through the heat medium pipe 21. The cooling water 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 30 to 60 ° C, preferably 35 to 55 ° C, more preferably 40 to 50 ° 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 adsorption-side relative vapor pressure φ2 (here, φ2 is the equilibrium vapor pressure of the adsorbed substance at the cold water temperature generated by the evaporator, which will be described later). Is divided by the equilibrium vapor pressure of the adsorbed material at the temperature of the cooling water of the adsorption tower. In the present invention, the adsorption-side relative vapor pressure φ2 is 0.1.

  The adsorption tower 1 in the desorption (regeneration) step is usually heated with hot water of 80 to 120 ° C., preferably 90 to 110 ° C., more preferably 95 to 105 ° C., and has an equilibrium vapor pressure corresponding to the temperature range, The condenser 5 is condensed with a saturated vapor pressure at a condensation temperature of 30 to 60 ° 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 temperature of the cooling water of the condenser 5 and the temperature of the hot water, the desorption side relative vapor pressure φ1 (where φ1 is described later, the equilibrium vapor pressure of the adsorbed material at the temperature of the cooling water of the condenser is determined as the hot water temperature). Determined by dividing by the equilibrium vapor pressure of the adsorbed material at temperature). In the present invention, the desorption side relative vapor pressure φ1 is 0.02.

  Next, in the second stroke, the control valves 31 to 34 and the switching valves 115, 116, 215, and 216 are switched so that the adsorption tower 1 becomes an adsorption process and the adsorption tower 2 becomes a desorption (regeneration) process. By such a switching operation, similarly, cold energy, that is, cooling output can be obtained from the evaporator 4. 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 adsorbent adsorbed by the adsorbent, one of the adsorption towers can maintain a state in which the adsorbent can be adsorbed. If possible, any number of adsorption towers may be installed.

  The adsorption heat pump of the present invention can be used as various conventionally known air conditioners equipped with an adsorption / desorption portion for adsorbing substances, specifically as a dehumidifying air conditioner (so-called desiccant air conditioner).

(Operation principle of adsorption heat pump)
The operation principle of the adsorption heat pump having such a configuration and operation method will be described.

  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. φ1 and φ2 can be calculated by the following equation, and the range between φ1a and φ2a is a relative vapor pressure range that can be operated.

Desorption side relative vapor pressure φ1 = Equilibrium vapor pressure (Tlowl) / Equilibrium vapor pressure (Thigh)
Adsorption side relative vapor pressure φ2 = Equilibrium vapor pressure (Tcool) / Equilibrium vapor pressure (Tlow2)
Here, Thigh (high temperature heat source temperature) is the temperature of the heat medium heated when desorbing the adsorbent from the adsorbent and regenerating the adsorbent, and Tlow1 (low temperature heat source temperature) is the adsorbent of the condensing part. Tlow2 (low temperature heat source temperature) is the temperature of the heat medium that cools the regenerated adsorbent when it is subjected to adsorption, and Tcool (cold heat generation temperature) is the temperature of the adsorbed material in the evaporation section, that is, generated. It is the temperature of cold. The equilibrium vapor pressure can be determined from the temperature using the equilibrium vapor pressure curve of the adsorbed substance.

  Hereinafter, the operation relative vapor pressure range when the adsorbing material is water will be exemplified. When the cold heat generation temperature (Tcool) is 10 ° C., the adsorption side relative vapor pressure φ2 is 0.10 when the low temperature heat source temperature (Tlow 2) is 50 ° C., and 0.08 when the cold heat source temperature (Tlow 2) is 55 ° C. When the low temperature heat source temperature (Tlow1) is 30 ° C., the desorption side relative vapor pressure φ1 is 0.02 when the high temperature heat source temperature is 120 ° C., and 0.03 when the temperature is 110 ° C.

  From the above, operating relative vapor pressure range for gas engine cogeneration, solid polymer fuel cell or automobile engine waste heat, especially in the case of a cold storage system that drives the adsorption cool storage system using the waste heat of the automobile engine (Φ1 to φ2) is 0.02 to 0.10, more preferably 0.03 to 0.08.

(Adsorbent capacity to be filled)
Next, the capacity of the adsorbent filled in the adsorption heat pump will be described. The cooling capacity R of a general automobile air conditioner is approximately 3.0 kW (= 10,800 kJ / hr). The capacity of the adsorption heat pump that obtains such cooling capacity is considered to be preferably at least 15 liters or less based on surveys of engine rooms of various vehicles.

  The adsorption heat pump mounted in the engine room of the vehicle includes an adsorption tower, an evaporator, a condenser, and control valves. In order to make the assembly in which these are integrally formed into a capacity of 15 liters or less, the size of the evaporator, the condenser and the valves are formed with about 4.5 liters, and the capacity of the adsorption tower body is about 10.5. Formed in liters or less. The filling rate of the adsorbent and the bulk density of the adsorbent in the adsorption tower are usually about 30% and about 0.6 kg / liter, respectively. Therefore, the adsorbent weight (W) that can be filled is approximately 10.5 × 30% × 0.6 = 1.89 kg.

(Adsorption amount difference of adsorbent)
Next, characteristics required for the adsorbent, particularly the difference in adsorption amount will be described. The cooling capacity R in the adsorption heat pump described above is expressed by the following formula A.

R = (W · ΔQ · ηc · ΔH / τ) · ηh (A)
Here, W is the weight of the adsorbent filled in one adsorption tower (one side), ΔQ is the equilibrium adsorption amount amplitude under the conditions of adsorption and desorption, and the adsorption amount difference (Q2−Q1), and ηc is the equilibrium Adsorption amplitude efficiency indicating the ratio of the actual adsorption amplitude within the switching time to the adsorption amplitude ΔQ, ΔH is the latent heat of vaporization of water, τ is the switching time between the adsorption process and the desorption process, ηh is the adsorbent or heat exchanger The heat mass efficiency which considered the heat mass loss by changing temperature between warm water temperature and cooling water temperature is shown.

As described above, R is 3 kW, and W is 1.89 kg / 2 = 0.95 kg. In addition, from our past studies, it is preferable that τ is short. For example, if it is approximately 120 s (seconds), the values of ΔH, ηc, and ηh are approximately 2500 kJ / k, 0.6, 0. It is obtained to be 85. When ΔQ is obtained from Formula A,
ΔQ = R / W / ηc / ΔH · τ / ηh = 3.0 / 0.95 / 0.6 / 2500/120 / 0.85 = 0.075 kg / kg
It becomes. That is, as an adsorbent used for an adsorption heat pump for automobiles, ΔQ is 0.08 g / g or more, preferably 0.12 g / g or more, more preferably 0.15 g / g or more.

  The description has been given on the assumption that the adsorption heat pump is applied to an automobile, but it goes without saying that the adsorption heat pump is sufficiently applicable to other uses such as stationary use as long as the above characteristics are satisfied.

  Adsorption heat pumps use the ability of adsorbents to adsorb and desorb adsorbed substances as a drive source. In the adsorption heat pump, water, ethanol, acetone, or the like can be used as the adsorbing material, and water is most preferable from the viewpoint of safety, price, and latent heat of evaporation. The adsorbed substance is adsorbed on the adsorbent as vapor, and 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.

  The adsorbent used in the adsorption heat pump of the present invention is used in a dehumidifier, desiccant air conditioner, humidity control building material, etc. that directly adsorbs water vapor in the atmosphere, and in an environment where only water vapor exists in a vacuum like an adsorption heat pump. Used as an adsorbent.

(Adsorbent-1)
The adsorbent for adsorption heat pump of the present invention is characterized by its adsorption / desorption characteristics. That is, in the adsorption isotherm measured at 55 ° C., (1) the adsorption amount of the adsorbed substance at a relative vapor pressure of 0.02 is 0.12 g / g or less, preferably 0.1 g / g or less, (2 ) The amount of adsorbed material adsorbed at a relative vapor pressure of 0.1 is 0.13 g / g or more, preferably 0.15 g / g or more. (3) In the range of relative vapor pressure of 0.02 or more and 0.1 or less. It has a relative vapor pressure region where the adsorption amount change of the adsorbed material is 0.08 g / g or more when the relative vapor pressure is changed by 0.05. Such an adsorbent is suitable as an adsorbent for an adsorption heat pump that is mounted on an automobile that generates a large amount of waste heat and has a problem that fuel consumption is further reduced by using an air conditioner.

  As described above, the adsorption heat pump has an adsorption / desorption part (part provided with an adsorbent for adsorbing and desorbing adsorbed substances), an evaporation part (part connected to the adsorption / desorption part and evaporating adsorbed substances) and a condensing part (absorption). It is connected to the desorption part and is composed of a part for condensing the adsorbed material.

  Below, when the adsorption heat pump which consists of the said structure is mounted in a motor vehicle, the relationship between each part of an adsorption heat pump and the characteristic of (i)-(iii) mentioned above is demonstrated.

  Feature (i)-Desorption performance: The adsorbent of the present invention has a desorption performance of an adsorbed substance at a relative vapor pressure of 0.02 of 0.12 g / g or less, particularly 0.1 g / g or less. Yes. In automobiles and the like, the adsorption tower is heated to about 80 to 120 ° C. by hot water of about 80 to 120 ° C. heated by waste heat, and the condensing part is 30 to 30 ° C. by cooling water of about 30 to 60 ° C. cooled by a radiator. When cooled to about 60 ° C., the temperature of the adsorption tower is 120 ° C., and the temperature of the condensing part is 30 ° C., the relative vapor pressure is about 0.02. Therefore, the adsorbent of the present invention in which the adsorption amount of the adsorbed substance at a relative vapor pressure of 0.02 is 0.12 g / g or less has excellent desorption performance under the relative vapor pressure. When the adsorption tower is at a low temperature of 120 ° C. or lower, for example, about 115 ° C., or when the temperature of the condensing part is higher than 30 ° C., for example, about 35 ° C., the relative vapor pressure between them is It becomes larger than 0.02. Therefore, since it is necessary to perform sufficient desorption with a relative vapor pressure higher than 0.02, the adsorption amount under the condition of relative vapor pressure 0.02 is a smaller value, for example, 0.05 g / g or less is preferable. In addition, the lower limit of these adsorption amounts is not particularly defined, but it is preferably as 0 or close to 0.

  Characteristic (ii) -Adsorption performance: The adsorbent of the present invention has an adsorption capacity of 0.13 g / g or more, particularly 0.15 g / g or more, with an adsorbed substance at a relative vapor pressure of 0.1. Yes. In automobiles and the like, the adsorption / desorption part is cooled to about 30 to 60 ° C. by cooling water cooled by a radiator, the evaporation part is about 10 ° C. by a heat exchanger, the temperature of the adsorption part is 50 ° C., and the temperature of the evaporation part is At 10 ° C., the relative vapor pressure between them is about 0.10. Therefore, the adsorbent of the present invention in which the adsorption amount of the adsorbed substance at a relative vapor pressure of 0.10 is 0.13 g / g or more has excellent adsorption performance under the relative vapor pressure. More preferably, the adsorption amount of the adsorbed substance at a relative vapor pressure of 0.10 is 0.15 g / g or more, and particularly preferably 0.20 g / g or more. Furthermore, the adsorbent is preferably an adsorbent having an adsorption performance of 0.2 g / g or more at a smaller relative vapor pressure (for example, 0.08). According to such an adsorbent, the adsorbent can be used as an adsorbent in a good and efficient manner even under relatively high cooling temperature conditions such as cooling with about 30 to 60 ° C. cooling water obtained by an automobile radiator. Can be adsorbed. In addition, although the upper limit of these adsorption amounts is not specified in particular, it is usually about 0.40 g / g.

  Feature (iii)-Rate of change: The adsorbent of the present invention has an adsorption amount change of 0.08 g when the relative vapor pressure is changed by 0.05 within the range of relative vapor pressure of 0.02 to 0.1. / G or more. As described above, in an automobile or the like, the difference between the relative vapor pressure 0.02 related to desorption and the relative vapor pressure 0.1 related to adsorption is small, and the rate of change (when the relative vapor pressure changes 0.05) (Adsorption amount change of adsorbed substance is 0.08 g / g or more) is large, so that it is possible to reduce the total amount of adsorbent necessary to obtain the same adsorption amount / desorption amount under the same conditions, and the cooling temperature for adsorption A good and efficient adsorption / desorption cycle can be achieved even when the difference between the heating temperature for desorption is small. As a result, the present invention can be preferably applied to a system having a temperature difference of about 120 ° C. for the adsorption / desorption portion, about 10 ° C. for the evaporation portion, and about 30 ° C. for the condensation portion, such as an automobile.

  As described above, in the adsorbent having the adsorption / desorption characteristics (i) to (iii), the adsorption process occurs under a lower relative vapor pressure condition and the desorption process is higher than the conventional adsorbent. It is characterized in that it occurs under conditions, and further, it is characterized in that the amount of adsorption changes due to a slight change in relative humidity. As a result, a large amount of waste heat is generated, and it is suitable as an adsorbent for an adsorption heat pump mounted on an automobile having a problem that the fuel consumption is further reduced by using an air conditioner.

(Adsorbent-2)
The adsorbent for an adsorption heat pump of the present invention is a zeolite, and the zeolite is a crystalline aluminophosphate, and in particular, the framework density is a numerical value indicated in ATLAS OF ZEOLITE FRAMEWORK TYPES Fifth Revised Edition 2001 of IZA. It is preferably 10 T / nm ³ (= 1000 ³ ) or more and 18.0 T / nm ³ or less, more preferably 10.0 T / nm ³ or more and 16.0 T / nm ³ or less. An adsorbent having a framework density in this range can exhibit the preferred adsorption / desorption characteristics described above. If the framework density is less than 10 T / nm ³ , it is likely to become structurally unstable even if synthesis is realized in the future, and if it exceeds 18.0 T / nm ³ , the adsorption amount is not sufficient.

The zeolite used in the present invention is a crystalline aluminophosphate, which may be a natural zeolite or an artificial zeolite. For example, in the case of an artificial zeolite, crystalline aluminophosphates defined by the International Zeolite Association (IZA) , etc. Is included. Further, the value of the framework density is determined by the structure of the zeolite. As the structure, as shown by the code defined by IZA, AFG, AEI, AFR, AFS, AFT, AFX, AFY, AHT, * BEA, BOG, CHA, DFO, EAB, ERI, EMT, FAU, GIS, GME, KFI, LEV, LIO, LOS, LTA, LTN, MEI, MER, OFF, PAU, PHI, RHO, THO, VFI, etc. it can. In addition, AEI, AFX, GIS, CHA, VFI, AFS, LTA, FAU, and AFY can be mentioned as a better thing from the viewpoint of the adsorption / desorption characteristic mentioned above, More preferably, CHA is mentioned. it can.

The framework density is the number of atoms (T atoms) other than oxygen that form a skeleton per 1 nm ³ (= 1000 ³ ), and therefore the framework density correlates with the pore volume. In general, zeolites with lower framework density are preferred because they have a higher pore volume, resulting in a higher adsorption capacity. Moreover, even if zeolite is not currently synthesized, it is expected that it can be suitably used as the adsorbent for the adsorption heat pump of the present invention if the framework density is within the above range when synthesized.

  The structure of such zeolite is determined by XRD (X-ray diffraction), and the framework density can be measured and evaluated by the structure. In addition, ATLAS OF ZEOLITE FRAMEWORK TYPES Fifth Revised Edition 2001 ELSEVIER describes the relationship between zeolite structure and framework density.

(Aluminophosphate)
As the adsorbent for the adsorption heat pump of the present invention, crystalline aluminophosphates are used. Crystalline aluminophosphates include aluminum (Al) and phosphorus (P) in the skeleton structure, and further include crystalline metalloaluminophosphates in which a part of Al or P is substituted with a heteroatom. In this case, the heteroatom is an atom substituted for further improving the hydrophilicity of the zeolite, and is silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, nickel, palladium, copper, zinc , Gallium, germanium, arsenic, tin, calcium, boron, and the like. In the present invention, iron (Fe) and silicon (Si) are particularly preferably used.

In the following, crystalline iron aluminophosphate (hereinafter referred to as FAPO) which is a zeolite using Fe as a hetero atom, crystalline silicon aluminophosphate (hereinafter referred to as SAPO) which is a zeolite using Si as a hetero atom. Will be described.

(Abundance ratio of each atom in FAPO)
In FAPO preferable as the adsorbent for the adsorption heat pump of the present invention, it is preferable that Fe, Al, and P contained in the skeleton structure are present in a molar ratio represented by the following formulas 1 to 3.

0.001 ≦ x ≦ 0.3… 1
(X represents the molar ratio of Fe to the total of Fe, Al and P)
0.2 ≦ y ≦ 0.6 2
(Y represents the molar ratio of Al to the total of Fe, Al and P)
0.3 ≦ z ≦ 0.6 3
(Z represents the molar ratio of P to the total of Fe, Al and P)

  Further, it is more preferably constituted by a molar ratio represented by the following formulas 1 'to 3' (wherein x, y and z are the same as above).

0.01 ≦ x ≦ 0.25… 1 ′
0.23 ≦ y ≦ 0.58… 2 ′
0.33 ≦ z ≦ 0.58… 3 ′

  Further, it is more preferably constituted by a molar ratio represented by the following formulas 1 ″ to 3 ″ (wherein x, y and z are the same as above).

0.03 ≦ x ≦ 0.20… 1 ”
0.25 ≦ y ≦ 0.55 2 ”
0.35 ≦ z ≦ 0.55… 3 ”

  FAPO shows a large amount of adsorption at a low relative humidity (relative vapor pressure), and becomes an adsorbent having an adsorption isotherm property at a very low humidity (low relative vapor pressure). For this reason, in the case where Fe in the above range exists in the skeleton structure, it is considered that the charge is apparently compensated between Fe existing in trivalent and P existing in pentavalent, and the same crystal structure However, the polarity of the skeletal structure is smaller than those containing elements other than Fe in the skeleton structure (for example, SAPO containing Si), and trivalent elements compared to AlPO containing only Al and P in the skeleton structure. This is considered to be because polarity is more likely to occur than AlPO because there are two types of Fe and Al.

  In addition, when the molar ratio of iron exceeds the above range, the structural stability tends to decrease. On the other hand, when the molar ratio of iron is smaller than the above range, the structural stability tends to be lowered, or the amount of iron is reduced, so the effect on the iron adsorption performance is reduced, which is not preferable.

  The skeleton structure of FAPO may contain elements other than Fe, Al, and P, and does not affect the adsorption / desorption characteristics. 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) and iron (Fe) is 3 or less, preferably 2 or less, more preferably 1 or less, and still more preferably 0.5 or less. When the molar ratio of the other elements is within such a range, there is an advantage that the effect on the iron adsorption performance is remarkably exhibited. When the molar ratio of the other elements to iron exceeds 3, the adsorption of iron The phenomenon that the effect on performance does not appear so much may occur.

The FAPO includes those having a cation species exchangeable with other cations. In this case, the cations include protons, alkaline elements such as Li, Na, and K, alkaline earth elements such as Mg and Ca, La, and the like. And rare earth elements such as Ce, and transition metal elements such as Fe, Co, and Ni. Of these, protons, alkali elements, and alkaline earth elements are preferable from the viewpoints of adsorption performance and stability.

  Each molar ratio of the above atoms is determined by elemental analysis, and elemental analysis can be determined by ICP analysis after dissolving a sample with an aqueous hydrochloric acid solution.

(Crystal structure of FAPO)
Among the FAPOs related to the adsorbent for the adsorption heat pump of the present invention, a particularly preferable one is characterized by having the following crystal structure.

  That is, the present invention includes an iron aluminophosphate having a powder X-ray diffraction pattern including at least iron, aluminum, and phosphorus in a skeletal structure and including at least an X-ray diffraction peak shown in Table 1, which is an iron aluminophosphate. Among these, it is a particularly preferable material.

  Table 1 shows the diffraction angle (2θ) at which the main diffraction peak of the FAPO obtained by powder X-ray diffraction measurement appears. In addition, since powder X-ray diffraction measurement is normally performed in air, the sample used for the measurement here is rehydrated in atmospheric air. The relative intensities in Table 1 are indicated by the symbols vs, s, m, w, vw, which correspond to very strong, strong, moderate, weak and very weak, respectively.

In Table 1, the second peak at the diffraction angle of 10.1 ± 0.3 is that the value of I / I ₀ × 100 described later is 10 or more from the viewpoint that this characteristic of the structure is well reflected. Preferably, it is 15 or more. The peak No. 4 at the diffraction angle of 19.5 ± 0.3 preferably has an I / I ₀ × 100 value of 10 or more from the viewpoint of well reflecting the characteristics of this structure, 15 or more. It is more preferable that

The fourth peak is usually often divided into two peaks, but the two peaks may overlap due to a slight difference in the state of the sample and the measurement conditions. In any case, it is sufficient that at least one satisfying the value of I / I ₀ × 100 within the diffraction angle range of 19.5 ± 0.3.

(Measurement of crystal structure)
The X-ray diffraction peaks in Table 1 described above are data obtained from X-ray diffraction patterns measured with a standard X-ray powder diffractometer. As a specific measurement method, Cu is used as a target, an X-ray tube set to output at 40 kV and 30 mA is used as a radiation source, and the diffracted X-ray diffracted by the sample is monochromatized into Kα rays by a monochromator. This is done by detecting the object. Optical conditions were measured with a divergence slit = 1 °, a scattering slit = 1 °, and a light receiving slit = 0.2 mm, and the position of the diffraction peak is expressed as 2θ (diffraction angle). Is the Bragg angle observed on the recording paper. The surface spacing (d) in angstrom units is obtained from Bragg's conditional expression: 2dsin θ = λ. Here, λ = 1.54184Å. The peak position is expressed as a peak top. The intensity is measured from the height of the diffraction peak after subtracting the background, and is expressed as a value of I / I ₀ × 100. Here, I ₀ is the intensity of the strongest peak, and I is the intensity of each of the other peaks. In the case of the present invention, I ₀ normally has a peak of 2θ = 9.5 ± 0.2 °. In general, the measurement of 2θ is subject to both human error and mechanical error. In consideration of the above errors and the like, the range of ± of the measured value is defined as about plus or minus 0.3 °.

  FAPO having the X-ray diffraction peak shown in Table 1 is also characterized in that the position of the powder X-ray diffraction peak changes due to adsorption / desorption of water. That is, when water is adsorbed, a powder X-ray diffraction pattern consisting of the X-ray diffraction peaks shown in Table 1 is shown, and when water is desorbed, powder X-ray diffraction consisting of the X-ray diffraction peaks shown in Table 2 is shown. Indicates a pattern. Such changes due to water adsorption / desorption can be measured by, for example, an XRD-DSC apparatus (Rigaku Corporation, RINT2000, heat flux DSC). The relative intensity symbols in Table 2 are the same as in Table 1. The X-ray diffraction peaks in Tables 1 and 2 are a type of CHA type.

  The FAPO having the X-ray diffraction peak shown in Table 2 may contain a template, or a part or all of the template may be removed by a method such as nitrogen baking.

  The FAPO showing at least the X-ray diffraction peak shown in Table 1 described above may contain other elements in the skeleton structure as long as it has such a crystal structure feature. Other elements include silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, cobalt, nickel, palladium, copper, zinc, gallium, germanium, arsenic, tin, calcium, boron, etc., as described above. can give. Usually, when other elements are contained exceeding the content limit, at least the X-ray diffraction peaks shown in Table 1 are not shown. The content limit of other elements is 1 or less in terms of molar ratio (M / Fe) of other elements (M) and iron (Fe), and the molar ratio is 0.7 or less, and further 0.5 or less Has the advantage of easily having the FAPO structure shown in Table 1.

Moreover, as long as it has such a crystal structure characteristic, the zeolite may include those having a cation species exchangeable with other cations. Examples of cations in such cases include protons, alkaline elements such as Li, Na, and K, alkaline earth elements such as Mg and Ca, rare earth elements such as La and Ce, and transition metal elements such as Fe, Co, and Ni. It is done. Among these, protons, alkali elements, and alkaline earth elements are preferable.

(Abundance ratio of each atom in SAPO)
Next, a preferred SAPO (crystalline silicon aluminophosphate) will be described as an adsorbent for the adsorption heat pump of the present invention.

  In SAPO, it is preferable that Si, Al, and P contained in the skeleton structure are present in a molar ratio represented by the following formulas 4-6.

0.09 <p ≦ 0.3 ... 4
(P represents the molar ratio of Si to the sum of Si, Al and P)
0.3 ≦ q ≦ 0.6 5
(Q represents the molar ratio of Al to the sum of Si, Al and P)
0.3 ≦ r ≦ 0.6 6
(R represents the molar ratio of P to the sum of Si, Al and P)

  Further, it is more preferable that Si and Al have a molar ratio represented by the following formulas 4 'and 5' (wherein p and q are the same as above).

0.092 ≦ p ≦ 0.25 ... 4 ′
0.33 ≦ q ≦ 0.58… 5 ′

Moreover, as long as it is in the range of Si, Al, and P having the above composition, other elements may be included in the skeleton structure, and the adsorption / desorption characteristics are not affected. Examples of other elements include lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, cobalt, nickel, palladium, copper, zinc, gallium, germanium, arsenic, tin, calcium, and boron. The zeolite includes those having a cation species that can be exchanged with other cations. In this case, the cations include alkaline elements such as protons, Li, Na, and K, and alkaline earth elements such as Mg and Ca. And rare earth elements such as La and Ce, and transition metal elements such as Fe, Co, and Ni. Among these, protons, alkali elements, and alkaline earth elements are preferable from the viewpoints of adsorption performance and stability.

  As described above, SAPO contains Al, P, and Si in its skeleton structure. In this SAPO, since Si is tetravalent, the Si has polarity by substituting trivalent Al or pentavalent P. Therefore, SAPO has a favorable tendency that the adsorption of water starts under a lower humidity condition (low relative vapor pressure condition) by increasing the amount of Si contained. In this SAPO, by making the molar ratio of Si to the total of Si, Al and P greater than 9%, an adsorbed substance (for example, water vapor) from an extremely low relative humidity region (low relative vapor pressure region) like Y-type zeolite. Adsorption can occur. Therefore, the Si content is preferably large, but if it is too large, the structure becomes unstable, so the upper limit is about 30%. A preferable Si molar ratio is 9.2% or more, and a more preferable Si molar ratio is 9.5% or more.

  This SAPO is slightly disadvantageous in the desorption process because adsorption occurs from a lower humidity region (low relative vapor pressure region) than FAPO. However, since it has temperature dependence like FAPO, it has the advantage that water can be easily desorbed even with exhaust heat of about 100 ° C., compared with the one having almost no temperature dependence such as Y-type zeolite.

  The molar ratio of SAPO is determined by elemental analysis. Elemental analysis can be determined by ICP analysis after dissolving a sample with an aqueous hydrochloric acid solution.

(Manufacturing conditions for FAPO and SAPO)
The production conditions of FAPO and SAPO are not particularly limited, but are usually produced by hydrothermal synthesis after mixing an aluminum source, an iron source or a silicon source, a phosphorus source and a template. Hereinafter, an example of the manufacturing method of FAPO and SAPO will be described by dividing it into a common part and a different part.

  First, an aluminum source, an iron source or a silicon 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. This is preferable because of its high reactivity.

  Iron source: Iron source is used as the main material in the case of FAPO. The iron source is also not particularly limited, and usually, inorganic acid iron such as iron sulfate, iron nitrate, iron phosphate, iron chloride and iron bromide, organic acid iron such as iron acetate, iron oxalate and iron citrate, iron penta Examples thereof include iron organometallic compounds such as carbonyl and ferrocene. Among these, inorganic acid irons and organic acid irons are preferable in that they are easily soluble 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.

  Silicon source: A silicon source is used as a main material of SAPO, and fumed silica, silica sol, colloidal silica, water glass, ethyl silicate, methyl silicate, and the like are used.

  Phosphorus source: Phosphoric acid is usually used as the phosphorus source, but aluminum phosphate may be used.

  Other elements: The skeleton structure of FAPO or SAPO may contain other elements as long as the above-described adsorption / desorption characteristics 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-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. Of these, morpholine, triethylamine, cyclohexylamine, isopropylamine, di-isopropyl-ethylamine, N-methyl-n-butylamine, and tetraethylammonium hydroxide are preferable in terms of reactivity, and are industrially cheaper morpholine and triethylamine. More preferred is cyclohexylamine. 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 aluminum source, iron source or silicon source, phosphorus source and template. 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 or silicon source and a template are mixed.

The composition of the aqueous gel related to FAPO is expressed as a molar ratio of the oxide, 0.01 ≦ FeO / P ₂ O ₅ ≦ 1.5, and 0.02 ≦ FeO from the viewpoint of ease of synthesis. / P ₂ O ₅ ≦ 1.0 is preferable, and 0.05 ≦ FeO / P ₂ O ₅ ≦ 0.8 is more preferable. The ratio of P ₂ O ₅ / Al ₂ O ₃ is 0.6 or more and 1.7 or less, and 0.7 to 1.6 or less is preferable from the viewpoint of ease of synthesis, and 0.8 More preferably, it is 1.5 or less. The lower limit of the proportion of water, relative to Al ₂ O _3, is 3 or more in molar ratio, preferably 5 or more from the viewpoint of ease of synthesis, and more preferably 10 or more. The upper limit of the ratio of water is 200 or less, preferably 150 or less, and more preferably 120 or less from the viewpoint of ease of synthesis and high productivity. The pH of the aqueous gel is 4 to 10, preferably 5 to 9 and more preferably 5.5 to 8.5 from the viewpoint of ease of synthesis.

The composition of the aqueous gel related to SAPO is 0.2 ≦ SiO ₂ / Al ₂ O ₃ ≦ 2 in terms of the molar ratio of the oxide, and 0.3 ≦ SiO ₂ / from the viewpoint of ease of synthesis. Al ₂ O ₃ ≦ 1.8 is preferable, and 0.4 ≦ SiO ₂ / Al ₂ O ₃ ≦ 1.5 is more preferable. The ratio of P ₂ O ₅ / Al ₂ O ₃ is 0.6 or more and 1.4 or less, preferably 0.7 or more and 1.3 or less, and preferably 0.8 or more from the viewpoint of ease of synthesis. 1.2 or less is more preferable. 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 ease of synthesis, and more preferably 10 or more. The upper limit of the ratio of water is 200 or less, preferably 150 or less, and more preferably 120 or less from the viewpoint of ease of synthesis and high productivity. The pH of the aqueous gel is 5 to 10, preferably 6 to 9 and more preferably 6.5 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 hydrothermal synthesis conditions are 100 to 300 ° C, and 120 to 250 ° C is preferable and 150 to 220 ° C is more preferable from the viewpoint of ease of synthesis.

  In FAPO, the reaction time is 3 hours to 30 days, preferably 5 hours to 15 days, more preferably 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 a method such as calcination to obtain a zeolite related to FAPO. On the other hand, the reaction time of SAPO is 3 hours to 30 days, preferably 5 hours to 7 days, and more preferably 7 hours to 3 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 material contained is removed by a method such as calcination to obtain a zeolite related to SAPO.

(Method for adjusting crystal structure of FAPO shown in Table 1)
According to the above method, FAPO and SAPO having various structures used in the present invention can be synthesized. However, FAPO having diffraction peaks shown in Table 1 can be synthesized from FAPO having diffraction peaks shown in Table 2 in the presence of a gas containing oxygen. It can be obtained by firing.

  The firing temperature is 200 ° C. or higher and 800 ° C. or lower, and is preferably 300 ° C. or higher and 700 ° C. or lower, and preferably 400 ° C. or higher and 650 ° C. from the viewpoint of ease of template removal and / or ease of change in crystal structure. More preferably, it is not more than The firing time is from 1 minute to 15 hours, and preferably from 2 minutes to 10 hours, and more preferably from 5 minutes to 8 hours, from the viewpoint of ease of template removal and / or ease of change of the crystal structure. Note that the firing time here is the apparent time that the material that is fired is present in the processing temperature environment. Depending on the amount of equipment and sample used, It is also set with attention that the actual processing time may be slightly different.

  The oxygen concentration in the gas is 2 vol% or more, preferably 3 vol% or more, and more preferably 5 vol% or more from the viewpoint of ease of template removal and / or ease of change of crystal structure. As the gas other than oxygen, an inert gas such as nitrogen, argon, or helium is used. However, depending on the case, water vapor or nitrogen oxide may be mixed up to 10% by volume. The firing gas may or may not be circulated in the processing apparatus, but when circulated, it is preferably circulated at a weight space velocity (WHSV) with respect to the sample to be fired. The weight space velocity (WHSV) is preferably 20 / h or less, and preferably 15 / h or less from the viewpoint of ease of template removal and / or ease of change of crystal structure. Is more preferable. As a baking apparatus, arbitrary heating apparatuses, such as a muffle furnace and a tubular furnace, are used, and it is performed by a fixed bed or a fluidized bed form.

(Method for producing FAPO in Table 2)
A preferable method for producing FAPO having the diffraction peaks shown in Table 2 is described below. As with the above, other FAPO manufacturing methods are usually manufactured by hydrothermal synthesis after mixing an aluminum source, an iron source, a phosphorus source and a template. This other manufacturing method is characterized by the template to be mixed. is there. This will be described in turn 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. Usually, aluminum alkoxide such as pseudoboehmite, aluminum isopropoxide, aluminum triethoxide, aluminum hydroxide, alumina sol, sodium aluminate, etc. are used. Among these, pseudoboehmite is preferable from the viewpoint of ease of handling and reactivity.

  Iron source: The iron source is also 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. Iron organometallic compounds such as iron pentacarbonyl and ferrocene are used. Among these, from the viewpoint of solubility in water, inorganic acid iron and organic acid iron are preferable, and among them, divalent iron compounds such as ferrous sulfate are more preferable.

  Phosphorus source: The phosphorus source is usually phosphoric acid, but aluminum phosphate may be used.

  Other elements: As long as it finally has a powder X-ray diffraction pattern composed of at least the X-ray diffraction peaks shown in Table 1 and Table 2, other elements may be included in the skeleton structure. 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.

  Template: As a template, tetraethylammonium salt, tetrapropylammonium salt, tetramethylammonium salt, quaternary ammonium salt such as tetrabutylammonium salt, various amines, and the like are used. Examples of amines include (1) an alicyclic heterocyclic compound containing nitrogen as a hetero atom, (2) an amine having a cycloalkyl group, and (3) an amine having an alkyl group. These may be used singly, but when a quaternary ammonium salt is used alone, it is likely to have poor crystallinity, so at least one of the three groups of amines is selected from each group. It is preferable to select and use one or more compounds for each.

  Here, each of the above amines will be described in more detail.

  First, an alicyclic heterocyclic compound containing nitrogen as a hetero atom will be described. The alicyclic heterocyclic compound containing nitrogen as a hetero atom is usually a 5- to 7-membered ring, preferably a 6-membered ring. The number of heteroatoms contained in the heterocycle is usually 3 or less, preferably 2 or less. The type of hetero atom is not particularly limited except nitrogen, but from the viewpoint of ease of synthesis, a hetero atom containing oxygen is preferable. The positions of the heteroatoms are not particularly limited, but those in which the heteroatoms are not adjacent to each other are preferable from the viewpoint of ease of synthesis. The molecular weight is 250 or less, preferably 200 or less, more preferably 150 or less from the viewpoint of ease of synthesis.

  Examples of such alicyclic heterocyclic compounds containing nitrogen as a heteroatom include morpholine, N-methylmorpholine, piperidine, piperazine, N, N′-dimethylpiperazine, 1,4-diazabicyclo (2,2,2) octane. , N-methylpiperidine, 3-methylpiperidine, quinuclidine, pyrrolidine, N-methylpyrrolidone, hexamethyleneimine and the like. Of these, morpholine, hexamethyleneimine, and piperidine are preferable from the viewpoint of ease of synthesis, and morpholine is particularly preferable.

  Next, an amine having a cycloalkyl group will be described. In the amine having a cycloalkyl group, the number of the cycloalkyl group is preferably 2 or less, more preferably 1 per amine molecule. Moreover, carbon number of a cycloalkyl group is 5-7 normally, Preferably it is 6. The number of cycloalkyl cyclo rings is not particularly limited, but is usually preferably 1. Moreover, it is preferable from the point of easiness of a synthesis | combination that the cycloalkyl group has couple | bonded with the nitrogen atom of the amine compound. The molecular weight is 250 or less, preferably 200 or less, more preferably 150 or less from the viewpoint of ease of synthesis.

  Examples of the amine having such a cycloalkyl group include cyclohexylamine, dicyclohexylamine, N-methylcyclohexylamine, N, N-dimethylcyclohexylamine, and cyclopentylamine, and cyclohexylamine is particularly preferable.

  Next, the amine having an alkyl group will be described. In the amine having an alkyl group, any number of the alkyl groups may be contained in one amine molecule, but 3 is preferred. The number of carbon atoms of the alkyl group is preferably 4 or less, and the total number of carbon atoms of all alkyl groups in one molecule is more preferably 10 or less. The molecular weight is 250 or less, preferably 200 or less, more preferably 150 or less from the viewpoint of ease of synthesis.

  Examples of amines having such alkyl groups include di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, triethanolamine, N, N-diethylethanolamine, N, N-dimethylethanol. Amine, N-methyldiethanolamine, N-methylethanolamine, di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, di-isopropyl-ethylamine, N-methyl-n -Butylamine and the like, di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, di-n-butylamine, isopropylamine, t-butylamine, ethylenediamine, di-isopropyl Le - ethylamine, preferably in that N- methyl -n- butylamine synthetic ease, triethylamine is particularly preferred.

  Each of these amines can be used as a template source by combining one or two or more thereof, and used as a raw material for hydrothermal synthesis. When one of these is used, (1) morpholine in an alicyclic heterocyclic compound containing nitrogen as a hetero atom, or (2) cyclohexylamine in an amine having a cycloalkyl group is preferable. Of these, morpholine is particularly preferred.

  Among these, a preferable combination is a group consisting of (i) an alicyclic heterocyclic compound containing nitrogen as a hetero atom, (ii) an amine having a cycloalkyl group, and (iii) an amine having an alkyl group. It is preferable to use one or more compounds from two or more groups. By combining in this way, there is an advantage / effect that it is easy to synthesize a desired element ratio or highly crystalline FAPO. Among these, (i) in the case of a combination of two or more containing an alicyclic heterocyclic compound containing nitrogen as a heteroatom, it is more preferable from the viewpoint of easy synthesis of a desired element ratio and highly crystalline FAPO. . As a specific preferred combination, a combination of two or more of morpholine, triethylamine and cyclohexylamine, more preferably a combination of two or more containing morpholine is more preferable. The mixing ratio of each group of these templates needs to be selected in a timely manner according to the conditions, but the molar ratio of the two types of templates to be mixed is in the range of 1:20 to 20: 1. From the viewpoint of easy synthesis of highly crystalline FAPO, 1:10 to 10: 1 is preferable, and 1: 5 to 5: 1 is more preferable. Although other templates may be contained, in that case, the molar ratio is usually 20% or less, preferably 10% or less. These templates are advantageous in that they are inexpensive and easy to handle and less corrosive than conventional ones (for example, tetraethylammonium hydroxide).

  By combining each template and reacting under favorable reaction conditions, it is advantageous to improve the crystallization rate, easily produce zeolite with the desired structure, stabilize the structure without breakage, suppress the generation of impurities, etc. Effects appear. However, a template composed of a single species is slightly inferior to a template formed by mixing a plurality of templates in terms of a wide range of reaction conditions, a high yield of a desired zeolite, a fast crystallization rate, and the like. Therefore, in the production of the FAPO of the present invention (especially those of XRD in Table 2), a template comprising a plurality of combinations is preferably used, and an effect that cannot be obtained by a single template is obtained due to the synergistic action exhibited by these templates. There is an advantage that you can.

  The hydrothermal synthesis in the other manufacturing method of FAPO is almost the same as the normal hydrothermal synthesis described above except that the manufacturing conditions differ.

  First, an aqueous gel is prepared by mixing an iron source, an aluminum source, a phosphoric acid source, a template and water. The mixing order is not limited and may be appropriately selected depending on the conditions to be used. Usually, however, first a phosphoric acid source and an aluminum source are mixed with water, and then an iron source and a template are mixed therewith.

The composition of the aqueous gel affects the ease of synthesis of the desired one. When the aluminum source, the iron source and the phosphate source are expressed in terms of the molar ratio of the oxide, the value of FeO / Al ₂ O ₃ is usually greater than 0. 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less.

The ratio of P ₂ O ₅ / Al ₂ O ₃ affects the ease of synthesis of the desired product, and is usually 0.6 or more, preferably 0.8 or more, more preferably 1 or more. It is 8 or less, preferably 1.7 or less, more preferably 1.6 or less.

The total amount of the template affects the ease of synthesis of the desired product and the economic efficiency, and the molar ratio of the template to P ₂ O ₅ is usually 0.2 or more, preferably 0.5 or more, more preferably 1 or more. Usually, it is 4 or less, preferably 3 or less, more preferably 2.5 or less. In addition, the mixing ratio of two or more types of templates affects the ease of synthesis of the desired one and needs to be appropriately selected according to the conditions. For example, when morpholine and triethylamine are used as described above, The molar ratio of morpholine / triethylamine is 0.05 to 20, preferably 0.1 to 10, and more preferably 0.2 to 9. The order of mixing one or more templates selected from each of the two or more groups is not particularly limited, and after preparing the template, it may be mixed with other substances, and each template may be mixed with other substances. May be mixed with.

Further, the proportion of water affects the ease of synthesis of desired products and the economic efficiency, and is usually 3 or more, preferably 5 or more, more preferably 10 or more in terms of molar ratio to Al ₂ O ₃ . 200 or less, preferably 150 or less, more preferably 120 or less. The pH of the aqueous gel affects the ease of synthesis of the desired gel, and is usually 4 or more, preferably 4.5 or more, more preferably 5 or more, and usually 10 or less, preferably 9 or less, more preferably 8 or less. It is.

In the aqueous gel, components other than those described above may coexist if desired. As an advantage of coexistence, there is a possibility that a new effect can be obtained. Examples of such components include hydrophilic organic solvents such as hydroxides and salts of alkali metals and alkaline earth metals, and alcohols. The coexistence ratio affects the ease of synthesis of the desired product. In the case of hydroxides or salts of alkali metals or alkaline earth metals, the molar ratio with respect to Al ₂ O ₃ is usually 0.2 or less, preferably In the case of a hydrophilic organic solvent such as alcohol, the molar ratio with respect to water is usually 0.5 or less, preferably 0.3 or less.

  Under such conditions, hydrothermal synthesis is performed by placing the aqueous gel in a pressure-resistant container and maintaining a predetermined temperature under stirring or standing under self-generated pressure or gas pressure that does not inhibit crystallization.

  The reaction temperature of hydrothermal synthesis affects the ease of synthesis of the desired product, and is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower. More preferably, it is 220 ° C. or lower. The reaction time affects the ease of synthesis of the desired product, and is usually 2 hours or more, preferably 3 hours or more, more preferably 5 hours or more, and usually 30 days or less, preferably 10 days or less, more preferably 4 days or less. The reaction temperature may be constant during the reaction or may be changed stepwise.

  After the hydrothermal synthesis, the product is separated. The method for separating the product is not particularly limited. Usually, it is separated by filtration, decantation, etc., washed with water, and dried at a temperature of room temperature to 150 ° C. or lower to obtain a zeolite containing the product template.

  By the production method described above, iron aluminophosphate (FAPO) having a powder X-ray diffraction pattern composed of at least the X-ray diffraction peaks shown in Table 2 is obtained.

  Further, the powder X-ray comprising at least the X-ray diffraction peaks shown in Table 2 can be obtained by baking this under the above-described baking conditions in the presence of an inert gas such as nitrogen and removing a part or all of the template. An iron aluminophosphate having a diffraction pattern is obtained.

(Adsorption and desorption characteristics of the obtained FAPO)
FAPO produced as described above is widely used for catalysts for oxidation reaction and acid reaction, and various adsorbents. In particular, it exhibits excellent performance as a water vapor adsorbent.

  When used as a water vapor adsorbent, it can be used together with a metal oxide such as silica, alumina and titania, a binder component such as clay, and a component having high thermal conductivity. At this time, the zeolite content is preferably 60% by weight or more of the entire water vapor adsorbent. In addition, it is more preferable that it is 70% or more, and 80% or more is further more preferable.

  The feature of the FAPO as a water vapor adsorbent of the present invention is that it hardly adsorbs in a region where the relative vapor pressure is extremely low, and that the adsorption occurs rapidly under a relative vapor pressure condition slightly higher than the relative vapor pressure. is there. Such characteristics generally indicate that adsorption is possible even in a low humidity and high temperature region where adsorption is difficult, and desorption is possible at a relatively low temperature of about 100 ° C. This is because the known Y-type zeolite has a very low relative vapor pressure and adsorbs abruptly from a region close to almost 0, so that a high temperature such as 120 ° C. or higher is usually required to desorb the adsorbed material. In contrast, the adsorbent according to the FAPO of the present invention can be adsorbed and desorbed at a temperature of about 100 ° C. or lower, and is therefore preferable in applications where such a temperature is supplied. Of the features of the FAPO of the present invention, the FAPO having the XRD structure shown in Table 1 is considered to be caused by the change in the structure that appears due to the change in the powder X-ray pattern due to the adsorption / desorption of water.

(Types of adsorbents and their adsorption / desorption characteristics)
The adsorption / desorption characteristics of each adsorbent described above will be described.

  The adsorbent composed of the above-described high Si-SAPO, FAPO and FAPO having at least the XRD pattern shown in Table 1 (hereinafter referred to as FAPO-2) has a relative vapor pressure of 0.02 on the adsorption isotherm measured at 55 ° C. The amount of adsorbed material adsorbed at 0.12 g / g or less, preferably 0.1 g / g or less, and the amount of adsorbed material adsorbed at a relative vapor pressure of 0.1 is 0.13 g / g or more, preferably 0. Relative steam in which the change in the amount of adsorption of the adsorbed material is 0.08 g / g or more when the relative vapor pressure is changed by 0.05 in the range of relative vapor pressure of 0.02 or more and 0.1 or less. It has a pressure region. In the case where the adsorbent is particularly high Si-SAPO, the adsorbent adsorbed at a relative vapor pressure of 0.02 is 0.1 g / g or less on the adsorption isotherm measured at 55 ° C. The amount of adsorbed material adsorbed when the vapor pressure is 0.07 is 0.15 g / g or more, and the relative vapor pressure changes by 0.05 in the range of relative vapor pressure of 0.02 to 0.1. It has a relative vapor pressure region where the adsorption amount change is 0.08 g / g or more.

  For the adsorbent composed of FAPO and FAPO-2, the adsorption isotherm at a relative vapor pressure of 0.02 is 0.05 g / g or less on the adsorption isotherm measured at 55 ° C. Adsorption of adsorbed material when the amount of adsorbed material at a pressure of 0.1 is 0.2 g / g or more and the relative vapor pressure is changed by 0.05 in the range of relative vapor pressure of 0.02 to 0.1. It has a relative vapor pressure region in which the amount change is 0.15 g / g or more, and exhibits excellent adsorption / desorption characteristics.

  Further, among the adsorbents described above, the adsorbent composed of FAPO-2 has an adsorption amount of the adsorbed substance of 0.05 g / g or less at a relative vapor pressure of 0.02 on the adsorption isotherm measured at 55 ° C. Yes, when the adsorption amount of the adsorbed substance at a relative vapor pressure of 0.08 is 0.2 g / g or more, and the relative vapor pressure changes by 0.02 in the range of the relative vapor pressure of 0.02 to 0.08. It has a relative vapor pressure region in which the adsorption amount change of the adsorbed substance is 0.15 g / g or more, and its rise is steep in the adsorption isotherm graph, showing extremely excellent adsorption / desorption characteristics. FAPO-2, which has such excellent adsorption / desorption characteristics, can be adsorbed even in low humidity and high temperature regions where adsorption is difficult, and can be desorbed at a relatively low temperature of about 100 ° C. It can be used as a water vapor adsorbent for adsorption-type cold storage devices, desiccants, dehumidifications, heat storage systems, etc., and it is possible to improve its efficiency or to operate under conditions that could not be applied so far.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, Table 17 shown at the end of the Example column is a list of characteristics of the adsorbents of Examples 1 to 10 and Comparative Example 1.

(Example 1)
Example 1 relates to FAPO-2 synthesized using morpholine and triethylamine as templates.

  To a mixture of 28.05 g of water and 11.53 g of 85% phosphoric acid, 6.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added and stirred. This was designated as liquid A. Separately from liquid A, a liquid in which 2.78 g of ferrous sulfate heptahydrate, 5.05 g of morpholine, 4.35 g of triethylamine, and 29 g of water were prepared. This was slowly added to the liquid A and stirred for 3 hours to obtain a starting reaction product having the following composition.

_{0.2FeSO 4: Al 2 O 3:} P 2 O 5: 1.16 morpholine: 0.86 triethylamine: _70H 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 160 ° C. for 4 days 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. The results of the powder XRD of the FAPO intermediate thus obtained are shown in Table 3 below.

  3g was collected from the FAPO intermediate containing the template, placed in a vertical quartz firing tube, heated to 550 ° C at 1 ° C / min in an air stream of 100ml / min, and baked at 550 ° C for 6 hours. Went. The XRD of the zeolite (FAPO-2) thus obtained was measured and was as shown in the following table.

  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 to the total of aluminum, phosphorus and iron in the skeleton structure was 13.8% for iron and aluminum for It was 37.4% and phosphorus was 48.8%.

  FIG. 2 is a water vapor adsorption isotherm at 55 ° C. obtained by measuring zeolite with an adsorption isotherm measuring apparatus (Belsorb 18: Nippon Bell Co., Ltd.). The adsorption isotherm is measured at 120 ° C. for 5 hours under a vacuum of 1 Pa or less, a high temperature air bath temperature of 60 ° C., an adsorption temperature of 55 ° C., an initial introduction pressure of 3.0 torr, an introduction pressure set point of 0, The saturation vapor pressure was 118.11 mmHg and the equilibration time was 500 seconds.

  Furthermore, DSC-XRD was measured. The specifications and conditions of the measuring device are as follows.

X-ray diffractometer: RINT2000 Ultimate + series
: DSC part: Heat flux type DSC
<XRD conditions>
X-ray used: CuKα
Tube voltage, tube current: 40 kV, 50 mV
Slit: DS = 0.5 degree, SS = 0.5 degree, RS = 0.3 mm
Measurement method: Monochromator method + continuous measurement
Scanning range: 5 to 40 degrees <DSC condition>
・ Desorption process
From room temperature to 150 ° C: humidity 0% nitrogen, rate of temperature increase 5 ° C / min
150 ° C. to 45 ° C .: humidity 0% nitrogen, heating rate 5 ° C./min
・ Adsorption process
45 ℃ constant humidity 0, 5, 10, 15, 20, 30%

  FIG. 3 shows the XRD- when the zeolite is set in the apparatus and the temperature is raised from room temperature (25 ° C.) to 150 ° C. in a nitrogen atmosphere of 0% humidity to desorb the water adsorbed on the zeolite. DSC change is shown. FIG. 4 shows the XRD-DSC change when the humidity is increased and the water is adsorbed on the sample after the water is desorbed under the above DSC conditions. 3 and 4, it can be seen that XRD changes with the desorption / adsorption of water, that is, the structure changes.

  FIG. 5 shows XRD diagrams of the state after desorption of water (measurement at 150 ° C. and 0% relative humidity) and the state after adsorption (measurement at 45 ° C. and 10% humidity).

  Tables 5 and 6 below show X-ray diffraction peaks after adsorption after desorption of water in FIG. 5, respectively. As shown in these figures, at least from the X-ray diffraction peaks shown in Table 2 due to desorption of water. A powder X-ray diffraction pattern consisting of at least the X-ray diffraction peaks shown in Table 1 due to adsorption of water is shown.

(Example 2)
Example 2 was prepared under the same conditions as in Example 1 except that the synthesized template-containing zeolite was calcined with nitrogen. Table 7 shows the XRD results of the obtained zeolite.

  FIG. 6 is a water vapor adsorption isotherm at 55 ° C. measured by an adsorption isotherm measuring device (Belsorb 18: Nippon Bell Co., Ltd.). The adsorption isotherm was measured at an air high temperature bath temperature of 60 ° C., an adsorption temperature of 55 ° C., an initial introduction pressure of 3.0 torr, an introduction pressure set point of 0, a saturated vapor pressure of 118.11 mmHg, and an equilibrium time of 500 seconds.

(Example 3)
In Example 3, the nitrogen fired sample obtained in Example 2 was refired with air under the same conditions as in Example 1. Table 8 shows the XRD results of the obtained zeolite. The recalcined zeolite was almost the same as in Example 1.

(Example 4)
Example 4 relates to FAPO-2 synthesized using morpholine alone as a template.

  To 210 g of water, 86.5 g of 85% phosphoric acid was added, and 51 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. To this was added a solution obtained by dissolving 41.7 g of ferrous sulfate heptahydrate in 218 g of water, and 75.7 g of morpholine was slowly added thereto, followed by further stirring for 3 hours. A gel-like starting reaction product having the following composition was obtained.

_{0.4FeSO 4: Al 2 O 3:} P 2 O 5: 2 -morpholin: _70H 2 O

  The mixture thus obtained was charged into a 1 liter stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and reacted at 180 ° C. for 24 hours while stirring at 100 rpm. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 9 shows the XRD measurement results of the zeolite thus obtained.

  This was fired under the same airflow as in Example 1. Table 10 shows the XRD measurement results of the obtained zeolite.

  This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the constituent ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron was 17.2% for iron, 29.4% for aluminum, and 53.4% for phosphorus.

  Furthermore, the water vapor adsorption isotherm at 55 ° C. measured under the same conditions as in Example 1 using the zeolite adsorption isotherm measuring apparatus (Belsorb 18: Nippon Bell Co., Ltd.) is shown in FIG.

(Example 5)
Example 5 relates to FAPO-2 synthesized using morpholine and triethylamine as templates.

  12.5 g of 85% phosphoric acid was added to 28.05 g of water, and 6.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. A solution prepared by dissolving 8.3 g of ferrous sulfate heptahydrate in 29 g of water was added thereto, and a solution obtained by mixing 5.05 g of morpholine and 4.35 g of triethylamine was slowly added thereto, followed by further stirring for 3 hours. A gel-like starting reaction product having the following composition was obtained.

0.6 FeSO ₄ : Al ₂ O ₃ : P ₂ O ₅ : 1.16 morpholine: 0.86 triethylamine: 70H ₂ O

  The mixture thus obtained was charged into a 0.2 liter stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and allowed to react at 160 ° C. for 4 days in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 11 shows the XRD measurement results of the obtained zeolite.

  This was fired under the same airflow as in Example 1. Table 12 shows the XRD measurement results of the zeolite thus obtained.

  This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron was 13.2% for iron, 38.3% for aluminum, and 48.5% for phosphorus.

  FIG. 8 shows a water vapor adsorption isotherm at 55 ° C. measured under the same conditions as in Example 1 with a zeolite adsorption isotherm measuring device (Belsorb 18: Nippon Bell Co., Ltd.) and at 25 ° C. measured with the same device. It is a water vapor adsorption isotherm. 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.

(Example 6)
Example 6 relates to FAPO-2 synthesized using morpholine and tricyclohexylamine as templates.

  11.5 g of 85% phosphoric acid was added to 26 g of water, and 5.44 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 2 hours. A solution prepared by dissolving 8.3 g of ferrous sulfate heptahydrate in 26 g of water was added thereto, and a solution obtained by mixing 2.18 g of morpholine and 7.43 g of cyclohexylamine was slowly added thereto, followed by further stirring for 2 hours. A gel-like starting reaction product having the following composition was obtained.

_{0.6FeSO 4: 0.8Al 2 O 3:} P 2 O 5: 0.5 morpholine: 1.5 cyclohexylamine: _60H 2 O

  The obtained mixture was charged in a 0.2 l stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and allowed to react at 190 ° C. for 1 day in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 13 shows the XRD measurement results of the obtained zeolite.

  This was fired under the same airflow as in Example 1. When the XRD of the zeolite thus obtained was measured, it was as shown in the following table.

  This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the constituent ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron was 14.1% for iron, 38.4% for aluminum, and 47.4% for phosphorus.

  FIG. 9 is a water vapor adsorption isotherm at 55 ° C. measured under the same conditions as in Example 1 using a zeolite adsorption isotherm measuring apparatus (Belsorb 18: Nippon Bell Co., Ltd.).

(Example 7)
Example 7 relates to Si-containing FAPO-2 synthesized using morpholine and triethylamine as templates.

  12.5 g of 85% phosphoric acid was added to 28.05 g of water, and 6.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. To this, 2.78 g of ferrous sulfate heptahydrate was dissolved in 29 g of water, 0.15 g of fumed silica (Aerosil 200) was added thereto, and 5.05 g of morpholine and 4.35 g of triethylamine were further mixed. The solution was added slowly and stirred for an additional 3 hours. A gel-like starting reaction product having the following composition was obtained.

0.2FeSO ₄ : 0.05SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 1.16 morpholine: 0.86 triethylamine: 70H ₂ O

  The obtained mixture was charged into a 0.2 l stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and allowed to react at 170 ° C. for 2 days in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Table 15 shows the XRD measurement results of the zeolite thus obtained.

  This was fired under the same airflow as in Example 1. Table 16 shows the XRD measurement results of the obtained zeolite.

  This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, iron, and silicon was 9.9% for iron, 2.8% for silicon, 40.7% for aluminum, and 46.7% for phosphorus. %Met.

FIG. 10 is a water vapor adsorption isotherm at 55 ° C. measured under the same conditions as in Example 1 using a zeolite adsorption isotherm measuring apparatus (Belsorb 18: Nippon Bell Co., Ltd.). In addition, all the zeolite obtained in the said Examples 1-7 was 1 type (framework density = 14.5 T / nm < ³ >) of the CHA type.

(Example 8)
Example 8 is an AEI type FAPO synthesized using diisopropylethylamine and methylbutylamine as templates.

  To 15 g of water, 8.07 g of 85% phosphoric acid was added, and 3.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. A solution prepared by dissolving 3.88 g of ferrous sulfate heptahydrate in 20 g of water was added thereto, and a solution obtained by mixing 4.55 g of diisopropylethylamine and 3.05 g of methylbutylamine was slowly added thereto, followed by further stirring for 3 hours. . A gel-like starting reaction product having the following composition was obtained.

_{0.4FeSO 4: 0.8Al 2 O 3:} P 2 O 5: 1 diisopropylethylamine: 1 methylbutylamine: _60H 2 O

  The mixture thus obtained was charged in a 0.2 l stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and allowed to react at 170 ° C. for 2 days in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C.

The obtained zeolite was calcined at 550 ° C. under an air stream. When the XRD was measured, it was AEI type (framework density = 14.8 T / nm ³ ). This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron was 9.2% for iron, 42.6% for aluminum, and 48.2% for phosphorus.

  FIG. 11 shows a water vapor adsorption isotherm at 55 ° C. measured under the same conditions as in Example 1 using a zeolite adsorption isotherm measuring device (Belsorb 18: Nippon Bell Co., Ltd.).

Example 9
Example 9 is a CHA-type Si-containing FAPO synthesized using morpholine and triethylamine as templates as templates.

  12.5 g of 85% phosphoric acid was added to 28.05 g of water, and 6.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. To this was added 1.4 g of ferrous sulfate heptahydrate dissolved in 29 g of water and 0.3 g of fumed silica (Aerosil 200) added thereto, and 5.05 g of morpholine and 4.35 g of triethylamine were mixed. The solution was added slowly and stirred for an additional 3 hours. A gel-like starting reaction product having the following composition was obtained.

0.1FeSO ₄ : 0.1SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 1.16 morpholine: 0.86 triethylamine: 70H ₂ O

  The obtained mixture was charged in a 0.2 l stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and allowed to react at 160 ° C. for 3 days in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C.

The obtained zeolite was calcined at 550 ° C. under an air stream. When the XRD was measured, it was a CHA type (framework density = 14.5 T / nm ³ ). This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron is 6.6% for iron, 4.6% for silicon, 43.6% for aluminum, and 43.6% for phosphorus. there were.

  FIG. 12 shows a water vapor adsorption isotherm at 55 ° C. measured under the same conditions as in Example 1 using a zeolite adsorption isotherm measuring device (Belsorb 18: Nippon Bell Co., Ltd.).

(Example 10)
Example 10 is a CHA-type high Si-SAPO synthesized using cyclohexylamine as a template.

  12.5 g of 85% phosphoric acid was added to 28.05 g of water, and 6.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. A solution prepared by mixing 3 g of fumed silica (Aerosil 200) with 22 g of water was added thereto, and a solution prepared by further mixing 9.9 g of cyclohexylamine was slowly added thereto, followed by further stirring for 2 hours. A gel-like starting reaction product having the following composition was obtained.

SiO ₂ : Al ₂ O ₃ : P ₂ O ₅ : 2 cyclohexylamine: 60H ₂ O

  The mixture thus obtained was charged into a 0.2 liter stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and allowed to react at 200 ° C. for 1 day in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C.

  The obtained zeolite was calcined at 550 ° C. under an air stream. When the XRD was measured, it was CHA type. This sample was subjected to elemental analysis by ICP analysis in the same manner as in Example 1. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and iron was 12.0% for silicon, 49.2% for aluminum, and 38.9% for phosphorus.

  FIG. 13 shows a water vapor adsorption isotherm at 55 ° C. measured under the same conditions as in Example 1 using a zeolite adsorption isotherm measuring apparatus (Belsorb 18: Nippon Bell Co., Ltd.).

(Comparative Example 1)
Comparative Example 1 is a conventional Y-type zeolite. FIG. 14 shows a measurement of Y type zeolite (320NAA, silica / alumina ratio = 5.5) manufactured by Tosoh Corporation under the same conditions as in Example 1 using an adsorption isotherm measuring device (Belsorb 18: Nippon Bell Co., Ltd.). The water vapor adsorption isotherm at 55 ° C is shown.

It is the schematic which shows an example of the adsorption heat pump of this invention. 3 is a 55 ° C. adsorption isotherm of water of Example 1. FIG. 3 is an XRD-DSC result in the water desorption process of Example 1. FIG. It is a XRD-DSC result in the water adsorption process of Example 1. It is XRD of the desorption of water of Example 1, and an adsorption state. 5 is a 55 ° C. adsorption isotherm of the water of Example 2. 5 is a 55 ° C. adsorption isotherm of water of Example 4. It is the adsorption isotherm of 55 degreeC and 25 degreeC of the water of Example 5. 5 is an adsorption isotherm of water of Example 6 at 55 ° C. FIG. 5 is an adsorption isotherm of water of Example 7 at 55 ° C. FIG. It is a 55 degreeC adsorption isotherm of the water of Example 8. It is a 55 degreeC adsorption isotherm of the water of Example 9. It is a 55 degreeC adsorption isotherm of the water of Example 10. It is a 55 degreeC adsorption isotherm of the water of the comparative example 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Adsorption tower 2 Adsorption tower 3 Adsorption substance 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 Adsorbing substance 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)

Claims (12)

An adsorbent, an adsorbing / desorbing part having an adsorbent for adsorbing / desorbing the adsorbing substance, an evaporating part connected to the adsorbing / desorbing part and evaporating the adsorbing substance, and connected to the adsorbing / desorbing part; In an adsorption heat pump with a condensing part that condenses substances,
Adsorbing the adsorbent is the zeolite crystalline iron aluminophosphate or crystalline silicon aluminophosphate zeolite, the framework density is 10T / nm ³ or more 18T / nm ³ or less, measured at 55 ° C. In the isotherm, the adsorption amount of the adsorbent at a relative vapor pressure of 0.02 is greater than 0 and 0.12 g / g or less, and the adsorption amount of the adsorbent at a relative vapor pressure of 0.1 is 0.13 g / g or more. Relative in which the adsorption amount change of the adsorbed material is 0.08 g / g or more when the relative vapor pressure is changed by 0.05 in the range of 0.4 g / g or less and the relative vapor pressure is 0.02 or more and 0.1 or less. An adsorption heat pump having a vapor pressure region. The crystalline iron aluminophosphate is at least 9.5 ± 0.3, 10.1 ± 0.3, 12.8 ± in powder X-ray diffraction measurement with Cu—Kα ray having an X-ray wavelength of 1.5418 mm. 0.3,19.5 diffraction peaks at diffraction angles (2 [Theta]) of ± 0.3,20.4 ± 0.3,24.3 ± 0.3 and 30.7 ± 0.4 appears claim 1 Adsorption heat pump described in 1. The adsorption amount of the adsorbing substance at a relative vapor pressure of 0.02 is greater than 0 g / g and 0.1 g / g or less, and the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.1 is 0.15 g / g or more and 0.0. The adsorption heat pump according to claim 1 or 2 , wherein the adsorption heat pump is 4 g / g or less. An adsorbent, an adsorbing / desorbing part having an adsorbent for adsorbing / desorbing the adsorbing substance, an evaporating part connected to the adsorbing / desorbing part and evaporating the adsorbing substance, and connected to the adsorbing / desorbing part; It is an adsorbent for use in an adsorption heat pump with a condensing part that condenses substances,
Adsorbing the adsorbent is the zeolite crystalline iron aluminophosphate or crystalline silicon aluminophosphate zeolite, the framework density is 10T / nm ³ or more 18T / nm ³ or less, measured at 55 ° C. In the isotherm, the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.02 is greater than 0 g / g and 0.12 g / g or less, and the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.1 is 0.13 g / g. g or more and 0.4 g / g or less, and when the relative vapor pressure is changed by 0.05 in the range of relative vapor pressure of 0.02 or more and 0.1 or less, the change in the amount of adsorption of the adsorbed substance is 0.08 g / g or more. An adsorbent characterized by having a relative vapor pressure region. The crystalline iron aluminophosphate is, contains at least Fe, Al and P in a framework structure, the framework density of 10T / nm ³ or more 16T / nm ³ or less, the adsorption material according to claim 4. The crystalline iron aluminophosphate is at least 9.5 ± 0.3, 10.1 ± 0.3, 12.8 ± in powder X-ray diffraction measurement with Cu—Kα ray having an X-ray wavelength of 1.5418 mm. 0.3,19.5 diffraction peaks at diffraction angles (2 [Theta]) of ± 0.3,20.4 ± 0.3,24.3 ± 0.3 and 30.7 ± 0.4 appears, claim 4 Or the adsorbent of 5 . The adsorbent according to any one of claims 4 to 6, wherein the Fe, Al, and P constitute a skeleton structure in a molar ratio of the following formulas 1 to 3.
0.001 ≦ x ≦ 0.3… 1
(X represents the molar ratio of Fe to the total of Fe, Al and P)
0.2 ≦ y ≦ 0.6 2
(Y represents the molar ratio of Al to the total of Fe, Al and P)
0.3 ≦ z ≦ 0.6 3
(Z represents the molar ratio of P to the total of Fe, Al and P) The crystalline silicon aluminophosphate is at least Si in the skeletal structure, containing Al and P, Si, molar ratio of Si to the sum of Al and P is greater than 9 percent, the framework density is 10T / nm ³ or more The adsorbent according to claim 4 , which is 16 T / nm ³ or less. The adsorbent according to claim 4 or 8 , wherein the Si, Al, and P constitute a skeleton structure in a molar ratio of the following formulas 4-6.
0.09 <p ≦ 0.30 4
(P represents the molar ratio of Si to the sum of Si, Al and P)
0.30 ≦ q ≦ 0.60… 5
(Q represents the molar ratio of Al to the sum of Si, Al and P)
0.30 ≦ r ≦ 0.60… 6
(R represents the molar ratio of P to the sum of Si, Al and P) The adsorption amount of the adsorbing substance at a relative vapor pressure of 0.02 is 0.0 g / g or more and 0.1 g / g or less, and the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.1 is 0.15 g / g or more and 0. The adsorbent according to claim 4 , wherein the adsorbent is 4 g / g or less. The adsorption amount of the adsorbing substance at a relative vapor pressure of 0.02 is 0.0 g / g or more and 0.05 g / g or less, and the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.1 is 0.2 g / g or more and 0. .4 g / g or less, and the amount of adsorption of the adsorbed material is 0.12 g / g or more when the relative vapor pressure is changed by 0.05 within the range of the relative vapor pressure of 0.02 or more and 0.1 or less. Item 11. The adsorbent according to any one of Items 4 to 10 . The adsorption amount of the adsorbing substance at a relative vapor pressure of 0.02 is 0.0 g / g or more and 0.1 g / g or less, and the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.07 is 0.15 g / g or more and 0. .4 g / g or less, and a change in the amount of adsorption of the adsorbent when the relative vapor pressure is changed by 0.05 within a range of relative vapor pressure of 0.02 or more and 0.1 or less, is 0.08 g / g or more. Item 11. The adsorbent according to any one of Items 4 to 10 .

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