JP2008267802A - Adsorption heat pump, air conditioner for vehicle, adsorption heat pump operating method, adsorbent for adsorption heat pump, and application method of adsorbent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adsorption heat pump of high efficiency using an adsorbent capable of adsorbing and desorbing an adsorbate in a low relative vapor pressure region. <P>SOLUTION: The adsorption heat pump is driven by a heat source of 100°C or lower, wherein the adsorbent, when measured at 25°C, gives a water vapor adsorption isotherm which, in a relative vapor pressure range of 0.05 to 0.30, has a relative vapor pressure region in which a change in a relative vapor pressure of 0.15 results in a change in a water adsorption amount of 0.18 g/g or larger, and the adsorbent is zeolite containing aluminum, phosphorus and a heteroatom in a framework structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an adsorption heat pump using a specific adsorbent, an operation method thereof, and a vehicle air conditioner using the adsorption heat pump. Furthermore, it is related with the adsorption material for adsorption heat pumps, and its usage .

  In an adsorption heat pump, in order to regenerate an adsorbate, for example, an adsorbent that has adsorbed water, the adsorbent is heated to desorb the adsorbate, and the dried adsorbent is cooled to a temperature used for adsorbate adsorption. Used again for adsorbate adsorption. Absorption heat pumps that utilize exhaust heat and heat at relatively high temperatures (120 ° C. or higher) as a heat source for regeneration of the adsorbent have already been put into practical use. However, the heat generated by cogeneration equipment, fuel cells, automobile engine cooling water, solar heat, etc. is relatively low at 100 ° C. or less, so it cannot be used as a driving heat source for absorption heat pumps currently in practical use. Therefore, effective utilization of low-temperature exhaust heat of 100 ° C. or lower, and further 60 ° C. to 80 ° C. has been demanded.

  Although the operation principle of the adsorption heat pump is the same, the adsorption characteristics required for the adsorbent differ greatly depending on the available heat source temperature. For example, the exhaust heat temperature of gas engine cogeneration used as a heat source on the high temperature side and the polymer electrolyte fuel cell is 60 ° C. to 80 ° C., and the temperature of the cooling water of the automobile engine is 85 ° C. to 90 ° C. The heat source temperature on the cooling side also varies depending on the installation location of the apparatus. For example, in the case of an automobile, the temperature is obtained by a radiator, and in a building or a house, the temperature is such as a water cooling tower or river water. That is, the operating temperature range of the adsorption heat pump is 25 ° C to 35 ° C on the low temperature side when installed in a building or the like, 60 ° C to 80 ° C on the high temperature side, 30 ° C to 40 ° C on the low temperature side when installed on an automobile, etc. The high temperature side is about 85 ° C to 90 ° C. Thus, in order to effectively use the exhaust heat, an apparatus that can be driven even if the temperature difference between the low temperature side heat source and the high temperature side heat source is small is desired.

  In order for the device to operate sufficiently even at a relatively high temperature around the adsorbent, it is necessary to adsorb the adsorbate at a low relative vapor pressure, and to reduce the size of the device by using a small amount of adsorbent. Needs a large amount of adsorption / desorption of the adsorbent. In order to use a low-temperature heat source for adsorbate desorption (regeneration of adsorbent), the desorption temperature needs to be low. That is, as an adsorbent used in an adsorption heat pump, (1) adsorbate is adsorbed at a low relative vapor pressure (can be adsorbed at a high temperature), (2) adsorbed and desorbed in a large amount, and (3) adsorbate is adsorbed at a high relative vapor pressure ( Adsorbents that can be desorbed at low temperatures are desired.

  Further, the use of various adsorbents as the adsorbent used in the adsorption heat pump has been studied, but there are various problems, and the solution is desired.

  The present invention has been made for the purpose of providing an efficient adsorption heat pump using an adsorbent capable of adsorbing and desorbing adsorbate in a low relative vapor pressure range.

As a result of intensive studies to solve the above problems, the present inventors have found an adsorbent suitable for an adsorption heat pump that uses adsorption / desorption of adsorbate as a drive source of the apparatus. That is, the gist of the present invention is that an adsorbate, an adsorption / desorption portion having an adsorbent for adsorbing and desorbing the adsorbate , an evaporation portion for evaporating the adsorbate connected to the adsorption / desorption portion, and the adsorption / desorption portion and a condensing unit that performs condensation of the concatenated adsorbate, at 100 ° C. adsorption heat pump driven by the following heat sources, adsorbing material, the relative vapor pressure less than 0.05 in water vapor adsorption isotherm measured at 25 ° C., When the relative vapor pressure changes 0.15 or less in the range of 0.30 or less, the water adsorption amount change has a relative vapor pressure range of 0.18 g / g or more, and the skeletal structure has aluminum, phosphorus and heteroatoms. exist at the adsorption heat pump, which is a zeolite containing and. Another gist of the present invention resides in a vehicle air conditioner characterized in that the adsorption heat pump is used for air conditioning in a vehicle compartment.

The other gist of the present invention includes an adsorbate, an adsorption / desorption portion having an adsorbent for adsorbing / desorbing the adsorbate, an evaporation portion for evaporating the adsorbate coupled to the adsorption / desorption portion, and the adsorption / desorption portion. An adsorption heat pump operating with a heat source of 100 ° C. or lower, wherein the adsorbent is a zeolite containing aluminum, phosphorus and heteroatoms in the skeleton structure. The operation method of the adsorption heat pump is characterized by operating under the condition that the difference between the adsorption amount at the desorption side relative vapor pressure φ1 and the adsorption amount at the adsorption side relative vapor pressure φ2 is 0.18 g / g or more. Still another gist of the present invention is that it is used in an adsorption heat pump driven by a heat source of 100 ° C. or less, and is relative to a water vapor adsorption isotherm measured at 25 ° C. in a range of relative vapor pressure of 0.05 or more and 0.30 or less. When the vapor pressure changes by 0.15, the adsorbent has a relative vapor pressure range in which the amount of adsorption of water is 0.18 g / g or more, and the adsorbent contains aluminum, phosphorus, and heteroatoms in the skeleton structure. It exists in the adsorption material for adsorption heat pumps characterized by being a zeolite containing.

Furthermore, another gist is to heat the adsorbent with a heat source of 100 ° C. or lower to desorb the adsorbate, cool the dried adsorbent to a temperature used for adsorbate adsorption, and use it again for adsorbate adsorption. In the method of using the adsorbent, when the adsorbent changes in the water vapor adsorption isotherm measured at 25 ° C. in the range of relative vapor pressure of 0.05 to 0.30, the relative vapor pressure changes by 0.15. The present invention resides in a method of using an adsorbent characterized in that the adsorbent change is a zeolite having a relative vapor pressure range of 0.18 g / g or more and containing skeleton structure containing aluminum, phosphorus and heteroatoms .

As adsorbents for adsorption heat pumps, silica gel and zeolite with a low silica alumina ratio have been generally used. However, adsorbents that have been used in conventional adsorption heat pumps have insufficient adsorption / desorption capability to use a relatively low-temperature heat source as a drive source for the adsorption heat pump.
For example, when a 13X water vapor adsorption isotherm is considered as a representative example of a zeolite for an adsorption heat pump, the water vapor adsorption amount of zeolite is rapidly adsorbed at a relative vapor pressure of 0.05 or less, and in a relative vapor pressure region higher than 0.05, It does not change. When regenerating the adsorbent, the relative humidity of the surrounding gas is lowered to remove the water once adsorbed, but it is necessary to lower the relative vapor pressure to desorb the water adsorbed on the zeolite 13X. Therefore, it is said that a heat source of 150 ° C. to 200 ° C. is necessary. In general, zeolite is excellent in water adsorption ability, but once adsorbed, adsorbate is difficult to desorb and has a drawback that a high-temperature heat source is required for regeneration.
Recently, mesoporous molecular sieves (FSM-10 and the like) synthesized using a surfactant micelle structure as a template (JP-A-9-178292) and a porous aluminum phosphate molecular sieve (commonly referred to as AlPO ₄ ) 11-197439) and the like are also being studied. Mesoporous molecular sieve (FSM-10) is a promising material with a relative vapor pressure in the range of 0.20 and 0.35 and a large adsorption amount difference of 0.25 g / g (Japanese Patent Laid-Open No. 9-178292: FIG. 14). Graph 4; FSM-10). However, the amount of adsorption is small in the range of relative vapor pressure of 0.05 to 0.30, which is an example of the operation of the adsorption heat pump of the present invention. Among them, the adsorption amount change is large in the range of the relative vapor pressure of 0.15 to 0.30, but the adsorption amount difference at this time is 0.08 g / g, and the performance of the adsorption heat pump has to be inferior. . In addition, it has been pointed out that the structure collapses and the function as an adsorbent decreases when used repeatedly, and durability is an issue.
For example, the adsorption isotherm (Colloid Poly Sci 277, p83-88) of ALPO-5, which is an AFI type (framework density = 17.5T / 1,000 ³ ) zeolite of the porous aluminum phosphate molecular sieve shown in FIG. (1999), FIG. 1 (adsorption temperature 30 ° C.)), the adsorption amount of ALPO-5 increases rapidly in the range of relative vapor pressure of 0.25 to 0.40. Although adsorption / desorption was possible within a pressure range of 0.05 to 0.3, a change in adsorption amount was 0.14 g / g within a relative vapor pressure range of 0.15 to 0.30.
A silica gel type A (Fuji Silysia Chemical Co., Ltd.), known as an adsorbent suitable for an adsorption heat pump, was measured with an adsorption isotherm (Belsorb 18: Nippon Bell Co., Ltd.). The adsorption isotherm is shown in FIG. This measurement was performed under the same conditions as SAPO-34 in FIG. According to the adsorption isotherm of the silica gel A type in FIG. 2, the silica gel A type can obtain an adsorption amount substantially proportional to the relative water vapor pressure in the range of the relative water vapor pressure of 0 to 0.7. However, in the same relative vapor pressure range of 0.15 to 0.30 as that of mesoporous molecular sieve and porous aluminum phosphate molecular sieve, the amount of adsorption of A-type silica gel is only 0.08 g / g. Adsorption heat pumps using silica gel as an adsorbent have been commercialized, but the apparatus must be large due to the small difference in adsorption amount.
The adsorption heat pump using the adsorbent exhibiting a large change in adsorption / desorption amount in the range of relative vapor pressure of 0.05 or more and 0.30 or less of the present invention has a large difference in moisture adsorption amount due to adsorption / desorption of the adsorbent, and is low. Since the adsorbent can be regenerated (desorbed) at a temperature, the adsorption heat pump can be driven efficiently by using a heat source having a temperature lower than that in the prior art. That is, according to the adsorbent of the present invention, an adsorption heat pump that is driven by a relatively low-temperature heat source of 100 ° C. or less can be provided.

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

φ1 and φ2 are the following desorption side relative vapor pressure φ1 = equilibrium vapor pressure (Tlow1) / equilibrium vapor pressure (High)
Adsorption side relative vapor pressure φ2 = equilibrium vapor pressure (Tcool) / equilibrium vapor pressure (Tlow2)
Is a relative vapor pressure range that can be operated between φ1 and φ2.
Here, the high temperature heat source temperature High is the temperature of the heat medium heated when desorbing the adsorbate from the adsorbent to regenerate the adsorbent, the low temperature heat source temperature Tlow1 is the temperature of the adsorbate in the condensing part, and the low temperature heat source temperature Tlow2. Means the temperature of the heat medium to be cooled when the adsorbent after regeneration is used for adsorption, and the cold generation temperature Tcool means the temperature of the adsorbate in the evaporation section, that is, the temperature of the generated cold. The equilibrium vapor pressure can be determined from the temperature using the equilibrium vapor pressure curve of the adsorbate.

  Hereinafter, the operating vapor pressure range when the adsorbate is water will be exemplified. When the high temperature heat source temperature is 80 ° C. and the low temperature heat source temperature is 30 ° C., the operating vapor pressure range is φ1 to φ2 = 0.09 to 0.29. Similarly, when the high-temperature heat source temperature is 60 ° C., the operation relative water vapor pressure range is φ1 to φ2 = 0.21 to 0.29. The case of driving the adsorption heat pump using the exhaust heat of the automobile engine is described in detail in Japanese Patent Application Laid-Open No. 2000-140625. Based on this report, the high temperature heat source temperature is about 90 ° C. and the low temperature heat source temperature is 30 ° C. In this case, the operation relative water vapor pressure range is φ1 to φ2 = 0.06 to 0.29.

  From the above, when the adsorption heat pump is driven using the exhaust heat of the gas engine cogeneration, the polymer electrolyte fuel cell or the automobile engine, the operation relative water vapor pressure range is φ1 to φ2 = 0.05 to 0.30. If limited, it is considered that φ1 to φ2 = 0.06 to 0.29. That is, a material having a large change in adsorption amount within this operating humidity range is preferable. Therefore, a material whose adsorption amount varies greatly in the range of relative vapor pressure of 0.05 to 0.30, preferably in the range of 0.06 to 0.29 is preferable.

  For example, it is assumed that a cooling capacity of 3.0 kW (= 10,800 kJ / hr) is obtained by an adsorption heat pump. Here, 3.0 kW is the cooling capacity of an air conditioner used for a general automobile air conditioner. It is considered that the capacity of the adsorption heat pump is desirably at least 15 liters or less based on engine room surveys of various vehicles.

Next, the adsorbent weight that can be filled in a volume of 15 liters or less is determined.
The parts to be mounted in the engine room include an adsorption tower body, an evaporator, a condenser, and control valves. It is necessary to make the assembly in which these are integrally formed into a capacity of 15 liters or less. In our study, it is considered that the size of the evaporator, condenser and valves can be formed with about 4.5 liters. Therefore, the capacity of the adsorption tower body is approximately 10.5 liters or less. Since the adsorbent packing ratio and the adsorbent bulk density in the adsorption tower are usually about 30% and about 0.6 kg / liter, respectively, the adsorbent weight (W) that can be packed is 10.5 × 30% × 0.6. = 1.89kg.

Next, characteristics required for the adsorbent will be described.
The cooling capacity R in the adsorption heat pump is expressed by the following formula A.
R = (W · ΔQ · η _C · ΔH / τ) · η _h (Formula A)
Here, W is the weight of the adsorbent packed in one adsorption tower (one side), ΔQ is the equilibrium adsorption amount amplitude in the conditions of adsorption and desorption, and the adsorption amount difference (Q2-Q1), and η _C is the equilibrium adsorption. Adsorption amplitude efficiency indicating the ratio of the actual adsorption amplitude within the switching time with respect to the amplitude ΔQ, ΔH is the latent heat of vaporization of water, τ is the switching time between the adsorption process and the desorption process, η _h is the hot water in the adsorbent and heat exchanger The heat mass efficiency which considered the heat mass loss by changing the temperature between temperature and cooling water temperature is shown.

As described above, R is 3 kW, and W is 1.89 kg / 2 = 0.95 kg. From our past studies, τ is appropriately about 60 seconds, and ΔH, η _C , and η _h are about 2500 kJ / kg, 0.6, and 0.85, respectively (Equation A). When ΔQ is obtained,
ΔQ = R / W / η _C / ΔH ・ τ / η _h = 3.0 / 0.95 / 0.6 / 2500 ・ 60 / 0.85 = 0.149kg / kg
It becomes. That is, as an adsorbent used in an adsorption heat pump for automobiles,
ΔQ is preferably 0.15 g / g or more, 0.18 g / g or more, and more preferably 0.20 g / g or more.

  Adsorption heat pumps use the ability of adsorbents to adsorb and desorb adsorbates as a drive source. In the adsorption heat pump, water, ethanol, acetone and the like can be used as the adsorbate which is an adsorbate. Among them, water is most preferable from the viewpoint of safety, price, and latent heat of evaporation. The adsorbate 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 which is one of the features of the present invention is a zeolite containing aluminum, phosphorus and heteroatoms in the skeleton structure. The zeolite here may be a natural zeolite or an artificial zeolite. For example, an artificial zeolite includes aluminosilicates and aluminophosphates according to International Zeolite Association (IZA) regulations.

Here, among the aluminophosphates, aluminophosphate (AlPO ₄ -5) containing no heteroatom exhibits hydrophobic adsorption characteristics and is not suitable as the adsorbent of the present invention. In order to use it suitably as the adsorbent of the present invention, a part of aluminum and phosphorus for imparting hydrophilicity is silicon, lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, nickel, palladium. It is necessary to substitute with copper, zinc, gallium, germanium, arsenic, tin, calcium, boron or the like.

  Among these, zeolite substituted with silicon, magnesium, titanium, zirconium, iron, cobalt, zinc, gallium, or boron is preferable, and zeolite substituted with silicon is most preferable, which is commonly referred to as SAPO. These heteroatoms may be substituted with two or more of aluminum and phosphorus in the skeleton.

The zeolite used as the adsorbent in the present invention is a zeolite containing aluminum, phosphorus and heteroatoms in the skeleton structure, and has an abundance ratio of atoms represented by the following formulas (1), (2) and (3) Those are preferred.
0.001 ≦ x ≦ 0.3 (1)
(Wherein x represents the molar ratio of heteroatoms to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
0.3 ≦ y ≦ 0.6 (2)
(Wherein y represents the molar ratio of aluminum to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
0.3 ≦ z ≦ 0.6 (3)
(Wherein z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
And among the above-mentioned proportions of atoms, the heteroatoms are represented by the following formula (4).
0.003 ≦ x ≦ 0.25 (4)
(Wherein x is as defined above)
Is preferably represented by the following formula (5):
0.005 ≦ x ≦ 0.2 (5)
(Wherein x is as defined above)
Is more preferable.

Further, the zeolite used as an adsorbent in the present invention, the framework density is preferably at 10.0T / 1,000Å ³ or 16.0T / 1,000Å ³ or less, more preferably 10.0T / 1, 000Å is ³ or more 15.0 / 1,000 Å ³ or less in the range of zeolites. Here, the framework density means the number of elements constituting a skeleton other than oxygen per 1,000 cm ³ of the zeolite, and this value is determined by the structure of the zeolite.

  The structure of such a zeolite can be represented by a code defined by IZA, AFG, MER, LIO, LOS, PHI, BOG, ERI, OFF, PAU, EAB, AFT, LEV, LTN, AEI, AFR, AFX, GIS , KFI, CHA, GME, THO, MEI, VFI, AFS, LTA, FAU, RHO, DFO, EMT, AFY, * BEA, etc., preferably AEI, GIS, KFI, CHA, GME, VFI, AFS, LTA , FAU, RHO, EMT, AFY, * BEA.

Framework density correlates with pore volume, and in general, lower framework density zeolites have greater pore volume and therefore higher adsorption capacity. Further, it is expected that zeolite that is not currently synthesized can be suitably used as an adsorbent in the present invention if the framework density is within this region when synthesized.
For example, in the case of an aluminophosphate having a CHA structure, a desired adsorption performance can be obtained by using a silicoaluminophosphate known as SAPO-34 in which atoms such as silicon are included in the skeleton. A method for synthesizing SAPO-34 is described in US Pat. No. 4,440,871 and the like.

The pore diameter of the adsorbent is preferably about 3 to 10 mm from the viewpoint of adsorption characteristics and strength.
Further, when the zeolite is an aluminosilicate, silicon in the skeleton, a part of aluminum (may be all in the case of aluminum) is another atom such as magnesium, titanium, zirconium, vanadium, chromium, manganese, iron, It may be substituted with cobalt, zinc, gallium, tin, boron or the like. In the case of aluminosilicate, if the molar ratio of silicon and aluminum (aluminum + heteroatom) is too small, it will be adsorbed rapidly in a too low humidity region, as in the case of 13X, and if it is too large It is too hydrophobic to absorb water very much. Therefore, the zeolite used in the present invention usually has a silicon / aluminum molar ratio of 4 or more and 20 or less, preferably 4.5 or more and 18 or less, and more preferably 5 or more and 16 or less.

  These zeolites include those having exchangeable cationic species. In this case, the cationic species include alkaline elements such as protons, Li and Na, alkaline earth elements such as Mg and Ca, and rare earths such as La and Ce. Examples thereof include transition metals such as elements, Fe, Co, and Ni, and protons, alkali elements, alkaline earth elements, and rare earth elements are preferable. Furthermore, proton, Li, Na, K, Mg, and Ca are more preferable. These zeolites may be used alone, in combination, or in combination with other silica, alumina, activated carbon, clay, or the like.

As an example of a particularly preferable adsorbent used in the present invention, an aluminophosphate having a CHA structure, in which atoms such as silicon are added to the framework structure of zeolite, SAPO-34 (framework density = 14.6T / 1,000Å). ³ ) Silicoaluminophosphate known as:
Furthermore, the adsorbent used in the present invention has a change in the amount of water adsorbed when the relative vapor pressure changes by 0.15 in the range of the relative vapor pressure of 0.05 to 0.30 on the water vapor adsorption isotherm measured at 25 ° C. Adsorbent having a relative vapor pressure region of 0.18 g / g or more, preferably 0.2 g / g or more, preferably a change in water adsorption amount of 0.18 g / g in the range of 0.05 to 0.20. As described above, the adsorbent is preferably 0.2 g / g or more.
A promising material with a difference in water adsorption amount of 0.18 g / g or more when the relative vapor pressure changes by 0.15 at a relative vapor pressure of 0.05 or more and 0.30 or less is zeolite. Since zeolite is a crystal, the pore volume contributing to adsorption depends on the framework density. The maximum adsorption amount of 13X (a framework density of 12.7 T / 1000 kg), which is an example of a zeolite having the smallest framework density, is about 0.30 g / g. Therefore, if the adsorption amount at the lower limit 0.05 of the relative vapor pressure defined by the present invention is more than 0.15 g / g, it is impossible to obtain an adsorption amount difference of 0.18 g / g. Therefore, the adsorption amount at a relative vapor pressure of 0.05 in the water vapor adsorption isotherm is preferably 0.15 g / g or less, preferably 0.12 g / g or less, and more preferably 0.05 g / g or less.
The adsorption isotherm of water vapor at 25 ° C. of SAPO-34 (manufactured by UOP LLC) measured by an adsorption isotherm measuring apparatus (Belsorb 18: Nippon Bell Co., Ltd.) is shown in FIG. The adsorption isotherm was measured at an air high temperature bath temperature of 50 ° C., an adsorption temperature of 25 ° C., an initial introduction pressure of 3.0 torr, an introduction pressure setting point of 0, a saturated vapor pressure of 23.76 mmHg, and an equilibrium time of 500 seconds. As can be seen from FIG. 1, water vapor is rapidly adsorbed at a relative vapor pressure of 0.07 to 0.10, and the amount of change in the adsorption amount in the relative vapor pressure range of 0.05 to 0.20 is 0.25 g / g. . SAPO-34 having such characteristics is one of the most preferable adsorbents used in the present invention.
As described above, since the adsorbent used in the present invention changes more in the same relative vapor pressure range than the conventional silica gel and zeolite, more dehumidification is achieved by using an adsorbent having substantially the same weight. An effect can be generated.

One of the features of the present invention is to use an adsorbent having the above characteristics as an adsorbent for an adsorbate adsorption / desorption portion of an adsorption heat pump. That is, since a large change in adsorption amount can be obtained with a relative vapor pressure change in a narrow range, it is suitable for an adsorption heat pump in which the amount of adsorbent filling is limited, for example, a vehicle air conditioner.
Hereinafter, the action of the adsorption heat pump of the present invention using the adsorbent described above will be specifically described with the adsorption heat pump having the apparatus configuration shown in FIG. 4, but the adsorption heat pump of the present invention is not limited to this.

The conceptual diagram of an example of the adsorption heat pump of this invention is shown in FIG. The adsorption heat pump shown in FIG. 4 includes an adsorbent capable of adsorbing and desorbing adsorbate, and adsorption towers 1 and 2 serving as adsorption / desorption sections filled with the adsorbent and transmitting heat generated by adsorption and desorption of the adsorbate to a heat medium. The evaporator 4 takes out the cold heat obtained by the evaporation of the adsorbate and the condenser 5 discharges the hot heat obtained by the condensation of the adsorbate to the outside. When operating the adsorption heat pump, the operation conditions are obtained from the adsorption isotherm at the ambient temperature so that the adsorption / desorption amount necessary for the operation can be obtained, and the maximum adsorption / desorption amount is usually obtained when the apparatus is operated. To be determined.
As shown in FIG. 4, the adsorption towers 1 and 2 filled with the adsorbent are connected to each other by an adsorbate pipe 30, and the adsorbate pipe 30 is provided with control valves 31 to 34. Here, the adsorbate exists as an adsorbate vapor or a mixture of adsorbate liquid and vapor in the adsorbate pipe.

The evaporator 4 and the condenser 5 are connected to the adsorbate pipe 30. The adsorption towers 1 and 2 are connected in parallel between the evaporator 4 and the condenser 5, and between the condenser 5 and the evaporator 4, the adsorbate condensed in the condenser is returned to the evaporator 4. The return pipe 3 is provided. Reference numeral 41 denotes an inlet of cold water that serves as a cooling output from the evaporator 4, and reference numeral 51 denotes an inlet of cooling water to the condenser 5. Reference numerals 42 and 52 denote outlets of cold water and cooling water, respectively. The cold water pipes 41 and 42 are connected to an indoor unit 300 for exchanging heat with the indoor space (air-conditioned space) and a pump 301 for circulating cold water.
A heat medium pipe 11 is connected to the adsorption tower 1, and a heat medium pipe 21 is connected to the adsorption tower 2. The heat medium pipes 11 and 21 are provided with switching valves 115 and 116, and 215 and 216, respectively. is there. The heat medium pipes 11 and 21 flow a heat medium serving as a heating source or a cooling source for heating or cooling the adsorbents in the adsorption towers 1 and 2, respectively. The heat medium is not particularly limited as long as the adsorbent in the adsorption tower can be effectively heated and cooled.
The hot water is introduced from the inlets 113 and / or 213 by opening and closing the switching valves 115, 116, 215, and 216, passes through the adsorption towers 1 and / or 2, and is led out from the outlets 114 and / or 214. The cooling water is also introduced from the inlets 111 and / or 211 by opening / closing similar switching valves 115, 116, 215, and 216, passes through the respective adsorbers 1 and / or 2, and is led out from the outlets 112 and / or 212. The Moreover, although not shown in figure, the outdoor unit arrange | positioned so that heat exchange with external air, the heat source which produces | generates warm water, and the pump which circulates a heat medium are connected to the heat medium piping 11 and / or 21. 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.
The operation method of the adsorption heat pump will be described with reference to FIG. In the first stroke, the control valves 31 and 34 are closed, the control valves 32 and 33 are released, and the regeneration process is performed in the adsorption tower 1 and the adsorption process is performed in the adsorption tower 2. Further, the switching valves 115, 116, 215, and 216 are operated, and hot water is circulated through the heat medium pipe 11 and cooling water is circulated through the heat medium pipe 21.
When the adsorption tower 2 is cooled, cooling water cooled by exchanging heat with the outside air, river water or the like by a heat exchanger such as a cooling tower is introduced through the heat medium pipe 21 and is usually cooled to about 30 to 40 ° C. The Moreover, the water in the evaporator 4 evaporates by opening operation of the control valve 32, flows into the adsorption tower 2 as water vapor, and is adsorbed by the adsorbent. Water vapor movement occurs due to the difference between the saturated vapor pressure at the evaporation temperature and the adsorption equilibrium pressure corresponding to the adsorbent temperature (generally 20 to 50 ° C., preferably 20 to 45 ° C., more preferably 30 to 40 ° C.). In the evaporator 4, cold heat corresponding to the heat of vaporization of evaporation, that is, cooling output is obtained. From the relationship between the temperature of the cooling water in the adsorption tower and the temperature of the cold water generated by the evaporator, the relative vapor pressure φ2 on the adsorption side (where φ2 is the equilibrium vapor pressure of the adsorbate at the cold water temperature generated by the evaporator, Calculated by dividing by the equilibrium vapor pressure of the adsorbate at the water temperature), but φ2 can be operated so that the adsorbent specified in the present invention is larger than the relative vapor pressure at which water vapor is adsorbed to the maximum. preferable. This is because when the adsorbent specified in the present invention is smaller than the relative vapor pressure at which water vapor is adsorbed at the maximum, the adsorbing capacity of the adsorbent cannot be used effectively and the operating efficiency is deteriorated. φ2 can be appropriately set according to the environmental temperature or the like, but the adsorption heat pump is operated under a temperature condition in which the adsorption amount at φ2 is usually 0.20 or more, preferably 0.29 or more, more preferably 0.30 or more.
The adsorption tower 1 in the regeneration step is usually heated with hot water of 40 to 100 ° C., preferably 50 to 98 ° C., more preferably 60 to 95 ° C., and has an equilibrium vapor pressure corresponding to the temperature range. It is condensed with a saturated vapor pressure at a condensation temperature of 30-40 ° C. (this is equal to the temperature of the cooling water cooling the condenser). Water vapor moves from the adsorption tower 1 to the condenser 5 and is condensed to become water. Water is returned to the evaporator 4 by the return pipe 3. From the relationship between the condenser cooling water temperature and the hot water temperature, the desorption side relative vapor pressure φ1 (where φ1 is the equilibrium vapor pressure of the adsorbate at the temperature of the condenser cooling water, and the equilibrium of the adsorbate at the temperature of the hot water) It is preferable to operate so that φ1 becomes smaller than the relative vapor pressure at which the adsorbent rapidly adsorbs water vapor. If, .phi.1 is because the relative vapor pressure is greater than the adsorption of water vapor sharply adsorption material, it can not be utilized effectively superior adsorption amount of the adsorbent. φ1 can be appropriately set depending on the environmental temperature or the like, but the adsorption heat pump is operated under a temperature condition in which the adsorption amount at φ1 is usually 0.06 or less, preferably 0.05 or less. The difference between the adsorbate adsorption amount at φ1 and the adsorbate adsorption amount at φ2 is usually 0.18 g / g or more, preferably 0.20 g / g or more, more preferably 0.25 g / g or more. To drive. The above is the first step.
In the next second step, the evaporators are similarly switched by switching the control valves 31 to 34 and the switching valves 115, 116, 215, and 216 so that the adsorption tower 1 is an adsorption process and the adsorption tower 2 is a regeneration process. From 4, it is possible to obtain cold heat, that is, cooling output. The adsorption heat pump is continuously operated by sequentially switching the first and second strokes.
Here, the operation method in the case where two adsorption towers are installed has been described. However, by properly desorbing the adsorbate adsorbed by the adsorbent, one of the adsorption towers can maintain a state in which the adsorbate can be adsorbed. If possible, any number of adsorption towers may be installed.

It is a water vapor adsorption isotherm of SAPO-34. It is a silica gel A-type water vapor adsorption isotherm. It is a water vapor adsorption isotherm of ALPO-5. It is a conceptual diagram of an adsorption heat pump.

Explanation of symbols

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

Claims (25)

An adsorbent, an adsorption / desorption part having an adsorbent for adsorbing / desorbing the adsorbate, an evaporation part for evaporating the adsorbate connected to the adsorption / desorption part, and a condensation of the adsorbate connected to the adsorption / desorption part In an adsorption heat pump that is driven by a heat source of 100 ° C. or less, and the adsorbent is within a range of a relative vapor pressure of 0.05 to 0.30 in a water vapor adsorption isotherm measured at 25 ° C. The zeolite has a relative vapor pressure range in which the amount of water adsorbed is 0.18 g / g or more when the relative vapor pressure changes by 0.15, and the framework structure contains aluminum, phosphorus and heteroatoms. Adsorption heat pump. Zeolite containing aluminum, phosphorus and heteroatoms in the skeleton structure has the following formulas (1), (2) and (3):
0.001 ≦ x ≦ 0.3 (1)
(Wherein x represents the molar ratio of the heteroatom to the total of aluminum, phosphorus and heteroatom in the skeleton structure)
0.3 ≦ y ≦ 0.6 (2)
(Wherein y represents the molar ratio of aluminum to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
0.3 ≦ z ≦ 0.6 (3)
(In the formula, z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
The adsorption heat pump according to claim 1, having an abundance ratio of atoms represented by: The adsorption heat pump according to claim 1 or 2, wherein the heteroatom is silicon. The adsorption heat pump according to any one of claims 1 to 3, wherein the adsorbent has an adsorption amount of 0.15 g / g or less at a relative vapor pressure of 0.05 on a water vapor adsorption isotherm measured at 25 ° C. The adsorption heat pump according to any one of claims 1 to 4, wherein a framework density of the zeolite is in a range of 10.0 T / 1,000 to ³ or more and 16.0 T / 1,000 to ³ or less. Adsorption heat pump as claimed in any one of 請 Motomeko 1-5 The zeolite Ru CHA structure der. An air conditioning apparatus for a vehicle, wherein the adsorption heat pump according to any one of claims 1 to 6 is used for air conditioning in a vehicle compartment. An adsorbent, an adsorption / desorption part having an adsorbent for adsorbing / desorbing the adsorbate, an evaporation part for evaporating the adsorbate connected to the adsorption / desorption part, and a condensation of the adsorbate connected to the adsorption / desorption part In the operation method of the adsorption heat pump that includes a condensing unit that is driven by a heat source of 100 ° C. or less, the adsorbent is a zeolite containing aluminum, phosphorus, and heteroatoms in a skeleton structure, and at a desorption side relative vapor pressure φ1 An operation method of the adsorption heat pump, wherein the operation is performed under a condition that a difference between the adsorption amount and the adsorption amount at the adsorption side relative vapor pressure φ2 is 0.18 g / g or more. Zeolite containing aluminum, phosphorus and heteroatoms in the skeleton structure has the following formulas (1), (2) and (3):
0.001 ≦ x ≦ 0.3 (1)
(Wherein x represents the molar ratio of the heteroatom to the total of aluminum, phosphorus and heteroatom in the skeleton structure)
0.3 ≦ y ≦ 0.6 (2)
(Wherein y represents the molar ratio of aluminum to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
0.3 ≦ z ≦ 0.6 (3)
(In the formula, z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
The operation method of the adsorption heat pump according to claim 8, which has an abundance ratio of atoms represented by: The operation method of the adsorption heat pump according to claim 8 or 9, wherein the hetero atom is silicon. The adsorption heat pump according to any one of claims 8 to 10, wherein the adsorbent has an adsorption amount of 0.15 g / g or less at a relative vapor pressure of 0.05 on a water vapor adsorption isotherm measured at 25 ° C. how to drive. The framework density of the zeolite is 10.0T / 1,000Å ^Three 16.0T / 1,000cm ^Three It is the following ranges, The operating method of the adsorption heat pump of any one of Claims 8-11. The operation method of the adsorption heat pump according to any one of claims 8 to 12, wherein the zeolite has a CHA structure. Used in an adsorption heat pump driven by a heat source of 100 ° C. or less, and when the relative vapor pressure changes by 0.15 in the range of relative vapor pressure of 0.05 to 0.30 in the water vapor adsorption isotherm measured at 25 ° C. And the adsorbent has a relative vapor pressure range of 0.18 g / g or more, and the adsorbent is a zeolite containing aluminum, phosphorus and heteroatoms in a skeleton structure. Adsorbent for adsorption heat pump. The adsorbent for adsorption heat pump according to claim 14 , wherein an adsorption amount at a relative vapor pressure of 0.05 is 0.15 g / g or less in a water vapor adsorption isotherm measured at 25 ° C. The adsorbent for an adsorption heat pump according to claim 14 or 15 , wherein a framework density of the zeolite is in a range of 10.0 T / 1,000 to ³ or more and 16.0 T / 1,000 to ³ or less. The zeolite has the following formulas (1), (2) and (3)
0.001 ≦ x ≦ 0.3 (1)
(Wherein x represents the molar ratio of the heteroatom to the total of aluminum, phosphorus and heteroatom in the skeleton structure)
0.3 ≦ y ≦ 0.6 (2)
(Wherein y represents the molar ratio of aluminum to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
0.3 ≦ z ≦ 0.6 (3)
(In the formula, z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
The adsorbent for adsorption heat pump according to any one of claims 14 to 16 , which has an abundance ratio of atoms represented by: The adsorbent for adsorption heat pump according to any one of claims 14 to 17 , wherein the hetero atom is silicon. Adsorption heat pump adsorbent according to any one of the zeolite CHA structure der Ru請 Motomeko 14-18. In the method of using the adsorbent, the adsorbent is desorbed by heating the adsorbent with a heat source of 100 ° C. or lower, and the dried adsorbent is cooled to a temperature used for adsorbate adsorption and used again for adsorbate adsorption. When the relative vapor pressure changes 0.15 g in the range of the relative vapor pressure of 0.05 to 0.30 on the water vapor adsorption isotherm measured at 25 ° C., the adsorbent changes 0.18 g of water. A method for using an adsorbent, characterized by being a zeolite having a relative vapor pressure region of at least / g and having a framework structure containing aluminum, phosphorus, and heteroatoms. Zeolite containing aluminum, phosphorus and heteroatoms in the skeleton structure has the following formulas (1), (2) and (3):
0.001 ≦ x ≦ 0.3 (1)
(Wherein x represents the molar ratio of the heteroatom to the total of aluminum, phosphorus and heteroatom in the skeleton structure)
0.3 ≦ y ≦ 0.6 (2)
(Wherein y represents the molar ratio of aluminum to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
0.3 ≦ z ≦ 0.6 (3)
(In the formula, z represents the molar ratio of phosphorus to the total of aluminum, phosphorus and heteroatoms in the skeleton structure)
The method for using an adsorbent according to claim 20, having an abundance ratio of atoms represented by: The method for using an adsorbent according to claim 20 or 21, wherein the heteroatom is silicon. The adsorbent according to any one of claims 20 to 22, wherein the adsorbent has an adsorption amount of 0.15 g / g or less at a relative vapor pressure of 0.05 on a water vapor adsorption isotherm measured at 25 ° C. how to use. The framework density of the zeolite is 10.0T / 1,000Å ^Three 16.0T / 1,000cm ^Three It is the following ranges, The usage method of the adsorption material of any one of Claims 20-23. The method for using an adsorbent according to any one of claims 20 to 24, wherein the zeolite has a CHA structure.

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