JP2012067002A - Zeolite, adsorbent, adsorption heat pump using adsorbent and method for operating absorption heat pump - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adsorbent for absorbing/desorbing adsorbate in a low relative vapor pressure area, and for sufficiently operating an absorption heat pump even under conditions that its low temperature side has a relatively high temperature, and its high temperature side has a relatively low temperature, and their temperature difference is small and a highly efficient absorption heat pump using this adsorbent.SOLUTION: There is disclosed an AFI type zeolite containing aluminum, phosphorous, iron and M (M is tin and/or titanium) in the skeleton structure, wherein the M/Fe molar ratio is 0.25< M/Fe <1.0, an absorbent using this zeolite, and an absorption heat pump using this absorbent. In this AFI type zeolite containing not only aluminum, phosphorus and iron but also tin and/or titanium at a prescribed ratio in the skeleton structure, the performance of the zeolite configured of only aluminum and phosphors and iron is improved, and the performance change of tin and/or titanium is larger than that of most of the other metals.

Description

  The present invention relates to a novel zeolite, an adsorbent using the zeolite, an adsorption heat pump using the adsorbent, and an operation method of the adsorption heat pump. Specifically, as the outside temperature increases due to global warming, , A novel zeolite-based adsorbent that can produce low-temperature cold water even at high temperatures in summer and exhibits excellent performance stability and durability even under repeated use conditions, and adsorption using the adsorbent It relates to a heat pump.

  Conventionally, zeolites having various properties have been synthesized as molecular sieves, ion exchange materials, catalysts, adsorbing materials, and the like, and have become industrially important substances. In addition, the use of each of the properties of the catalyst, catalyst carrier, wastewater treatment, exhaust gas treatment, freshness preservation (ethylene adsorption), detergent (builder cleanser), antibacterial, desiccant, deodorant, soil Applications such as improvers are known, and applications to other applications are also being studied.

  On the other hand, in recent years, cogeneration systems have effectively used low-temperature exhaust heat emitted from internal combustion engines, etc., using the heat storage function of adsorbents to cope with the summer power demand bias in winter. Utilization is under consideration. In an environmentally symbiotic thermal energy utilization system including a cogeneration system, the adsorption heat pump is one of the best exhaust heat recovery means that can operate with low-quality thermal energy as a heat source without using auxiliary power, and its full introduction Is expected.

  Adsorption heat pump is a system that pumps heat by using the phase change that accompanies the adsorption / desorption phenomenon of adsorbent. Adsorber that adsorbs / desorbs adsorbate such as water with adsorbent, and adsorber Is mainly composed of an evaporator that generates cold by evaporation of the adsorbate in accordance with the adsorption operation, and a condenser that condenses the vapor of the adsorbate desorbed by the adsorber and supplies it to the evaporator. In the operation process of the adsorption heat pump, when the adsorbent is heated and regenerated, exhaust heat from the engine or the like may be recovered.

The temperature of the heat source that can be used for such an adsorption heat pump varies greatly depending on the system on the exhaust heat generation side. For example, the exhaust heat temperature of gas engine cogeneration or a polymer electrolyte fuel cell used as a heat source on the high temperature side is 60 ° C. to 80 ° C., and the temperature of the cooling water of the automobile engine is 85 ° C. to 90 ° C. On the other hand, 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. Therefore, the operating temperature range of the adsorption heat pump is generally 25 to 40 ° C. on the low temperature side when installed in a building, 60 to 80 ° C. on the high temperature side, and 30 to 40 ° C. on the low temperature side when installed in an automobile or the like. The side is about 85-90 ° C.
In order to efficiently use the exhaust heat by the adsorption heat pump, it is desired to be able to drive even when the temperature difference between the low temperature side heat source and the high temperature side heat source is small.

  When the adsorption heat pump is applied to a cogeneration system or the like, the adsorption characteristic of the adsorbent is an important factor.

  That is, as a characteristic of the adsorbent for efficiently using the exhaust heat as described above, the temperature difference between the low temperature side heat source and the high temperature side heat source around the adsorbent is small, for example, the cooling capacity of the low temperature side heat source is Even in the case of an air-cooled type that is relatively weak and has a relatively high temperature, it is necessary to adsorb the adsorbate with a low relative vapor pressure in order to operate the apparatus sufficiently, and to reduce the size of the apparatus, the adsorbent It is necessary that the amount of adsorption / desorption of is sufficiently large. And since a low-temperature heat source is utilized for reproduction | regeneration of adsorption material, the desorption temperature needs to be low.

  With respect to such required characteristics, a general adsorbent, for example, Y-type zeolite, needs to have a high temperature of 150 to 200 ° C. or higher in order to make the relative vapor pressure 0 in order to desorb the adsorbed material. Is not suitable for low-temperature exhaust heat. In addition, zeolites such as A-type silica gel and 13X have low adsorption performance, so if they are to be applied to the above system, a large amount of adsorbent is required, including the refrigerant used during adsorption, which leads to problems such as large equipment. To provoke. In addition, mesoporous silica (FSM-16, etc.) studied for the same purpose is synthesized using a micelle structure of a surfactant as a template and does not adsorb at a low relative vapor pressure. There is a problem that it is difficult to use low-temperature exhaust heat obtained from cooling water such as fuel cells.

  Attempts have also been made to improve the adsorption characteristics of these adsorbents themselves, but it has also been pointed out that adsorbents such as zeolite are fragile in structure and are difficult to manufacture industrially, resulting in increased costs. Yes.

For the above problems, the present inventors previously adsorbed adsorbate at a lower relative vapor pressure or higher temperature and adsorbed at a higher relative vapor pressure or lower temperature as an adsorbent for an adsorption heat pump. As an adsorbent with a large amount of adsorption and desorption, an adsorbent using zeolite containing aluminum, phosphorus and heteroatoms in the framework structure, and an adsorption heat pump using the adsorbent were proposed ( Patent Document 1). Such an adsorbent has a relative vapor pressure in a range of 0.05 to 0.30 on a water vapor adsorption isotherm at 25 ° C., and the adsorption amount change when the relative vapor pressure changes 0.15 is 0.18 g / and a relative vapor pressure range of g or more, and a framework density of 10.0 T / 1,000 to ³ or more and 16.0 T / 1,000 to ³ or less.

  Patent Document 2 and Patent Document 3 describe an adsorbent composed of zeolite containing aluminum, phosphorus, and iron in a skeleton structure. In addition to the aluminum, phosphorus, and iron, “other elements (M) are included. There is a description that "may be used", and titanium and tin are also exemplified as the other element, but there is no description of a specific example including another element (M). In addition, the molar ratio of M / Fe is “3 or less, preferably 1.5 or less, more preferably 0.5 or less. If M / Fe is not in this range, the adsorption performance in the present invention does not appear sufficiently. As is clear from the description, the other element (M) here is described as not contributing to the improvement of the performance of the iron aluminophosphate but rather needing to be contained. Further, Patent Documents 2 and 3 do not suggest that tin or titanium, among other elements (M), particularly improves performance or is effective for AFI-type zeolite. .

  Patent Document 4 describes an adsorbent made of zeolite containing aluminum, phosphorus and gallium in the skeleton structure, but does not describe a combination of iron and tin or iron and titanium.

JP 2002-372332 A JP 2004-136269 A JP 2005-205331 A Japanese Patent Laying-Open No. 2005-230738

  In recent years, in the use of exhaust heat of a cogeneration system, a technique for effectively using lower temperature exhaust heat in a higher temperature environment has been demanded from the viewpoint of further energy saving. Specifically, the exhaust heat temperature as the high temperature side heat source is 60 to 80 ° C., whereas the low temperature side heat source temperature is, for example, when an adsorption heat pump is used for air conditioning in a factory or a house, Considering the heat insulation effect of the building, the temperature is about 10 ° C. higher than the outside air temperature. Therefore, compared to conventional zeolite, a new adsorbent that can utilize lower-temperature exhaust heat and has a large difference in adsorption amount in adsorption / desorption, which can exhibit greater adsorption performance, The adsorbate can be adsorbed and desorbed in a low relative vapor pressure range, for example, the heat source temperature on the low temperature side is 35 ° C., the heat source temperature on the high temperature side is 75 ° C., the high temperature side is relatively high, and the high temperature side is relatively low, There is a demand for an adsorbent capable of operating the adsorption heat pump sufficiently even under such a small temperature difference. Also, the generated cold water is required to have a low temperature of 10 ° C. or lower, preferably 8 ° C. or lower, and in some cases 6 ° C. or lower. In this respect, it can be adsorbed at a lower relative vapor pressure and can be desorbed at a low temperature. New adsorbents are desired.

  The present invention can adsorb and desorb the adsorbate in such a low relative vapor pressure region, and the low temperature side is not air-cooled or water-cooled, and the high temperature side is relatively low and the temperature difference between them is relatively low. It is an object of the present invention to provide an adsorbent that can sufficiently operate an adsorption heat pump even under small conditions, and an efficient adsorption heat pump that uses this adsorbent.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that AFI-type zeolite having tin and / or titanium in a predetermined ratio in addition to aluminum, phosphorus and iron in the skeleton structure is aluminum and The performance of zeolite consisting only of phosphorus and iron is improved, and tin and / or titanium have a large performance change compared to many other metals, and this effect is unique to AFI-type zeolite. As a result, the present invention was completed.

That is, the first invention of the present invention is an AFI type zeolite containing aluminum, phosphorus, iron and M (M is tin and / or titanium) in the skeleton structure, and the M / Fe molar ratio is 0.25 <M. /Fe<1.0
Preferably, 0.5 <M / Fe <1.0
The zeolite is characterized by the following:
The second invention of the present invention resides in an adsorbent using the zeolite.
The third invention of the present invention resides in an adsorption heat pump using the adsorbent.
A fourth invention of the present invention resides in an operation method of the adsorption heat pump.

  The zeolite of the present invention is useful as an adsorbent, a separating agent, a catalyst, a catalyst carrier, and the like, and is used in various fields of application. Among them, an adsorbent using the zeolite has, for example, a low-temperature heat source temperature of 35 ° C. The temperature difference of the heat source on the high temperature side is 75 ° C. or less, the adsorbate can be adsorbed / desorbed in a low relative vapor pressure region, and the adsorption amount difference in adsorbate adsorption / desorption is large. Low-temperature heat can be used effectively, and the adsorption heat pump can be driven efficiently. In addition, since this adsorbent has high durability in the repeated adsorption and desorption of adsorbate, it is highly practical and reliable when used as an adsorption heat pump.

  According to such an adsorption heat pump using the adsorbent of the present invention, since it is driven efficiently by low-temperature heat, exhaust heat from a cogeneration system or the like can be effectively used, and further energy saving can be achieved.

It is a flowchart which shows one structural example of the adsorption heat pump as an application example of the adsorption material for adsorption heat pumps concerning this invention. It is a lineblock diagram showing an example of a cold heat generation system using exhaust heat of a polymer electrolyte fuel cell as a heat source of an adsorption heat pump concerning the present invention. It is a lineblock diagram showing an example of a cold heat generation system using the heat of a solar water heater as a heat source of an adsorption heat pump concerning the present invention. It is a block diagram which shows an example of the cold-heat generation system using the low-temperature waste heat of the cogeneration system using an internal combustion engine as a heat source of the adsorption heat pump which concerns on this invention. It is a lineblock diagram showing an example of a heat generation system using an adsorption heat pump concerning the present invention. 2 is an X-ray diffraction (XRD) pattern of the crystalline iron tin aluminophosphate obtained in Example 1. FIG. 2 is a graph of a water vapor adsorption isotherm in an adsorption process at 35 ° C. and a water vapor desorption isotherm in a desorption process at 75 ° C. in Example 1 and Comparative Example 1. 4 is a graph of a water vapor adsorption isotherm in an adsorption process at 35 ° C. in Example 2. It is a graph of the water vapor adsorption isotherm in the adsorption process at 35 ° C. in Comparative Example 3. It is a graph of the water vapor adsorption isotherm in the adsorption process at 35 ° C. in Example 3. It is a graph which shows the evaluation result of the cooling output performance with respect to the cooling water temperature of the adsorption heat pump of Example 4 and Comparative Example 5. It is a graph which shows the evaluation result of the cooling output performance with respect to the cold water temperature of the adsorption heat pump of Example 4 and Comparative Example 5.

  Hereinafter, the zeolite, the adsorbent, the adsorption heat pump, and the operation method of the adsorption heat pump of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of the embodiment of the present invention. However, the present invention is not limited to these contents.

A first invention of the present invention is an AFI-type zeolite containing aluminum (Al), phosphorus (P), iron (Fe), and M (M is tin and / or titanium) in a skeleton structure, and M / Fe The molar ratio is
0.25 <M / Fe <1.0
Preferably, 0.5 <M / Fe <1.0
It can be rephrased as a zeolite having an AFI structure, which is an aluminophosphate containing iron (Fe) and heteroatom M (M is tin and / or titanium) in the skeleton structure. it can.

  The AFI type zeolite has an AFI structure classified by Database of Zeolite Structures by the International Zeolite Association (IZA), and is determined by XRD (X-ray diffraction) analysis.

M / Fe molar ratio in the zeolite of the present invention is:
0.55 ≦ M / Fe ≦ 0.95
More preferably,
0.60 ≦ M / Fe ≦ 0.90
It is particularly preferred that When the M / Fe molar ratio is larger than the lower limit, the amount of adsorption in a low relative vapor pressure region is increased, and when the M / Fe molar ratio is smaller than the upper limit, the desorption temperature can be lowered.

  Further, M may be either tin (Sn) or titanium (Ti), but tin is more preferable than titanium in terms of adsorption amount and durability.

As described above, the AFI-type zeolite of the present invention having a predetermined amount of tin and / or titanium in addition to aluminum, phosphorus and iron in the framework structure of the zeolite is compared with a zeolite consisting only of aluminum, phosphorus and iron. The performance is excellent, and the effect of tin and / or titanium has a large change in performance compared to many other metals.
The performance change is particularly effective as an adsorbent, and is particularly effective as an adsorbent for an adsorption heat pump. That is, the zeolite of the present invention is a zeolite that adsorbs and desorbs in a specific temperature range, has a large difference in the amount of adsorbate adsorbed during adsorption and desorption, and has high durability under repeated adsorption and desorption conditions. The durability is preferably 90% or more, particularly preferably 93% or more, under the conditions of the water vapor repeated adsorption / desorption test in the examples described later.
Further, this change in performance improvement is not necessarily recognized even in the case of zeolites having other general framework structures, but is an effect peculiar to AFI zeolite.

  Further, the constituent ratio (molar ratio) of M, Al, P and Fe constituting the skeleton structure of the AFI-type zeolite of the present invention is preferably in a range satisfying the following formulas (1) to (3), In particular, the formula (1) is preferably represented by the formula (1-1) and further by the formula (1-2).

0.001 ≦ x ≦ 0.3 (1)
(X represents (Fe + M) / (M + Al + P + Fe) (molar ratio))
0.03 ≦ y ≦ 0.6 (2)
(Y represents Al / (M + Al + P + Fe) (molar ratio))
0.03 ≦ z ≦ 0.6 (3)
(Z represents P / (M + Al + P + Fe) (molar ratio)))
0.003 ≦ x ≦ 0.2 (1-1)
0.005 ≦ x ≦ 0.1 (1-2)

  When x, y, and z are within the above ranges, desired adsorption characteristics can be obtained, zeolite can be formed, and durability can be sufficient.

  In addition, each molar ratio of said atom can be specified by elemental analysis. Usually, in elemental analysis, a sample is heated and dissolved in an aqueous hydrochloric acid solution, and then ICP analysis is performed.

The method for producing the zeolite of the present invention is not particularly limited. Usually, an aluminum source, an iron source, a phosphorus source, an M (tin and / or titanium) source and a template are mixed and then hydrothermally synthesized. Manufactured.
An example will be described below.

  First, an aluminum source, an iron source, a phosphorus source, an M (tin and / or titanium) source, and a template are mixed.

  Although it does not specifically limit as an aluminum source, Usually, aluminum alkoxides, such as pseudo boehmite, aluminum isopropoxide, aluminum triethoxide, aluminum hydroxide, alumina sol, sodium aluminate, etc. are mentioned. These may be used alone or in combination of two or more. Pseudoboehmite is preferred as the aluminum source in terms of easy handling and high reactivity.

  Although it is not particularly limited as an iron source, it is usually an inorganic acid iron such as iron sulfate, iron nitrate, iron phosphate, iron chloride or iron bromide, an organic acid iron such as iron acetate, iron oxalate or iron citrate, iron Examples thereof include iron organometallic compounds such as pentacarbonyl and ferrocene. These may be used alone or in combination of two or more. Among these, inorganic acid irons and organic acid irons are preferable in that they are easily dissolved in water, and inorganic acid iron compounds such as ferric nitrate and ferrous sulfate are more preferable. In some cases, colloidal iron hydroxide or the like may be used.

  As the phosphorus source, phosphoric acid is usually used, but aluminum phosphate can also be used. Also about a phosphorus source, 1 type may be used independently and 2 or more types may be mixed and used for it.

As the source of M (tin and / or titanium), when M is tin, tin (II) sulfate, tin (II) chloride, tin chloride (IV), tin oxalate (II), tin oxide (II), Tin oxide (IV), tin stearate (II), and the like can be mentioned. Tin (II) sulfate is preferred because it is relatively easily dissolved in water and hardly corrodes.
When M is titanium, titanium alkoxides such as titanium isopropoxide, titanium ethoxide and titanium butoxide, and titanium salts such as titanium chloride and titanyl sulfate can be mentioned. From the viewpoint of reactivity and ease of handling, titanium alkoxide Is preferred.
Also about these M sources, 1 type may be used independently and 2 or more types may be mixed and used for them.

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

  An aqueous gel is prepared by mixing the above aluminum source, iron source, phosphorus source, M source, and template. The mixing order varies depending on conditions, but usually, a phosphorus source and an aluminum source are first mixed, and then an iron source and an M source are mixed with a template. The iron source and the M source may be mixed in advance and then mixed with the mixture of the phosphorus source and the aluminum source. However, the iron source and the M source may be mixed simultaneously or sequentially, preferably It is preferable to mix the M source after mixing the iron source.

  Water is preferably present when the phosphorus source and the aluminum source are mixed, and water may be added to the mixture when the iron source and the M source are further mixed. The phosphorus source or the like may be used for mixing in the form of an aqueous solution.

The composition of the above aqueous gel is usually expressed as a molar ratio of the oxide, and 0.01 ≦ FeO / P ₂ O ₅ ≦ 1.5. Further, from the viewpoint of ease of synthesis, 0.02 ≦ FeO / P ₂ O ₅ ≦ 1.0 is preferable, and 0.05 ≦ FeO / P ₂ O ₅ ≦ 0.5 is more preferable. The molar ratio of P ₂ O ₅ / Al ₂ O ₃ is 0.6 or more and 1.7 or less, and from the viewpoint of ease of synthesis, 0.7 or more and 1.6 or less. Is preferably 0.8 or more and 1.5 or less.

The amount of the template is 0.1 to 3 in molar ratio with respect to _P 2 _{O 5,} preferably 0.5 to 2, more preferably 0.7 to 1.5. When the amount of the template used is not less than the above lower limit, the amount of the template is sufficient, and when it is not more than the above upper limit, the alkali concentration can be suppressed, and therefore, satisfactory crystallization can be performed by being within the above range.

The lower limit of the proportion of water is at least 3 in a molar ratio to Al ₂ O _3, preferably 5 or more from the viewpoint of ease of synthesis, and more preferably 10 or more. The upper limit of the molar ratio of water to Al ₂ O ₃ is usually 200 or less, preferably 150 or less, and more preferably 120 or less from the viewpoint of ease of synthesis and high productivity.
Moreover, pH of aqueous gel is 4-10, 4.5-9 are preferable from a viewpoint of the ease of a synthesis | combination, and 5.0-8.5 are more preferable.

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

  Hydrothermal synthesis is carried out by placing the above aqueous gel in a pressure-resistant container and maintaining a predetermined temperature under stirring or standing under self-generated pressure or pressurized gas that does not inhibit crystallization. The temperature at the time of hydrothermal synthesis is usually 100 to 300 ° C, and is preferably 150 to 250 ° C, more preferably 170 to 220 ° C from the viewpoint of ease of synthesis. The reaction time is 3 to 30 days, preferably 5 to 15 days, more preferably 7 to 7 days from the viewpoint of ease of synthesis.

  After hydrothermal synthesis, the product is separated, then washed with water, dried, and then subjected to calcination using air or the like to remove part or all of the organic matter contained therein, thereby obtaining the zeolite of the present invention. Can do.

  The adsorbing material according to the second invention of the present invention is basically composed of the above-mentioned zeolite of the present invention, but within the range not impairing its performance, other adsorbing materials may be mixed, if necessary. And may contain other components. The use of the adsorbent is not particularly limited, but it is preferably used for an adsorption heat pump.

  The adsorption heat pump in which the adsorbent of the present invention is used includes an adsorption operation for adsorbing the adsorbate to the adsorbent while releasing heat of adsorption, and a desorption operation for desorbing the adsorbate from the adsorbent by external heat. The adsorber which repeats, the cold heat obtained by the evaporation of the adsorbate is taken out to the outside, the generated adsorbate vapor is recovered by the adsorber, and the adsorbate vapor desorbed by the adsorber An adsorption heat pump according to the present invention is provided that includes a condenser that is condensed by external cold heat and that supplies the condensed adsorbate to the evaporator.

  In the adsorption heat pump using the adsorbent, the operation vapor pressure range of the adsorption heat pump is the desorption side determined 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). It is determined by the relative vapor pressure (φ1) and the adsorption side relative vapor pressure (φ2). The desorption side relative vapor pressure (φ1) and the adsorption side relative vapor pressure (φ2) are calculated by the following equations (a) and (b), and the desorption side relative vapor pressure (φ1) and the adsorption side relative vapor pressure (φ2) are calculated. The relative vapor pressure range that can be operated is between

Desorption-side relative vapor pressure (φ1) = equilibrium vapor pressure (Plow1) / equilibrium vapor pressure (High)
... (a)
Adsorption side relative vapor pressure (φ2) = equilibrium vapor pressure (Pcool) / equilibrium vapor pressure (Plow2)
... (b)

Here, the high temperature heat source temperature (High) means the temperature of the heating medium that is heated when the adsorbate is desorbed from the adsorbent to regenerate the adsorbent, and the low temperature heat source temperature (Tlow1) is the temperature of the condenser. The temperature of the adsorbate means the low temperature heat source temperature (Tlow2) means the temperature of the heat medium that cools the adsorbent after regeneration for adsorption, and the cold heat generation temperature (Tcool) means the temperature of the evaporator. It means the temperature of adsorbate, that is, the temperature of the generated cold. In the above equation, the equilibrium vapor pressures (Plow1), (Phigh), (Pcool) and (Plow2) are the equilibrium vapor pressures at the respective temperatures (Tlow1), (High), (Tcool) and (Tlow2), respectively. These can be determined from the temperature using the equilibrium vapor pressure curve of the adsorbate.
Usually, Tlow1 and Tlow2 often have the same temperature, and hence may be collectively referred to as Tlow.

  The adsorbent of the present invention is particularly suitable for an adsorption heat pump when Tcool is lower than 10 ° C., Tlow is relatively high, and High is relatively low. In this adsorption heat pump, when the adsorbate is the most common water, an operation vapor pressure range in which Tcool is lower than 10 ° C., Tlow is relatively high, and High is relatively high is exemplified. (Φ2) is 0.17 when the cold heat generation temperature (Tcool) is 6 ° C. and the low temperature heat source temperature (Tlow 2) is 35 ° C. Further, the desorption side relative vapor pressure (φ1) is 0.15 when the low temperature heat source temperature (Tlow1) is 35 ° C. and the high temperature heat source temperature (High) is 75 ° C. Therefore, the relative water vapor pressure range (the range from the desorption side relative vapor pressure (φ1) to the adsorption side relative vapor pressure (φ2)) for operating the adsorption heat pump is 0.15 to 0.17. A material having a large change in amount, specifically preferably 0.07 g / g or more, more preferably 0.09 g / g or more.

  The operation method of the adsorption heat pump using the adsorbent using the zeolite of the present invention exhibits particularly excellent performance when used under the following conditions.

  In the present invention, since the adsorption heat pump is used in a relatively high temperature environment, the adsorption temperature (Tlow) of the adsorbent is preferably 25 to 45 ° C. The upper limit of the adsorption temperature (Tlow) is determined according to the outdoor air temperature in summer, and is about 35 to 45 ° C. in consideration of the change in conditions of the location where the cogeneration apparatus is installed. The lower limit of the adsorption temperature (Tlow) is not particularly limited. For example, it is assumed that a polymer electrolyte fuel cell incorporated in a home cogeneration system operates in the summer morning and is relatively hot. Assuming that the adsorption temperature (Tlow) is used, the lower limit of the adsorption temperature (Tlow) is usually 25 to 30 ° C., preferably 30 ° C. or higher. That is, the adsorption temperature (Tlow) is generally 25 to 45 ° C, preferably 30 to 43 ° C, more preferably 35 to 40 ° C.

  Specifically, in the case of an adsorption heat pump that operates by adsorbing and desorbing water vapor, when the water vapor adsorption temperature (Tlow) is 25 to 45 ° C., the water vapor desorption temperature (High) and the cold heat generation temperature (Tcool) are In this case, the difference between the water vapor adsorption amount at the adsorption temperature (Tlow) and the water vapor adsorption amount at the desorption temperature (High) is 0.07 g / g. As mentioned above, Preferably it becomes 0.09 g / g or more.

High ≦ 100 ° C. (1)
0 ° C. ≦ Tcool ≦ 10 ° C. (2)
(Preferably 0 ° C. ≦ Tcool ≦ 8 ° C., more preferably 0 ° C. ≦ Tcool ≦ 6 ° C.)
On the other hand, in the conventional technology, at most, Tlow-25 ° C <Tcool <25 ° C.
Met. That is, if Tlow ≦ 30 ° C., the operation under the condition of the formula (2) is possible, but if Tlow ≧ 35 ° C., the operation under such condition is impossible.

  In addition, if the operating condition is such that the temperature difference between the adsorption temperature (Tlow) and the desorption temperature (High) is large and the desorption temperature (High) is greater than 100 ° C., there is no advantage over the prior art and practical operating conditions. Therefore, the present invention is preferably characterized in that it is used under a condition where the difference in adsorption / desorption temperature (High-Tlow) is extremely small (that is, the difference in relative vapor pressure between adsorption and desorption is very small). Operating conditions.

  When the adsorbent of the present invention is used, it is characterized in that it is possible to take out extremely low heat for a relatively high adsorption temperature (Tlow).

  The cold heat generation temperature (Tcool) is the temperature of the adsorbate when the adsorbate is adsorbed and cooled by being deprived of latent heat of vaporization, that is, the average temperature before and after the adsorption of water to be adsorbed, The temperature is uniquely determined from the relationship between the adsorption mass and the adsorption amount. The lower the temperature, the greater the value as generated heat, but the lower limit is determined based on the value of the available temperature. Therefore, since Formula (2) is an adsorption heat pump using water vapor, the cold heat generation temperature (Tcool) needs to be 0 ° C. or higher. On the other hand, the cold heat generation temperature (Tcool) is 10 ° C. or less, preferably 8 ° C. or less, more preferably 6 ° C. or less.

  One of the characteristics required for the adsorbent is an adsorption amount difference, that is, a difference between the water vapor adsorption amount at the adsorption temperature (Tlow) and the water vapor adsorption amount at the desorption temperature (High). The adsorption amount difference is determined by using [1] adsorption isotherm at the adsorption temperature (Tlow) and [2] adsorption isotherm at the desorption temperature (High), and [a] cold generation temperature (Tcool) and adsorption temperature (Tlow). ) Adsorption amount at relative humidity (relative vapor pressure on the adsorption side) determined from), and [b] Adsorption at relative humidity (desorption side relative vapor pressure) determined from the adsorption temperature (Tlow) and desorption temperature (High) It means the difference in quantity.

Specifically, the adsorption amount difference is obtained according to the following 1) to 4).
1) The adsorption isotherm at the adsorption temperature (Tlow) and the adsorption isotherm at the desorption temperature (High) are measured.
2) The relative vapor pressure determined from the set cold generation temperature (Tcool) and the adsorption temperature (Tlow) is obtained, and the water vapor adsorption amount at the relative vapor pressure (adsorption side relative vapor pressure) is obtained from the Tlow adsorption isotherm. .
3) Similarly, the relative vapor pressure determined from the desorption temperature (High) and the adsorption temperature (Tlow) is obtained, and the water vapor adsorption amount at the relative vapor pressure (desorption side relative vapor pressure) is obtained from the High adsorption isotherm. .
4) The difference between the respective water vapor adsorption amounts obtained in the above 2) and 3) is obtained. The water vapor adsorption amount at the adsorption-side relative vapor pressure can be obtained from “adsorption isotherm measured by adsorption temperature (Tlow)”, that is, for example, an adsorption isotherm at an adsorption temperature (Tlow) = 35 ° C. In the case of Example 1, the relative vapor pressure is 0.24, and the water vapor adsorption amount at that time can be read as 0.12 g / g. Similarly, the desorption side relative vapor pressure can be obtained from the “adsorption isotherm measured by desorption temperature (High)”, that is, the adsorption isotherm at, for example, desorption temperature (High) = 75 ° C. The water vapor adsorption amount at 15 can be read as about 0.04 g / g. From this, the adsorption amount difference between them is 0.08 g / g.

The adsorbent of the present invention has an adsorption amount of 0.10 [g · H ₂ O / g · adsorbent] or more, particularly 0.12 g at a relative vapor pressure of 0.17 on a water vapor adsorption isotherm measured at 35 ° C. / G or more is preferable. When the adsorption amount is equal to or more than the lower limit value, it is possible to reduce the volume of the adsorbent required for the adsorption heat pump having a predetermined capacity, and to prevent the apparatus from becoming large.

More specifically, the difference in the adsorption amount affects the following in the adsorption heat pump.
For example, assuming a case where an adsorption heat pump is used as a cooling device and a cooling capacity of 5.0 kW (= 18,000 kJ) is obtained (a cooling capacity of about 16 tatami mats facing the south of a wooden building), the adsorption amount difference between adsorbents is 0. In the case of 0.08 g / g, the necessary amount of adsorbent in the adsorption heat pump is 15.0 kg according to the following equation. However, the latent heat of vaporization of water is about 2500 kJ / kg, and the adsorption / desorption switching cycle is 10 minutes (6 times / hour).

Required amount of adsorbent =
18000 kJ / (2500 kJ × 0.08 kg / kg × 6 times / hr) = 15.0 kg

  In an adsorption heat pump, the larger the amount of adsorption, the better, but the smaller the weight and volume of the adsorbent, the better. That is, in an adsorption heat pump, since there are many cases where the installation area is limited, greater performance is required after further downsizing. Therefore, an adsorbent that satisfies the above-described requirements regarding the difference in adsorbed amount is preferable. When the difference in adsorption amount is small, the necessary amount of adsorbent becomes large and the apparatus becomes large, which is not preferable. For example, when the adsorption amount difference of the adsorbent is 0.05 g / g, the necessary amount of the adsorbent calculated by the above formula is 24 kg.

  Since the adsorbent of the present invention has the above-mentioned adsorption characteristics, as described above, the adsorption heat pump can be used even under severe conditions where the temperature of the low-temperature side heat source is 35 ° C. and the temperature of the high-temperature side heat source is 75 ° C. The adsorption heat pump can be configured more compactly because it can be operated and has a large adsorption amount difference as described above.

  Moreover, since the adsorbent of the present invention is also a heat storage material, its characteristics can be defined from the aspect of output. That is, the output density (output per unit mass) of the adsorbent can be specified by the adsorption amount difference, the latent heat of vaporization, and the adsorption / desorption cycle in the adsorption heat pump. For example, if the adsorption amount difference is 0.08 g / g, the latent heat of vaporization of water is about 2500 kJ / kg, and water is adsorbed in a 10 minute cycle, the output density of the adsorbent is 0. 33 kw / kg. The power density of the adsorbent is desirable to be larger, as is the case with the difference in adsorbed amount, but it is about 1.5 kw / kg or less due to restrictions on the adsorbent material and the design of the adsorption cycle in the adsorption heat pump. .

Adsorbent power density: difference in adsorption amount x latent heat of vaporization / cycle time
= 0.08 x 2500/600 = 0.33 kW / kg

  Further, the power density of the adsorbent needs to be designed in consideration of the size of the apparatus when the adsorption heat pump is actually operated. Usually, in the adsorption heat pump, at least two adsorbers (adsorber modules) for adsorbing and desorbing adsorbate are provided, and the adsorption function is continuously exhibited as a whole apparatus by these switching operations. Moreover, each adsorber has an adsorbent attached to the surface of a heat exchange member composed of a large number of fins and the like, as described in, for example, JP-A-2001-213149, and the heat exchange member is placed in a sealed container. It has a housed structure. In the adsorber, there are a portion occupied by the adsorbent and a portion occupied by the heat exchange member itself, and the volume occupied by the adsorbent is substantially about 50%.

Therefore, when the actual scale, packing density of the adsorbent in the adsorber is at most 800 kg / ^{m 3,} minimum 500 kg / ^{m 3,} since the average is 600 kg / ^{m 3,} the unit volume required for adsorber The per unit power density is about 100 kw / m ³ from the following formula, assuming that the power density of the adsorbent is 0.33 kw / kg. The upper limit and lower limit of the output density of the adsorber depend on the output density of the adsorbent, and are usually about 80 to 450 kw / m ³ .

Adsorber (adsorber module) power density:
Adsorbent output density x packing density x volume fraction of adsorbent
= 0.33 x 600 x 0.5 = 99 kW / m ³

  Next, as an application example of the above adsorbent, the adsorption heat pump of the present invention will be described with reference to FIG. FIG. 1 is a flowchart showing an example of the configuration of the adsorption heat pump of the present invention to which the adsorbent of the present invention is suitably applied.

  The adsorption heat pump of the present invention is an adsorption heat pump using the above-mentioned adsorbent, and is generally filled with an adsorbent as shown in FIG. 1, and adsorbate is adsorbed on the adsorbent while releasing the adsorption heat. Adsorbers (1) and (2) for repeating the adsorption operation for adsorbing and the desorption operation for desorbing the adsorbate from the adsorbent by external warm heat and transferring the heat generated by the adsorbate adsorption operation to the heat medium; The evaporator (4) in which the cold heat obtained by the evaporation of the adsorbate is taken out and the generated adsorbate vapor is recovered in the adsorbers (1) and (2), and the adsorbers (1) and ( A condenser (2) that condenses the vapor of the adsorbate desorbed in 2) by external cold heat, supplies the condensed adsorbate to the evaporator (4), and releases the heat obtained by the condensation of the adsorbate to the outside. 5).

  In the adsorbers (1) and (2) filled with the adsorbent, the inlet side and the outlet side are connected to each other by the adsorbate pipe (30), and the adsorbate pipe (30) includes a control valve (31 ) To (34) are provided. In the adsorbate pipe (30), the adsorbate exists as a vapor or a mixture of liquid and vapor.

  A heat medium pipe (11) is connected to one adsorber (1), and a heat medium pipe (21) is connected to the other adsorber (2). The heating medium pipe (11) is provided with switching valves (115) and (116), and the heating medium pipe (21) is provided with switching valves (215) and (216). The heat medium pipes (11) and (21) are respectively a heat medium serving as a heating source for heating the adsorbent in the adsorbers (1) and (2), or for cooling the adsorbent. A heat medium as a cooling source is made to flow. As the heat medium, various media can be used as long as the adsorbent in the adsorbers (1) and (2) can be effectively heated or cooled.

  The adsorber (1) is configured to introduce, for example, hot water as a medium from the inlet (113) and discharge it to the outlet (114) by opening and closing the switching valves (115) and (116) during the desorption operation. Yes. Further, during the adsorption operation, the switching valves (115) and (116) are opened and closed so that, for example, cooling water is introduced as a medium from the inlet (111) and discharged to the outlet (112). On the other hand, the adsorber (2) is configured to introduce hot water, for example, as a medium from the inlet (213) and discharge it to the outlet (214) by opening and closing the switching valves (215) and (216) during the desorption operation. Has been. In addition, during the adsorption operation, the switching valves (215) and (216) are opened and closed so that, for example, cooling water is introduced as a medium from the inlet (211) and discharged to the outlet (212).

  Although not shown, the heat medium pipes (11) and (21) are connected to a heat source that generates hot water and a pump that circulates the hot water in order to supply hot water. And an outdoor unit capable of heat exchange. As the heat source, as will be described later, a cogeneration device such as a gas engine or a gas turbine, a fuel cell, or the like can be used.

  The evaporator (4) is connected to the adsorbate pipe (30) on the inlet side of the adsorbers (1) and (2), and is connected to the adsorbate pipe (30) on the outlet side of the adsorbers (1) and (2). Is connected to a condenser (5). That is, the above-mentioned adsorbers (1) and (2) are arranged in parallel between the evaporator (4) and the condenser (5), and the condenser (5) and the evaporator (4). A return pipe (3) for returning the adsorbate condensed in the condenser (5) to the evaporator (4) is provided in between. Reference numeral (41) indicates a chilled water pipe serving as a cooling output from the evaporator (4), and reference numeral (42) indicates a chilled water pipe serving as an outlet of the chilled water, and is provided between the chilled water pipe (41) and the chilled water pipe (42). Are provided with an indoor unit (300) for exchanging heat with the indoor space (air-conditioned space) and a pump (301) for circulating cold water. Moreover, the code | symbol (51) shows the inlet piping of the cooling water with respect to a condenser (5), and the code | symbol (52) shows the outlet piping of a cooling water.

  Next, an operation method of the above adsorption heat pump will be described. In the first stroke, the adsorber (2) performs an adsorption process by closing the control valves (31) and (34) and opening the control valves (32) and (33). In (1), a desorption (regeneration) step is performed. 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).

  In the adsorption process of the adsorber (2), the adsorber (21) is introduced into the adsorber (cooling water or cold air) by introducing a cooling fluid (cooling water or cold air) cooled by an external heat exchanger such as a cooling tower. Cool 2). The temperature of the cooling fluid is determined from the ambient temperature, and is, for example, 25 to 45 ° C. when it is assumed to be incorporated in a household fuel cell. On the other hand, when the control valve (32) is opened, water (adsorbate) in the evaporator (4) evaporates and flows into the adsorber (2) as water vapor and is adsorbed by the adsorbent. The water vapor movement from the evaporator (4) to the adsorber (2) is generally 25 to 45 ° C., preferably 30, regardless of the saturated vapor pressure at the evaporation temperature and the adsorbent temperature (water cooling type or air cooling type). To 43 ° C., more preferably 35 to 40 ° C.), and in the evaporator (4), the cooler according to the heat of vaporization accompanying the evaporation of water, that is, the cooling output is obtained. Obtainable.

  Adsorption side relative vapor pressure (φ2) (by dividing the equilibrium vapor pressure of the adsorbate at the cold water temperature generated by the evaporator (4) by the equilibrium vapor pressure of the adsorbate at the cooling water temperature of the adsorber (2) The required value) is determined from the relationship between the temperature of the cooling water in the adsorber (2) and the temperature of the cold water generated in the evaporator (4). Usually, the adsorption-side relative vapor pressure (φ2) is the adsorbent. It is preferable to operate so that the pressure is higher than the relative vapor pressure for adsorbing water vapor at the maximum. The reason is as follows. That is, when the adsorption side relative vapor pressure (φ2) is smaller than the relative vapor pressure at which the adsorbent adsorbs water vapor to the maximum, the adsorption function of the adsorbent cannot be used effectively, and the operation efficiency is lowered. The adsorption side relative vapor pressure (φ2) can be appropriately set according to the environmental temperature or the like.

  In the regeneration step of the adsorber (1), the adsorber (1) is usually heated with warm water of 53 to 100 ° C, preferably 58 to 85 ° C, more preferably 60 to 80 ° C. Thereby, the adsorbent of the adsorber (1) has an equilibrium vapor pressure corresponding to the above temperature range, and the condensation temperature of the condenser (5) is 25 to 45 ° C. (cooling water for cooling the condenser (5)). Desorb water (adsorbate) with saturated vapor pressure at (temperature). The desorbed water moves from the adsorber (1) to the condenser (5) in the form of water vapor, and is condensed to become water. The water obtained in the condenser (5) is circulated and supplied to the evaporator (4) through the return pipe (3).

  The desorption side relative vapor pressure (φ1) (value obtained by dividing the equilibrium vapor pressure of the adsorbate at the cooling water temperature of the condenser (5) by the equilibrium vapor pressure of the adsorbate at the temperature of the hot water) is condensed. The desorption side relative vapor pressure (φ1) is determined so as to be smaller than the relative vapor pressure at which the adsorbent adsorbs water vapor rapidly. It is preferable to drive. The reason is as follows. That is, when the desorption side relative vapor pressure (φ1) is larger than the relative vapor pressure at which the adsorbent adsorbs water vapor rapidly, the excellent adsorption function of the adsorbent cannot be effectively used.

  The desorption side relative vapor pressure (φ1) can be appropriately set depending on the environmental temperature or the like, but the adsorption amount at the desorption side relative vapor pressure (φ1) is usually 0.14 g / g or less, preferably 0.8. It is operated under a temperature condition such that it is 10 g / g or less. Further, the operation is performed so 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 usually 0.07 g or more, preferably 0.09 g / g or more. To do.

  In the next second step, the control valves (31) to (34) and the switching valves (115) and (116) are used so that the adsorber (1) is an adsorption process and the adsorber (2) is a regeneration process. By switching between (215) and (216), it is possible to obtain cooling from the evaporator (4), in other words, cooling output, in the same manner as described above. That is, in the second stroke, the adsorption process is performed in the adsorber (1) by closing the control valves (32) and (33) and opening the control valves (31) and (34). A regeneration process is performed in the adsorber (2). Further, at that time, the switching valves (115), (116), (215) and (216) are operated, warm water is circulated through the heat medium pipe (21), and cooling water is supplied to the heat medium pipe (11). Circulate.

  As described above, the adsorption heat pump can be continuously operated by sequentially switching the first and second strokes. In addition, in FIG. 1, although illustrated about the adsorption heat pump provided with the two adsorbers (1) and (2), in the adsorption heat pump of the present invention, the adsorbate adsorbed by the adsorbent is appropriately desorbed, Any number of adsorbers may be installed as long as any adsorber can maintain the adsorbate adsorbate.

  The adsorber of the adsorption heat pump of the present invention as shown in FIG. 1 is generally a finned tube heat exchanger filled or coated with an adsorbent.

  When the zeolite of the present invention is applied to the heat exchanger as an adsorbent, for example, a slurry is prepared together with an inorganic or organic binder, and applied to the fin surface and dried to form a fixed film (coating mold). Heat exchanger).

  On the other hand, pellet-shaped (granular) zeolite (adsorbent) may be closely packed between fins, but when the adsorbent is pellets, small particles are closely packed in the gap formed between the continuous fins and the tube surface. A method of filling and wrapping the entire heat exchanger with a fine mesh net is often used. With this method, the heat exchanger can be manufactured quickly and easily. However, in such a system, the heat exchange performance is not so high due to the point contact between the particles of the adsorbent and between the particles and the metal (fin or tube) surface of the heat exchanger body, and the heat transfer is poor. . The thermal efficiency is also affected by the internal diffusion of the pellets.

  On the other hand, in the case of a coating-type heat exchanger, as long as the coating film is uniformly applied to the surface of the heat exchanger, it will have a large heat transfer area, so the heat transfer difficulties pointed out above Is preferable.

  The binder used in producing the coating type heat exchanger is not particularly limited as long as it satisfies the practically required durability and adhesiveness for the coating film to be formed. Alternatively, an organic binder can be used.

  Examples of the inorganic binder include metal oxides such as silica, alumina, and titania, and clay.

  Examples of organic binders include epoxy resins, phenol resins, polyimide resins, polyester resins, polyether sulfone resins, urethane resins, melamine resins, fluororesins, polycarbonate resins, (meth) acrylic resins, polyvinyl alcohol, silicone resins, Examples thereof include vinyl acetate resin, polyolefin resin, polystyrene resin, latex, cellulose, maleimide compound and the like.

In general, from the viewpoint of maintaining the strength of the coating film, the binder is preferably a thermosetting resin that can increase the cohesive force by curing. For example, the heat exchanger substrate to be applied such as fins is made of copper, aluminum, or the like. When it is a metal fin, it is preferably an epoxy resin, a phenol resin, a urethane resin, a silicone resin, or a derivative thereof.
In addition, these binders may be used individually by 1 type, and may be used in combination of 2 or more type.

  When using a binder, it may be used after diluting in a solvent, but when using a solvent, in order to expose the surface of the zeolite and obtain a coating film with little adsorption inhibition, an aqueous emulsion may be used. preferable.

  It is preferable that the usage-amount of a binder shall be 5 to 30 weight% as content in the coating film formed. When the amount of the binder is less than 5% by weight, sufficient coating strength cannot be obtained, and when it is more than 30% by weight, the porosity of the coating is decreased and the adsorption / desorption rate is lowered, which is not preferable.

  Various additives can be used as other additives for forming the coating film. For example, rheology additives, surfactants, antifoaming agents, curing agents, antioxidants, pH adjusters, rust inhibitors and the like can be added to the slurry for forming a coating film.

  Examples of the application method of the slurry for forming the coating film in the case of the application type include known methods, such as dip (impregnation, immersion), knife coating, spray coating, roll coating, screen printing, pad printing, offset printing, and the like. The method is mentioned.

  As the type of the base material of the heat exchanger, a plate shape, a sheet shape, a plate shape, an erofin tube type, a corrugated type, and the like used in known heat exchangers can be used without limitation. The material of the substrate is not particularly limited, and composite materials such as metal, ceramics, graphite, resin, and carbon fiber reinforced resin (CFRP) can be used.

  Since the adsorption heat pump of the present invention as described above can be driven using low-temperature exhaust heat as a heat source, it can be applied to various systems such as a cogeneration system that requires energy saving. Hereinafter, as an application example of the adsorption heat pump according to the present invention, a cold generation system using exhaust heat of a polymer electrolyte fuel cell, a cold generation system using the temperature of a solar water heater, a cogeneration system using an internal combustion engine A cold heat generation system using low-temperature exhaust heat and a heat generation system will be described with reference to FIGS.

  FIG. 2 is a configuration diagram of a cold heat generation system using exhaust heat of a polymer electrolyte fuel cell as a heat source of an adsorption heat pump according to the present invention, and FIG. 3 is a cold heat generation system using the heat of a solar water heater. FIG. FIG. 4 is a configuration diagram of a cold heat generation system using low-temperature exhaust heat of the engine. FIG. 5 is a configuration diagram of a thermal generation system using the adsorption heat pump according to the present invention. In addition, in FIGS. 2-5, the adsorption | suction heat pump of this invention is shown with a code | symbol (1A).

  The cold heat generation system shown in FIG. 2 is a cogeneration system in which a polymer electrolyte fuel cell (PEFC) (81) is incorporated in a household power source. Such a system is disclosed in Japanese Patent Laid-Open Nos. 6-74597 and 2001-213149. PEFC (81) has a power generation efficiency of about 40%, and the total efficiency is improved to about 80% by efficiently using waste heat. There are few uses for low-temperature exhaust heat of 80 ° C. or less, and effective use of such low-temperature exhaust heat is desired.

  Therefore, as shown in FIG. 2, in the present invention, heat of 80 ° C. or less discharged from the PEFC (81) is used for the adsorption heat pump (1A). That is, in the adsorption heat pump (1A) of the present invention, the adsorbers (1) and (2) use the low-temperature exhaust heat generated from the polymer electrolyte fuel cell (PEFC) (81) as external heat. Has been made. Specifically, the exhaust heat of the PEFC (81) is recovered by the heat exchanger (82) and, for example, hot water from the heat exchanger (82) is introduced into the adsorbers (1) and (2), thereby adsorbing material. It is used as a heating source when water (adsorbate) is desorbed from water. Since the adsorbers (1) and (2) need to remove heat of adsorption during adsorption, cooling water is supplied to perform heat exchange. The cooling water is supplied from a car radiator. A method of circulating a refrigerant serving as a cold heat source, such as water or tap water, is generally used. In some cases, external cold water can be used. In addition to the water-cooling method described above, an air-cooling method that uses air to cool can also be employed.

  Since the adsorption heat pump (1A) is a cold heat generation device, cold heat generation by utilizing exhaust heat becomes possible by incorporating it into a system as shown in FIG. In addition, in the conventional cold heat generating device, a compressor for compressing the refrigerant is necessary. However, according to the system shown in FIG. Since water can be used as a heat medium, it is preferable for the environment even from the viewpoint of defluorocarbon.

  The cold heat generation system shown in FIG. 3 is a system that generates cold using the heat of a solar water heater. A solar water heater system is disclosed in Japanese Patent Laid-Open No. Sho 63-118564. The water heater system includes a heat collecting circuit including a heat collector (83) and a hot water supply circuit including a hot water storage tank (84), and detects a hot water temperature of the hot water storage tank (84) and a water temperature to be replenished by a sensor. Then, by controlling the amount of water circulated from the hot water storage tank (84) to the heat collector (83), the hot water storage tank (84) always stores a constant amount of hot water at a constant temperature. The hot water in the hot water storage tank (84) can be adequately used by hot water supply, but the hot water supply demand varies depending on the season. Specifically, although it can be used sufficiently in the winter season, there is a fact that in the summer season, heat is surplus due to a decrease in heat demand, and as a result, energy saving has not been achieved.

  Therefore, as shown in FIG. 3, in the present invention, the hot water temperature stored in the hot water storage tank (84) is used for the adsorption heat pump (1A). That is, in the adsorption heat pump (1A) of the present invention, the adsorbers (1) and (2) are provided with excess heat stored in the hot water storage tank (84), in other words, low-temperature exhaust heat generated from the solar water heater. It is designed to be used as external heat. Specifically, the hot water temperature stored in the hot water storage tank (84) is recovered by a heat exchanger such as a bellows tube structure, and the hot water of the heat exchanger, for example, is introduced into the adsorbers (1) and (2). Thus, it is used as a heating source when water (adsorbate) is desorbed from the adsorbent. As described above, various cooling waters can be used to remove the heat of adsorption in the adsorbers (1) and (2), and the water newly supplied to the hot water storage tank (84) is used as the cooling water. You can also

  By incorporating the adsorption heat pump (1A) of the present invention into a system as shown in FIG. 3, it is possible to generate cold using surplus heat. That is, efficient cooling can be performed by using surplus heat in the summer. Moreover, since the surplus heat of the water heater system is used, further energy saving can be promoted. Furthermore, according to the system shown in FIG. 3, since no apparatus or power such as a compressor is required, it is possible to save power, and since water can be used as a heating medium, the environment can be reduced even from the viewpoint of removing chlorofluorocarbons. Is preferable.

  The cold heat generation system shown in FIG. 4 is a low-temperature exhaust heat utilization system constructed in a gas turbine cogeneration system that generates electric power using an internal combustion engine and manufactures steam, hot water, and cold water. A gas turbine cogeneration system is disclosed in Japanese Patent Application Laid-Open No. 2002-266656. As is well known, such a system, for example, generates power by driving a generator by a gas turbine (internal combustion engine), recovers the heat of the combustion exhaust gas of the gas turbine with an exhaust heat recovery boiler, generates steam, Cold water is produced by an absorption refrigeration machine using steam supplied from an exhaust heat recovery boiler as a driving heat source, and heat of exhaust gas that has passed through the exhaust heat recovery boiler is further recovered by a hot water boiler to produce hot water, and Cold water is produced by an adsorption refrigerator (adsorption heat pump) using hot water produced by a hot water boiler as a driving heat source.

  In this invention, as shown in FIG. 4, the heat | fever of the hot water collect | recovered with the hot water boiler (85) of the cogeneration system using an internal combustion engine is utilized for an adsorption heat pump (1A). That is, in the adsorption heat pump (1A) of the present invention, the adsorbers (1) and (2) use low-temperature exhaust heat generated from a cogeneration system using an internal combustion engine as external heat. Specifically, by collecting hot heat with a heat exchanger such as a bellows tube structure in a hot water boiler (85) and introducing, for example, hot water as a heat medium from the heat exchanger to the adsorbers (1) and (2). It is used as a heating source when desorbing water (adsorbate) from the adsorbent. In addition, various cooling fluids can be used for the removal of the heat of adsorption in the adsorbers (1) and (2) as described above.

  By incorporating the adsorption heat pump (1A) of the present invention into a cogeneration system as shown in FIG. 4, the low-temperature exhaust heat of the hot water, which has conventionally been of low utility value, can be used more effectively to generate cold at low cost. Can do. And since water can be used as a heat carrier, it is preferable also from a viewpoint of environmental protection. Moreover, since an absorption liquid such as lithium bromide is not used unlike an absorption refrigerator, maintenance management is not required and maintenance costs can be reduced. Furthermore, since it can be started substantially simultaneously with the gas turbine, it can respond quickly to load fluctuations.

  The thermal generation system shown in FIG. 5 is a system that generates thermal energy using the adsorption heat of the adsorbent. As described above, the adsorption heat pump (1A) reduces the temperature of the adsorbent by removing the heat of adsorption with cooling water or the like during normal operation so that the adsorbent exhibits a predetermined adsorption capacity during the adsorption operation. By using the heat of adsorption effectively, it is possible to generate warm heat.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by the following Examples, unless the summary is exceeded.

[Example 1]
To a mixture of 90 g of water and 46 g of 85 wt% phosphoric acid aqueous solution, 24.5 g of pseudoboehmite (water content 25 wt%, manufactured by Sasol) was slowly added and stirred. The mixture was stirred for 2 hours, and an aqueous solution in which 5.6 g of ferrous sulfate heptahydrate was dissolved in 37 g of water was added, and a mixture of 4.3 g of tin (II) sulfate in 40 g of water was added and stirred. Further, 24.2 g of triethylamine was mixed and stirred for 1 hour to obtain an aqueous gel (pH 5). This was charged into a 1 L induction stirring stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, rotated at 100 rpm, and reacted at 190 ° C. for 20 hours. After the reaction, the mixture was cooled and the precipitate was collected by filtration, washed with water and filtered repeatedly, and dried at 100 ° C.

When the XRD of the crystalline iron tin aluminophosphate thus obtained was measured under the following conditions, it was as shown in FIG.
<XRD measurement method>
X-ray source: Cu-Kα ray (λ = 1.54Å)
Output setting: 40 kV, 30 mA
Optical conditions during measurement: Divergent slit = 1 °
Scattering slit = 1 °
Receiving slit = 0.2mm
Diffraction peak position: 2θ (diffraction angle)
Measurement range: 2θ = 3-50 °

Furthermore, 3 g of the obtained dried product was put into a vertical quartz tube, heated from room temperature at 1.5 ° C./min, and air-fired at 550 ° C. for 6 hours.
This was heated and dissolved in an aqueous hydrochloric acid solution and subjected to elemental analysis by ICP analysis. As a result, the molar ratio of (Fe + Sn) / (Al + P + Fe + Sn) was 0.079, the molar ratio of Sn / Fe was 0.51, the molar ratio of Al / (Al + P + Fe + Sn) was 0.44, and the molar ratio of P / (Al + P + Fe + Sn). Was 0.48.

  Further, the water vapor adsorption isotherm at 35 ° C. of the obtained zeolite was measured with an adsorption isotherm measuring apparatus (Bell Soap 18: manufactured by Nippon Bell Co., Ltd.), and the results are shown in FIG. Moreover, the water vapor adsorption isotherm at the time of desorption at 75 ° C. was also measured with an adsorption isotherm measuring device (manufactured by Nippon Bell Co., Ltd.) using a porcelain floating balance, and the results are shown in FIG. The measurement was performed under the conditions of an air thermostat temperature of 50 ° C., an adsorption temperature of 35 ° C., an initial introduction pressure of 3 torr, a saturated vapor pressure of 42.181 torr, and an equilibrium time of 500 seconds.

  Further, when the following water vapor repeated adsorption / desorption test was conducted, the maintenance ratio was 96.1%.

<Water vapor repeated adsorption / desorption test>
The operation of holding the sample in a vacuum container maintained at 90 ° C. and exposing it to a 5 ° C. saturated water vapor atmosphere and an 80 ° C. saturated water vapor atmosphere for 90 seconds is repeated. At this time, part of the water adsorbed on the sample when exposed to a saturated water vapor atmosphere at 80 ° C. is desorbed in a saturated water vapor atmosphere at 5 ° C. and moves to a water reservoir maintained at 5 ° C. From the m-th adsorption to the n-th desorption, the average amount of adsorption per time (Qn; m (g)) and the dry weight (W (g)) of the sample transferred to the 5 ° C. water sump Cn; m (g / g)) is determined as follows.
[Cn; m] = [Qn; m] / (n−m + 1) / W
The maintenance rate of the adsorption / desorption test is a ratio of the average adsorption amount of 1001 to 2000 times to the average adsorption amount of 1 to 1000 times of the water vapor repeated adsorption / desorption test.

[Example 2]
To a mixture of 16.8 g of water and 9.2 g of 85% by weight phosphoric acid aqueous solution, 4.9 g of pseudoboehmite (water content 25% by weight, manufactured by Sasol) was slowly added and stirred. This was stirred for 2 hours, and an aqueous solution in which 2.2 g of ferrous sulfate heptahydrate was dissolved in 7.6 g of water was added thereto, and further 0.86 g of tin (II) sulfate was mixed with 9.0 g of water. Was added and stirred, and 4.8 g of triethylamine was further mixed and stirred for 1 hour to obtain an aqueous gel (pH 5). This was charged into a 100 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and the whole autoclave was rotated at 15 rpm and reacted at 190 ° C. for 20 hours. After the reaction, the mixture was cooled and the precipitate was collected by filtration, washed with water and filtered repeatedly, and dried at 100 ° C.

The XRD of the crystalline iron tin aluminophosphate thus obtained was measured and found to be AFI type.
The obtained dried product was air calcined in the same manner as in Example 1.
As a result of performing the elemental analysis in the same manner as in Example 1, the molar ratio of (Fe + Sn) / (Al + P + Fe + Sn) was 0.053, the molar ratio of Sn / Fe was 0.86, and the molar ratio of Al / (Al + P + Fe + Sn) was The molar ratio of 0.46, P / (Al + P + Fe + Sn) was 0.49.

  The water vapor adsorption isotherm at 35 ° C. of the obtained zeolite was measured with an adsorption isotherm measuring device (Bell Soap 18: manufactured by Nippon Bell Co., Ltd.), and the results are shown in FIG. The measurement was performed under the conditions of an air thermostat temperature of 50 ° C., an adsorption temperature of 35 ° C., an initial introduction pressure of 3 torr, a saturated vapor pressure of 42.181 torr, and an equilibrium time of 500 seconds.

  Moreover, when the water vapor | steam repeated adsorption / desorption test was done like Example 1, the maintenance factor was 96.9%.

[Example 3]
To a mixture of 10 g of water and 8.6 g of 85 wt% phosphoric acid aqueous solution, 4.9 g of pseudoboehmite (water content 25 wt%, manufactured by Sasol) was slowly added and stirred. This was stirred for 1 hour, and then an aqueous solution in which 2.2 g of ferrous sulfate heptahydrate was dissolved in 23.5 g of water was added, and 4.8 g of triethylamine was further mixed, followed by stirring for 1 hour. Further, 1.8 g of tetraisopropyl orthotitanate was added and stirred for 1 hour to obtain an aqueous gel (pH 5). This was charged into a 100 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and the whole autoclave was rotated at 15 rpm and reacted at 190 ° C. for 20 hours. After the reaction, the mixture was cooled, the supernatant was removed by decantation, the precipitate was collected, washed with water and filtered repeatedly, and dried at 100 ° C.

3 g of the obtained dried product was put into a vertical quartz tube, heated from room temperature at a heating rate of 1 ° C./min, and air fired at 550 ° C. for 6 hours.
When the XRD of the crystalline iron titanium aluminophosphate thus obtained was measured, it was AFI type (the framework density was 17.3 T / 1000 Å ³ ).
This was heated and dissolved in an aqueous hydrochloric acid solution and subjected to elemental analysis by ICP analysis. As a result, the molar ratio of (Fe + Ti) / (Fe + Ti + Al + P) was 0.056, the molar ratio of Ti / Fe was 0.30, the molar ratio of Al / (Fe + Ti + Al + P) was 0.43, and the molar ratio of P / (Fe + Ti + Al + P). Was 0.51.

Moreover, the water vapor adsorption isotherm at 35 ° C. of the obtained zeolite was measured with an adsorption isotherm measuring device (Bell Soap 18: manufactured by Nippon Bell), and the results are shown in FIG. The measurement was performed under the conditions of an air high temperature bath temperature of 50 ° C., an adsorption temperature of 35 ° C., an initial introduction pressure of 3 torr, a saturated vapor pressure of 42.181 Torr, and an equilibrium time of 500 seconds.
FIG. 10 shows that the water adsorption amount is as large as 0.13 g / g even in the case of 0.17 corresponding to the relative vapor pressure when cold water as low as 6 ° C. is obtained at the adsorption temperature of 35 ° C.

  Moreover, when the water vapor | steam repeated adsorption / desorption test was done like Example 1, the maintenance factor was 95.7%.

[Comparative Example 1: Comparative example of tin-free AFI zeolite]
In Example 2, the synthesis was performed in the same manner except that tin (II) sulfate was not added.
When the XRD of the crystalline iron aluminophosphate thus obtained was measured, it was an AFI type.

The obtained dried product was air calcined in the same manner as in Example 1.
With respect to the obtained zeolite, a water vapor adsorption isotherm at 35 ° C. was measured with an adsorption isotherm measuring apparatus (Bell Soap 18: manufactured by Nippon Bell Co., Ltd.), and the results are shown in FIG. Moreover, the water vapor adsorption isotherm at the time of desorption at 75 ° C. was also measured by the same method as in Example 1, and the results are shown in FIG. The measurement was performed under the conditions of an air thermostat temperature of 50 ° C., an adsorption temperature of 35 ° C., an initial introduction pressure of 3 torr, a saturated vapor pressure of 42.181 torr, and an equilibrium time of 500 seconds.

  Moreover, when the water vapor | steam repeated adsorption / desorption test was done like Example 1, the maintenance factor was 94.6%.

[Comparative Example 2: Comparative example of silica tin aluminophosphate having a skeleton structure of CHA type]
To a mixture of 20 g of water and 10.1 g of 85 wt% phosphoric acid aqueous solution, 6.5 g of pseudo boehmite (water content 25 wt%, manufactured by Sasol Corporation) was slowly added and stirred. This was stirred for 2 hours, to which was added a dispersion of 0.75 g of fumed silica (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) in 12 g of water, and further 1.1 g of tin (II) sulfate mixed in 10 g of water. And a mixture of 5.1 g of triethylamine and 4.4 g of morpholine was added and stirred for 1 hour to obtain an aqueous gel.
This was charged into a 100 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, rotated at 15 rpm together with the autoclave, and reacted at 190 ° C. for 48 hours. After the reaction, the mixture was cooled and the precipitate was collected by filtration, washed with water and filtered repeatedly, and dried at 100 ° C.

When the XRD of the crystalline silica tin aluminophosphate thus obtained was measured, it was a CHA type.
The obtained dried product was air calcined in the same manner as in Example 1.

  Moreover, when the water vapor | steam repeated adsorption / desorption test was done like Example 1, the maintenance factor was 21.9%.

In the case of the CHA type silica aluminophosphate obtained by synthesizing in the same manner as described above except that tin was not added, the retention rate was 100%.
Therefore, it can be seen that the inclusion of tin does not increase the durability of any structure of aluminophosphate, but rather may decrease the durability, and the effect of tin is unique to the AFI type. It was confirmed that.

[Comparative Example 3: Comparative Example of AFI Zeolite with Sn / Fe ≦ 0.5]
To a mixture of 15 g of water and 9.2 g of 85% by weight phosphoric acid aqueous solution, 4.9 g of pseudoboehmite (water content 25% by weight, manufactured by Sasol Corporation) was slowly added and stirred. This was stirred for 2 hours, and an aqueous solution in which 2.2 g of ferrous sulfate heptahydrate was dissolved in 10 g of water was added thereto, and a mixture of 0.43 g of tin (II) sulfate in 8 g of water was added and stirred. Further, 4.8 g of triethylamine was mixed and stirred for 1 hour to obtain an aqueous gel.
This was charged into a 100 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and the whole autoclave was rotated at 15 rpm and reacted at 190 ° C. for 20 hours. After the reaction, the mixture was cooled and the precipitate was collected by filtration, washed with water and filtered repeatedly, and dried at 100 ° C.

The XRD of the crystalline iron tin aluminophosphate thus obtained was measured and found to be AFI type.
The obtained dried product was air calcined in the same manner as in Example 1.
Further, as a result of elemental analysis as in Example 1, the molar ratio of (Fe + Sn) / (Al + P + Fe + Sn) was 0.052, the molar ratio of Sn / Fe was 0.11, and the molar ratio of Al / (Al + P + Fe + Sn) was The molar ratio of 0.45, P / (Al + P + Fe + Sn) was 0.50.

  The water vapor adsorption isotherm at 35 ° C. of the obtained zeolite was measured with an adsorption isotherm measuring device (Bell Soap 18: manufactured by Nippon Bell Co., Ltd.), and the results are shown in FIG. The measurement was performed under the conditions of an air thermostat temperature of 50 ° C., an adsorption temperature of 35 ° C., an initial introduction pressure of 3 torr, a saturated vapor pressure of 42.181 torr, and an equilibrium time of 500 seconds.

  From the results shown in FIG. 7, the zeolite of Example 1 of the present invention is a curve in which the adsorption isotherm at 35 ° C. rapidly adsorbs water vapor in the range of the relative vapor pressure of 0.1 to 0.18, particularly 35 ° C. Even in the case of 0.17 corresponding to the relative vapor pressure when obtaining cold water as low as 6 ° C. at an adsorption temperature of 0.15 g / g, the adsorption amount is as large as 0.122 g / g, whereas in Comparative Example 1, it is only 0.015 g / g. I understand that. Further, the difference between the adsorption amount in the case of the relative vapor pressure 0.17 at the time of adsorption at 35 ° C. and the adsorption amount in the case of the relative vapor pressure 0.15 at the time of desorption at 75 ° C. is 0 in Example 1. It can be seen that it is as small as 0.01 g / g in Comparative Example 1 while it is 0.08 g / g.

  That is, when the zeolite of the present invention is used as an adsorbent, even when a relatively low temperature exhaust heat is used, in other words, even when the desorption temperature of water vapor is relatively low, the adsorption temperature (Tlow) and the desorption temperature (High). It can be seen that the adsorption amount difference is large and the output density is large. Zeolite having the above characteristics has a sufficiently large power density and is one of the most preferable adsorbents of the present invention.

  8 and 9, the case of Comparative Example 3 in which the tin content is smaller than that of Example 2 corresponds to the relative vapor pressure particularly when cold water of 6 ° C. is obtained at an adsorption temperature of 35 ° C. The adsorption amount in the case of 0.17 is 0.15 g / g in Example 2, whereas 0.07 g / g is not sufficient in Comparative Example 3, and there is a sufficient adsorption amount difference in the target region. It cannot be obtained, and it is understood that sufficient performance cannot be exhibited as an adsorbent when the low temperature side is high temperature.

In addition, the zeolite of the present invention is also excellent in stability (durability) after repeated water vapor adsorption / desorption tests, so that it can withstand long-term use when used in an adsorption heat pump, etc. Also excellent.
It is clear from the results of Comparative Example 2 that such an effect is not an effect obtained with any zeolite if tin or titanium is added.

[Comparative Example 4: Adsorption performance and durability comparison of various Fe-Me-AFI type zeolites]
In the same manner as in Example 1, components of nickel, silicon, cobalt, copper, magnesium and zirconium (the above are collectively referred to as “Me”) so that the hetero atoms have the same molar ratio instead of tin. ) Was added to synthesize Fe-Me-AFI type aluminophosphate zeolite.
As raw materials for each of Me, nickel nitrate, fumed silica, cobalt nitrate, copper nitrate, magnesium nitrate, and zirconyl nitrate were used.
Water vapor adsorption isotherms during adsorption of these zeolites at 35 ° C. were measured.
Moreover, the water vapor | steam repeated adsorption / desorption test was done like Example 1, and the maintenance factor was calculated | required.
Table 1 below shows the amount of adsorption and the maintenance rate of each zeolite at a relative vapor pressure of 0.17 on a 35 ° C. water vapor adsorption isotherm. Table 1 shows the values of the zeolite of Comparative Example 1 and the zeolite of Example 1.
In this comparative example, various Me described in Patent Documents 2 and 3 were subjected to a comparative test. At 35 ° C. relative vapor pressure of 0.17, the adsorption amount was 0.1 g / g or more and the maintenance rate was 90% or more. There was no one.

[Example 4, Comparative Example 5: Application example of adsorption heat pump]
Adsorbent (zeolite) of the present invention obtained in Example 1 (Example 4) or known adsorbent (AQSOA (registered trademark) -Z01, AFI type iron aluminophosphate manufactured by Mitsubishi Plastics) Using Example 5), a heat exchanger was prepared as follows, and an application experiment was performed when it was used in a 1 kW class adsorption refrigerator having the configuration shown in FIG.

The adsorbent (zeolite) of the present invention is characterized in that it adsorbs adsorbate at a low relative vapor pressure. This "adsorbs adsorbate with low relative vapor pressure"
(1) The adsorbent and the ambient atmosphere (cooling fluid) can be adsorbed at high temperatures.
Or (2) It indicates that adsorption is possible under the condition of cold water at a lower temperature.
The conditions in Table 2 below are experimental examples in the state (1), and the conditions in Table 5 are experimental examples in the state (2).

<Creation of heat exchanger>
Add 1000g of adsorbent and 1000g of ion-exchanged water, and after cooling the temperature generated by adsorption heat sufficiently, add an aqueous emulsion of jER1256 (Mitsubishi Chemical Corporation product name, bisphenol A type epoxy resin) as an organic binder. And uniformly mixed to prepare a slurry.
Using the above slurry, a total of four heat exchangers were applied to aluminum flat fins that were applied and heat-dried to a coating weight of 165 g. Two of these were installed in each of the adsorbers (1) and (2) in FIG. 1 to prepare an adsorption heat pump.

<Conditions for (1)>
Measurement was performed by varying the temperature (inlet temperature) of the cooling water supplied through the heat medium pipe (11) or (21) as a low-temperature heat source during adsorption (27 ° C, 30 ° C, 32 ° C, 35 ° C). . Table 2 shows the main experimental conditions.
In the experimental conditions, the values other than the cooling water temperature were set to constant values. The hot water temperature was set to the lowest temperature at which the output of the adsorbent reached the limit under each condition and could not be further improved. The temperature of the hot water is the temperature of hot water (inlet temperature) supplied through the heat medium pipes (11) and (21) as a high-temperature heat source during desorption, and the temperature of the cold water is the cold water pipe (41 ), The output performance (kW) is evaluated as the temperature (inlet temperature) of the cold water supplied to the evaporator (4) and the cold water temperature (outlet temperature) of the evaporator (4) passing through the cold water pipe (42). The results (Table 3) when using a known adsorbent (Comparative Example 5) and the results (Table 4) when using the adsorbent of the present invention (Example 4) are shown. The results are collectively shown in FIG.

  As a result, if the cooling water temperature (adsorbent temperature), which is a low-temperature heat source, is low, there is no significant difference in cooling output between the known adsorbent (Comparative Example 5) and the adsorbent of the present invention (Example 4). It was found that the higher the water temperature, the higher the cooling output, and the difference is remarkable.

<Condition (2)>
For the condition (1) above, the cooling water temperature (low temperature heat source) is fixed at 32 ° C., the flow rate of the cold water is kept constant, and the hot water temperature (high temperature heat source temperature) is adsorbed in a known adsorbent (Comparative Example 5). The minimum temperature at which the output of the material reaches the limit and cannot be improved any further, the adsorbent of the present invention (Example 4) is set to a temperature at which the output is 80%, and the cold water temperature is The conditions (Table 5) and results (Comparative Example 5 = Table 6, Example 4 = Table 7) when the cooling output was measured at 9 ° C. or 7 ° C. were shown.
These results are shown in FIG.

  As a result, as is apparent from FIG. 12, the lower the chilled water temperature that can be taken out from the adsorption chiller is, the lower the chilled water temperature (when the chilled water inlet temperature is 7 ° C., 7 ° C.) It can be seen that the adsorbent of the present invention (Example 4) has a relatively high cooling output (kW) and the difference is larger than that of Comparative Example 5).

DESCRIPTION OF SYMBOLS 1 Adsorber 11 Heating medium piping 115 Switching valve 116 Switching valve 2 Adsorber 21 Heating medium piping 215 Switching valve 216 Switching valve 3 Return piping 30 Adsorbate piping 31 Control valve 32 Control valve 33 Control valve 34 Control valve 300 Indoor unit 301 Pump 4 Evaporator 41 Chilled water piping 42 Chilled water piping 5 Condenser 51 Inlet piping 52 Outlet piping 81 Polymer electrolyte fuel cell (PEFC)
82 Heat exchanger 83 Heat collector 84 Hot water storage tank 85 Hot water boiler 86 Hot water storage tank

Claims (9)

AFI-type zeolite containing aluminum, phosphorus, iron and M (M is tin and / or titanium) in the skeleton structure, and the M / Fe molar ratio is 0.25 <M / Fe <1.0.
Zeolite characterized by being. AFI-type zeolite containing aluminum, phosphorus, iron and M (M is tin and / or titanium) in the skeleton structure, and M / Fe molar ratio is 0.50 <M / Fe <1.0.
Zeolite characterized by being.   The zeolite according to claim 1 or 2, wherein M is tin.   An adsorbent using the zeolite according to any one of claims 1 to 3.   The adsorbent according to claim 4, wherein an adsorption amount at a relative vapor pressure of 0.17 is 0.10 g / g or more in a water vapor adsorption isotherm measured at 35 ° C.   In the water vapor adsorption isotherm in the adsorption process at 35 ° C., the adsorption amount at a relative vapor pressure of 0.17 and in the water vapor adsorption isotherm in the desorption process at 75 ° C., the adsorption amount at a relative vapor pressure of 0.15. The adsorbent according to claim 4 or 5, wherein the difference is 0.07 g / g or more. An adsorption heat pump using the adsorbent according to any one of claims 4 to 6,
An adsorber that repeats an adsorption operation for adsorbing the adsorbate to the adsorbent while releasing heat of adsorption, and a desorption operation for desorbing the adsorbate from the adsorbent by external heat,
Taking out the cold heat obtained by the evaporation of the adsorbate to the outside, an evaporator in which the generated adsorbate vapor is collected in the adsorber,
An adsorption heat pump comprising: a condenser for condensing the adsorbate vapor desorbed by the adsorber with external cold heat and supplying the condensed adsorbate to the evaporator.   An operation method of the adsorption heat pump according to claim 7, wherein the adsorption heat pump is operated.   9. The operation method of the adsorption heat pump according to claim 8, wherein the adsorption heat pump using the adsorbent according to claim 5 is configured such that the adsorption temperature of water vapor is Tlow, the desorption temperature of water vapor is High, and the cold heat generation temperature is An operation method of the adsorption heat pump, characterized in that when Tcool is set, and when High ≦ 100 ° C. and Tlow is 25 to 45 ° C., the operation is performed under the condition of 0 ° C. ≦ Tcool ≦ 10 ° C.

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