JP2000262892A - Adsorbent and air conditioner for vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve water absorption efficiency in a low humidity condition by forming an adsorbent which desorbs water by heating and adsorbs water by cooling as a porous composite comprising an organic substance which generates a sol-gel phase transition by a temperature change and an inorganic substance having three-dimensional network structure. SOLUTION: An adsorbent which adsorbs water when temperature is low and humidity is high and desorbs water when temperature is high and humidity is low is formed as a porous composite comprising an organic substance which generates a sol-gel phase transition by a temperature change and an inorganic substance having three-dimensional network structure. In the three-dimensional structure of the inorganic substance, the organic substance is dispersed. For example, in the adsorption type refrigeration cycle 100 of an air conditioner for vehicles, cooling water for an engine E is circulated to the heat exchange part 301 of an adsorption core 30 through a fluid circulating passage (a), and water is desorbed by heating the adsorbent S of the adsorption core 30. By cooling another adsorption core 20 by an adsorption core cooler 25, water is adsorbed by the adsorbent S.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorbent and a method for producing the adsorbent, which utilizes the fact that an adsorbent adsorbs and desorbs water when cooled and heated, and a vehicle air conditioner using the same.

[0002]

2. Description of the Related Art Conventionally, an adsorption-type refrigeration apparatus includes an adsorption core having an adsorbent for adsorbing water during cooling and releasing water when heated, and an evaporating condenser for evaporating and condensing water. Are known. In such a refrigerator, when water is adsorbed by the adsorption core, the water evaporates in the evaporative condenser. At this time, the indoor air can be cooled by circulating the heat exchange fluid, which has been cooled by heat exchange with water in the evaporative condenser, to the indoor heat exchanger provided in another portion.

[0003] Further, the adsorption core to which water is adsorbed is heated,
Regenerated by desorbing water. At this time, the desorbed water is condensed in the evaporative condenser. When such an adsorption refrigeration apparatus is mounted on a vehicle or the like, for example, engine cooling water (about 90 ° C.) is used as a heating source for desorbing water from the adsorption core.

On the other hand, as a heat absorbing source for cooling the adsorption core and adsorbing water, for example, engine cooling water (about 30 ° C.) cooled in an outdoor heat exchanger or a separately provided vapor compression type Low pressure side water (for example, 20
(About 25 ° C.) is used. Therefore, when the above-mentioned adsorption refrigeration apparatus is applied to an air conditioner for a vehicle, the relative humidity near the adsorbent is 0.1%.
Desorption / adsorption of water is performed in the range of 08 to 0.30.

Conventionally, as an adsorbent used in the above-mentioned adsorption refrigerating apparatus, for example, silica gel obtained by firing silicon oxide has been used.

[0006]

[Problems to be solved] However, silica gel has a uniform pore size distribution over a wide range,
In particular, the pore volume occupied by a small pore diameter (2 nm or less) is small. Therefore, when silica gel is used as the water absorbing material, the water absorbing efficiency at low humidity is poor. In addition, zeolite has a relatively small pore size and is uniform, but requires a large amount of heat for dehydration because of its large interaction with water. For these reasons, when zeolite is used as the water absorbing material, the efficiency of water absorption / desorption is very low. Further, when zeolite is used as a water-absorbing material for an air conditioner for a water refrigerant, the size of the product is increased, and the use is limited.

SUMMARY OF THE INVENTION In view of the conventional problems, the present invention has an adsorbent having high water absorption efficiency at low humidity and capable of efficiently adsorbing and desorbing water, a method for producing the same, and a vehicle air conditioner using the same. It is intended to provide a device.

[0008]

According to the present invention, as set forth in claim 1,
An adsorbent that desorbs water when heated and adsorbs water when cooled. The adsorbent is composed of an organic substance that can cause a sol-gel phase transition due to a temperature change and a three-dimensional network structure. An adsorbent, which is a porous composite comprising an inorganic substance having the organic substance dispersed in a three-dimensional network structure of the inorganic substance.

The operation and effect of the present invention will be described.
The adsorbent of the present invention is a porous composite, and adsorbs and desorbs water by a combination of capillary condensation and sol-gel phase transition. The sol-gel phase transition of the adsorbent is caused by a change in temperature. Here, the “sol-gel phase transition due to temperature change” means that when the temperature is higher than the phase transition temperature, the phase changes to a sol, and when the temperature is lower than the phase transition temperature, the phase changes to a gel. Along with this phenomenon, a phenomenon occurs in which the adsorbent absorbs water at a low temperature and swells, and desorbs and shrinks at a high temperature. The adsorption / desorption of water occurs reversibly, and the above-mentioned phase transition temperature is between the temperature at which the water is adsorbed and the temperature at which the water is desorbed.

This phenomenon will be described by taking as an example a case where a crosslinked polymer of N-isopropylacrylamide is used as an adsorbent. As shown in FIG. 1, the crosslinked polymer of N-isopropylacrylamide has a sol-gel phase transition temperature of 3
At a temperature lower than 5 ° C (for example, 20 ° C).
C.), and becomes a sol at a high temperature (for example, 40 ° C.).

When the temperature is lower than the sol-gel phase transition temperature and the humidity is high, water molecules first enter the pores of the porous adsorbent by capillary action. At this time, many water molecules are
It is adsorbed around the organic polymer chains in the pore walls, and the pores are also filled with water. Next, when the temperature is increased and the humidity is decreased from this state, the water molecules in the pores are desorbed, and then the water molecules adsorbed in the pore walls are desorbed by the sol-gel phase transition.

As described above, the adsorbent of the present invention has both a function of causing a difference in the amount of adsorption due to a capillary phenomenon due to a change in humidity and a function of causing a sol-gel phase transition due to a change in temperature. Therefore, the adsorbent of the present invention can be used as a sol of the adsorbent.
Water can be adsorbed in an environment at a temperature lower than the gel phase transition temperature and in a high humidity, and desorbed in an environment at a high temperature and a low humidity. Therefore, the adsorbent of the present invention having both these functions exhibits higher adsorption / desorption performance than when the two functions are used alone.
Therefore, the adsorbent of the present invention has excellent water adsorption / desorption performance.

As described above, according to the present invention, it is possible to provide an adsorbent having high water absorption efficiency at low humidity and capable of efficiently adsorbing and desorbing water.

The organic substance of the present invention has a property of causing a sol-gel phase transition by a change in temperature. As such an organic substance, for example, the organic substance is preferably a polymer having a hydrophilic group and a hydrophobic group in a molecule. Thereby, the adsorption and desorption of water can be performed efficiently.

[0015] As described in claim 3, the organic substance is preferably a crosslinked polymer. The crosslinked polymer has a property of swelling due to solvation upon water adsorption. In the present invention, such a swellable crosslinked polymer is dispersed in a three-dimensional network structure of an inorganic substance. Thereby, the crosslinked polymer is arranged so as to sew the mesh of the inorganic three-dimensional network structure. Therefore, the three-dimensional network structure of the inorganic material functions as a solid support for the crosslinked polymer, and captures the crosslinked polymer. therefore,
The crosslinked polymer does not flow out of the inorganic structure. For this reason, the swelling of the crosslinked polymer during water adsorption can be suppressed as much as possible, and it does not swell as much as the free crosslinked polymer. Therefore, the size of the suction core for containing the adsorbent can be reduced.
The above “crosslinked polymer” refers to a polymer in which the polymers are linked to each other by a crosslinking bond.

According to a fourth aspect of the present invention, the organic material is poly (N-isopropylacrylamide), poly (Nt
-Butylacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-diethylacrylamide), polyethylene glycol, cellulose, or a polymer composed of polymethyl vinyl ether, or any one or more of such polymers. It is preferable that it is composed of one or more selected from crosslinked polymers obtained by crosslinking. Thereby, water can be efficiently adsorbed and desorbed. The sol-gel phase transition temperature of the above organic substance is
The temperature is preferably from 30 to 60 ° C. Thereby, water can be adsorbed and desorbed in a suitable environment for use.

Further, the inorganic substance needs to have a three-dimensional network structure. As such an inorganic substance, for example, silica (SiO 2)
₂ ), alumina (Al ₂ O ₃ ), titania (Ti
O ₂ ) or 1 selected from zirconia (ZrO ₂ )
Species or two or more can be used. In addition,
“Three-dimensional network structure” refers to a robust structure having a three-dimensional network structure.

The adsorbent is a porous composite comprising the organic substance and the inorganic substance. Regarding the pore characteristics of such a porous composite, the pore volume is preferably 0.20 cm ³ / g or more when the pore diameter is in the range of 1.0 nm to 1.5 nm. Thereby, water can be efficiently adsorbed and desorbed.

Next, in producing the adsorbent, for example, an organic substance capable of causing a sol-gel phase transition due to a temperature change in a three-dimensional network structure of an inorganic substance and a solvent-extractable solvent are described. Obtaining a complex comprising the inorganic substance, the organic substance capable of causing the sol-gel phase transition, and the solvent-extractable organic substance, and extracting the solvent-extractable organic substance from the composite substance. And then converting the composite to a porous body.

In the present invention, an organic substance which can be extracted with a solvent, an organic substance which can cause a sol-gel phase transition, and an inorganic substance having a three-dimensional network structure are mixed to form a complex comprising a ternary hybrid, and thereafter the solvent is extracted. Possible organics are removed by solvent extraction. As a result, a porous composite having a large number of pores can be obtained in which an organic substance capable of causing a sol-gel phase transition is left in an inorganic three-dimensional network structure. As described above, an adsorbent having the above excellent properties can be manufactured.

In addition, the method of forming a porous composite having pores by using such an organic substance which can be extracted with a solvent makes it possible to recover the organic substance during the manufacturing process, and to remove the organic substance by burning it out. Hydroxyl groups in inorganic substances tend to remain. Therefore, a hydrogen bond between the hydroxyl group and water is easily generated, and the water adsorption efficiency is improved.

Examples of the organic substance that can be extracted with a solvent include poly (N, N-dimethylacrylamide), poly (N-isopropylacrylamide) and poly (Nt-t-acrylamide).
Butylacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-diethylacrylamide), polystyrenes, polyvinyl chloride, poly (2-methyl-2-oxazoline), poly (2-ethyl-2- Oxazoline) or poly (1-vinyl-2-pyrrolidone) can be used. This allows extraction with water or an organic solvent.

According to a seventh aspect of the present invention, in the step of obtaining the complex, an uncrosslinked substance which can be an organic substance capable of causing a sol-gel phase transition in the presence of the inorganic substance and the organic substance which can be extracted by a solvent is used. Crosslinking is preferred.
When the uncrosslinked substance is mixed with the inorganic substance and the solvent-extractable organic substance, the uncrosslinked substance and the solvent-extractable organic substance are compatible in the three-dimensional network structure of the inorganic substance. When a cross-linking reaction occurs in the uncross-linked material in this state,
The crosslinked polymer is formed in a state of being dispersed in the network of the three-dimensional network structure. Therefore, when the solvent extractable organic matter is removed from these complexes, the crosslinked polymer is captured and supported by the three-dimensional network structure.
Therefore, the crosslinked polymer does not flow out of the three-dimensional network structure of the inorganic substance, and swelling of the crosslinked polymer upon water adsorption can be suppressed as much as possible. Therefore, the size of the suction core for containing the adsorbent can be reduced.

The uncrosslinked material may be a monomer or a polymer. In the case of a monomer, polymerization and crosslinking are performed in a three-dimensional network structure of an inorganic substance. In the case of a polymer, crosslinking is performed in a three-dimensional network structure of an inorganic substance. Uncrosslinked materials include poly (N-isopropylacrylamide), poly (Nt-butylacrylamide), poly (N, N-dimethylacrylamide),
There is a polymer made of poly (N, N-diethylacrylamide), polyethylene glycol, cellulose, or polymethyl vinyl ether. In addition, "crosslinking an uncrosslinked substance" means that polymers are crosslinked with each other by a crosslinking agent or the like, or by a crosslinking agent and a polymerizing agent.
It means that the monomer is polymerized and the polymer obtained by the polymerization is crosslinked.

Next, as a vehicle air conditioner using the adsorbent, there is provided an adsorbent core provided with an adsorbent, and a temperature control mechanism for controlling the temperature of the adsorbent core. An evaporating condenser, an indoor heat exchanger, a communicating portion for circulating water between the adsorption core and the evaporating condenser, and a heat exchange fluid between the evaporating condenser and the indoor heat exchanger. The adsorbent has the property of desorbing water by heating and adsorbing water by cooling. The water is evaporated when adsorbed, and condensed when the water is desorbed by the adsorption core. The heat exchange fluid is cooled by depriving the latent heat of evaporation by evaporation of the water in the evaporative condenser. , In the above-mentioned indoor heat exchanger A vehicle air conditioner for performing air heat exchanger, the adsorbent is a vehicle air conditioner which is a sorbent according to any one of claims 1 to 5.

The adsorbent provided in the vehicle air conditioner includes:
The temperature control mechanism is controlled so that heating and cooling are repeated as appropriate. When the temperature control mechanism lowers the temperature of the adsorption core, the adsorbent in the adsorption core adsorbs water in the adsorption core, the communication section, and the evaporative condenser. The humidity in the communication section decreases, and the internal pressure decreases accordingly. Thereby, the liquid water in the evaporative condenser also evaporates. At this time, the heat exchange fluid in the evaporative condenser is deprived of latent heat by the evaporating water and cooled. The cooled heat exchange fluid flows to the indoor heat exchanger, where it exchanges heat with the vehicle interior air to cool the vehicle interior.

On the other hand, when the temperature adjusting mechanism raises the temperature of the adsorption core, the water adsorbed on the adsorbent evaporates and desorbs from the adsorbent, and the adsorbent is regenerated. On the other hand, the vaporized water flows to the evaporative condenser through the communicating portion, where the heat exchange fluid deprives the heat of the heat and condenses into liquid water.

Therefore, when the temperature cycle of the adsorption core is repeated by the temperature control mechanism, as described above, the adsorption and desorption of water by the adsorbent and the corresponding evaporation and liquefaction of water in the evaporative condenser, Cooling of the heat exchange fluid by the latent heat during evaporation occurs continuously. Further, when the heat exchanger exchanges heat with the vehicle interior air, the vehicle interior is cooled. As described above, according to the present apparatus, continuous cooling of the vehicle interior can be performed by repeatedly increasing and decreasing the temperature of the suction core at predetermined time intervals by the temperature adjustment mechanism.

This apparatus uses an adsorbent having excellent water adsorption / desorption performance as described above. This adsorbent efficiently adsorbs and desorbs water circulating between the heat of the adsorption core and the evaporative condenser. Therefore, according to the present device, it is possible to provide an air conditioner for a vehicle that exhibits a more excellent cooling effect.

In the present apparatus, the temperature adjusting mechanism has a heating source and a heat absorbing source. As the heating source, for example, engine cooling water after engine cooling can be used. Further, as the heat absorbing source, for example, engine cooling water after cooling outdoors and a refrigeration cycle can be used. As the adsorption core, for example, a core in which an adsorbent is accommodated in a support having good heat conductivity can be used. The adsorbing core, the evaporative condenser, and the communicating portion that performs water lubrication between the adsorbing core and the evaporating condenser may be one set, or a plurality of sets.

The temperature control mechanism controls the temperature of the adsorbent in the adsorption core between a temperature lower than the sol-gel phase transition temperature of the adsorbent and a temperature higher than the sol-gel phase transition temperature at predetermined time intervals. It is preferred that Thereby, the water adsorption / desorption performance of the adsorbent of the present invention can be effectively exhibited, and the vehicle interior can be efficiently cooled.

The time required for one temperature cycle is preferably, for example, 1 to 30 minutes. If the time is less than 1 minute, water adsorption to the adsorbent becomes insufficient, so
The cooling capacity per cycle may be reduced. If the time exceeds 30 minutes, the latent heat of evaporation of water obtained per unit time is reduced, so that the cooling capacity per unit time may be reduced.

Further, as a vehicle air conditioner using the adsorbent obtained by the above manufacturing method, for example, an adsorbent core provided with an adsorbent and the temperature of the adsorbent core are controlled. Temperature control mechanism, evaporative condenser, indoor heat exchanger, communication part for circulating water between adsorption core and evaporative condenser, and heat exchange between evaporative condenser and indoor heat exchanger The adsorbent has the property of desorbing water by heating and adsorbing water by cooling, and the evaporative condenser is formed by the adsorption core. The water is evaporated when the water is adsorbed, and condensed when the water is desorbed by the adsorption core. The heat exchange fluid is deprived of the latent heat of evaporation by the evaporation of the water in the evaporative condenser. Cooled and sent to the indoor heat exchanger A vehicle air conditioner that exchanges heat with vehicle interior air, wherein the adsorbent is an adsorbent manufactured by the manufacturing method according to one of claims 6 and 7. There is a device.

This vehicle air conditioner uses the adsorbent obtained by the above-mentioned manufacturing method to constitute the same device as that of the eighth aspect. Therefore, air conditioning of vehicle interior air can be performed efficiently as in the above-described device.

The adsorbent of the present invention can be used not only for the above-mentioned air conditioner for a vehicle but also for a ventilation air purifier, a dehumidifier, and the like. When the adsorbent is used in a vehicle air conditioner, the sol-gel phase transition temperature is preferably 40 to 60 ° C. Thereby, the cooling in the vehicle air conditioner can be performed more efficiently.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 An adsorbent of the present invention and a vehicle air conditioner using the same will be described with reference to FIGS. The adsorbent of this example is an adsorbent that adsorbs water at low temperature and high humidity and desorbs water at high temperature and low humidity. The adsorbent is a porous composite composed of an organic substance capable of causing a sol-gel phase transition due to a temperature change and an inorganic substance having a three-dimensional network structure. In the three-dimensional network structure of the inorganic substance, an organic substance capable of causing the sol-gel phase transition is dispersed.

The organic substance is N-isopropylacrylamide.
And N, N'-methylenebisacrylamide
It is a polymer having a hydrophilic group and a hydrophobic group in the molecule.
The sol-gel phase transition temperature is 35 ° C. Inorganic substances are tertiary
It is a porous silica material having an original network structure. adsorption
The agent has a pore volume in the range of pore diameter 1.0 to 1.5 nm.
Product is 0.22cm ³/ G of pore characteristics.

Next, the method for producing the adsorbent will be described.
You. First, in a predetermined container, N-isopropyl acrylic
0.9 g of amide, N, N'-methylenebis as a crosslinking agent
0.1 g of acrylamide, and 2,
A method comprising 15 mg of 2'-azobisisobutyronitrile
Tanol solution 20cm ³Was prepared. This methanol solution
1.0 g of poly N, N-dimethylacrylamide
After addition, a further 2.0 g of tetramethoxysilane and 0.1 g
1N hydrochloric acid 0.5cm³And stir at room temperature for 24 hours.
Was.

Thereafter, the solution was allowed to stand at 60 ° C. for 7 days to evaporate the solvent, and the resulting transparent gel was immersed in water for 72 hours using Soxhlet to extract and remove poly N, N-dimethylacrylamide. As a result, a porous silica material having a three-dimensional network structure is formed, in which N-
A porous composite in which a crosslinked copolymer of isopropylacrylamide and N, N'-methylenebisacrylamide was dispersed, that is, an adsorbent was obtained.

Next, an embodiment in which the adsorbent thus obtained is applied to a vehicle air conditioner will be described. In FIG. 2, reference numeral 1 denotes a vehicle air conditioner, which is mounted, for example, below a dashboard in a vehicle compartment. The air-conditioning duct 2 of the vehicle air-conditioning device 1 is an air-conditioning passage for guiding conditioned air into the vehicle interior. At one end of the air-conditioning duct 2, suction ports 4 and 5 for sucking inside and outside air are provided. The intake ports 4 and 5 are switched and opened / closed by an inside / outside air switching door 6.

Reference numeral 3 denotes a blower, which blows air into the air-conditioning duct 2 by driving a centrifugal fan 3b by a motor 3a. On the other hand, on the other end side of the air conditioning duct 2,
A plurality of blowing openings 7, 8, 9 communicating with the vehicle interior are formed, and are selectively opened and closed by opening switching doors 10, 11, 12, respectively.

An indoor heat exchanger 16 and a heater core 31 are provided downstream of the blower 3 in the air. The indoor heat exchanger 16 cools the air in the air-conditioning duct 2 with the heat exchange fluid cooled by the evaporative condensers 60 and 70 of the adsorption refrigeration cycle 100 described later. The heater core 31 circulates heated engine cooling water to heat the air in the air conditioning duct 2. The air mixing door 31a adjusts the amount of air passing through the heater core 31 and the amount of air bypassing the heater core 31, thereby controlling the temperature regulation in the vehicle cabin.

Next, the adsorption refrigeration cycle 100 will be described in detail. The adsorption refrigeration cycle 100 includes first and second adsorption cores 20 and 30 and first and second evaporative condensers (evaporators and condensers) 60 and 70. First
The adsorption core 20 and the first evaporative condenser 60 are provided in the first closed vessel 6.
01, and the second adsorption core 30 and the second evaporative condenser 70 are accommodated inside the second closed vessel 602. A predetermined amount of water is sealed in each of the first and second closed containers 601 and 602.

The first and second closed containers 601 and 602 contain first and second adsorption core chambers 62 and 63 for accommodating the first and second adsorption cores 20 and 30, and first and second evaporative condensers 60. , 70
And first and second evaporative condensation chambers 66 and 67 for accommodating the same. In addition, the first and second closed containers 601 and 602 include first and second communication portions 86 that communicate the first and second adsorption core chambers 62 and 63 and the first and second evaporative condensation chambers 66 and 67, respectively. 87. The first and second evaporative condensers 60 and 70 are devices for evaporating and condensing water. When one of them functions as an evaporator for evaporating water, the other functions as a condenser for condensing water. The first and second evaporative condensers 60 and 70 are connected to the indoor heat exchanger 16 via a second fluid circulation path b for circulating a heat exchange fluid.
Is connected to

As shown in FIGS. 3A to 3C, the first,
The heat exchange units 201 and 301 of the second adsorption cores 20 and 30
A plurality of flat tubes 222 through which a heat exchange fluid (for example, engine cooling water) flows, and a corrugated heat transfer fin 2 between header tanks 221 provided at both ends.
23 are alternately stacked. And the tube 222
The gap between the heat transfer fins 223 is filled with the adsorbent S of this example. The adsorbent S is a particle having a uniform diameter formed by compacting each of the powdery adsorbents and granulating the adsorbent S on the surfaces of the tube 222 and the heat transfer fins 223 with an adhesive (for example, epoxy resin). Adhesively fixed.

FIG. 3B shows the suction cores 20 and 3.
The tube 222 of the heat exchange units 201 and 301 of No. 0 is simplified. As shown in FIG. 2, the engine E, the heat exchange section 201 (or 301) of the first adsorption core 20 (or the second adsorption core 30), the heater core 31, and the radiator 32 are connected in series by piping, and the first fluid circulation path is provided. a. The indoor heat exchanger 16 and the first evaporative condenser 60 (or the second evaporative condenser 70) are connected in series by pipes to form a second fluid circulation path b.

An adsorbing core / evaporative condenser cooler (hereinafter, abbreviated as an adsorbing core cooler) 25, which is a radiator, will be described later.
Heat exchange section 2 of adsorption core 20 (or second adsorption core 30)
01 (or 301) are connected in series by piping,
A third fluid circulation path (cooling fluid circulation path) c is configured.

A vapor compression refrigeration cycle 200 described later,
The adsorption core cooler 25 and the first evaporative condenser 60 (or the second evaporative condenser 70) are connected in series by piping,
A fourth fluid circulation path (cooling fluid circulation path) d is configured. The third fluid circulation path c and the fourth fluid circulation path d join at a junction e and branch at a branch f. The adsorbent core cooler 25 is provided in a merging flow path g downstream of the merging portion e and upstream of the branching portion f.

The electric pump 3 is provided in the first fluid circulation path a.
3, an electric pump 34 is provided in the merging path g, and an electric pump 35 is provided in the second fluid circulation path b.
(A) The flow of the heat exchange fluid in the middle arrow direction is generated. In the middle of the first and third fluid circulation paths a and c, a four-way valve 3 is provided.
The four-way valves 36 and 37 switch the supply source of the heat exchange fluid flowing into the first and second adsorption cores 20 and 30 to the engine E or the adsorption core cooler 25. ing. In other words, the four-way valve 3
The suction and desorption processes of the first and second suction cores 20 and 30 are switched by the control units 6 and 37.

The four-way valves 38 and 39 are provided in the middle of the fluid circulation paths b and d, and the four-way valves 38 and 39 allow heat exchange flowing out of the first and second water condensing evaporators 60 and 70 to flow. The supply destination of the fluid is switched to the indoor heat exchanger 16 or the adsorption core cooler 25. In other words, the four-way valves 38 and 39 switch the evaporation and condensation of water by the first and second water condensation / evaporators 60 and 70.

The radiator 32 arranged outside the vehicle compartment for cooling the engine cooling water is cooled by the outside air blown by the blower fan 43. Thermostat 42
When the temperature of the engine cooling water is lower than the predetermined temperature, the engine cooling water flows through the bypass circuit 41.

The first and second adsorption cores 20 and 30 are composed of an adsorption type refrigeration cycle 100 and a vapor compression type refrigeration cycle 200.
The temperature is controlled by First and second evaporative condensers 6
Reference numerals 0 and 70 evaporate the water when the water is adsorbed by the first and second adsorption cores 20 and 30, and condense the water when the water is desorbed by the first and second adsorption cores 20 and 30. . The heat exchange fluid flowing through the circulation path b is cooled by depriving latent heat of evaporation by evaporation of water in the first and second evaporative condensers 60 and 70, and exchanges heat with the vehicle interior air in the indoor heat exchanger 16. .

The vapor compression refrigeration cycle 200
Compressor 21 for compressing the refrigerant, blower fan 2 for supplying the high-pressure refrigerant
2a, a condenser 22 for condensing by exchanging heat with the outside air blown by 2a, a receiver 23 for gas-liquid separation, an expansion valve 24 for reducing the pressure of the refrigerant, first and second adsorption cores 20, 3.
It is composed of an adsorption core cooler 25 that cools the zero and first and second evaporative condensers 60 and 70. Each of these devices is connected by a pipe to form a refrigerant circuit R. Each device of the vapor compression refrigeration cycle 200 is installed outside the vehicle compartment (in the engine room).

In the adsorption core cooler 25, the expansion valve 24
Low-temperature refrigerant decompressed in (about 20-25 ° C)
And the refrigerant passage is formed such that the refrigerant passing through the joint flow path g comes into contact with the refrigerant. Therefore, in the adsorption core cooler 25, the heat of water adsorption in the first and second adsorption cores 20 and 30 and the heat of condensation of water in the first and second evaporative condensers 60 and 70 are reduced by the low temperature on the downstream side of the expansion valve 24. Heat is absorbed by the refrigerant.

Next, the operation of the vehicle air conditioner will be described. In the adsorption type refrigeration cycle 100, the first adsorption core 20 performs the adsorption step, the second adsorption core 30 performs the desorption step, the first adsorption core 20 performs the desorption step, and the second adsorption core performs the adsorption step. The second step to be performed is performed for a predetermined time (for example, 6
0 seconds). That is, the first stroke is performed by operating the electric pumps 33 to 35 to circulate the heat exchange fluid in the fluid circulation paths a to d and setting the four-way valves 36 to 39 to the solid line positions in FIG. .

In the first stroke, the engine cooling water of the engine E (about 90 ° C.) is circulated to the heat exchange section 301 of the second adsorption core 30 via the fluid circulation path a, so that the adsorption of the second adsorption core 30 is performed. The agent S is heated to desorb water. The water desorbed from the adsorbent S flows into the second evaporative condenser chamber 67. At this time, since the heat exchange fluid passing through the second evaporative condenser 70 is cooled by the adsorption core cooler 25, the water is condensed in the second condenser chamber 67. As the water is desorbed from the adsorbent S, the adsorbent S
The relative humidity in the vicinity becomes about 0.08, and it is regenerated.

On the other hand, since the first suction core 20 is cooled by the suction core cooler 25,
Adsorbent S adsorbs water. As a result, the pressure in the space formed by the first adsorption core chamber 62, the first communication portion 86, and the first evaporative condensation chamber 66 decreases, and the water in the first evaporative condensation chamber 66 evaporates.

At this time, in the first evaporative condenser 60, the heat exchange fluid is deprived of water by latent heat of evaporation and cooled. The cooled heat exchange fluid is transferred to the indoor heat exchanger 1 through the fluid circulation path b.
Flow into 6. As a result, the air flowing through the air conditioning duct 2 is cooled and dehumidified by the cooled heat exchange fluid flowing through the indoor heat exchanger 16. As a result of the water being adsorbed on the adsorbent S, the relative humidity near the adsorbent S becomes about 0.30.

In the second stroke, the four-way valves 36 to 39 are connected as shown in FIG.
(B) This is performed by setting the position of the middle dotted line. In the second step, the adsorption and desorption, evaporation and condensation in the first step are only interchanged, and the description of the second step is omitted. In the second step, the water adsorbed by the first adsorption core 20 in the first step is desorbed, and the second adsorption core 30 regenerated in the first step adsorbs water. The adsorption device for a vehicle is a device that simultaneously adsorbs water on one of the first and second adsorption cores 20 and 30 and regenerates the adsorbent on the other, and performs continuous operation of cooling.

Next, the operation and effect of this embodiment will be described. The adsorbent of this example is a porous composite that adsorbs water by using a combination of capillary action and sol-gel phase transition. Therefore, higher water absorption / desorption performance can be exhibited than when these two functions are used alone. Therefore, the adsorbent of this example is excellent in water adsorption / desorption performance.

The organic substance capable of causing the sol-gel phase transition is a crosslinked polymer, which is dispersed in an inorganic three-dimensional network structure and supported in the three-dimensional network structure. Therefore, swelling of the crosslinked polymer due to water adsorption is suppressed.

When the above adsorbent is used in a vehicle air conditioner, the adsorbent S efficiently adsorbs water by cooling. Therefore, the adsorption chamber refrigeration cycle 100 operates efficiently, and the air in the passenger compartment is efficiently cooled. Also,
The adsorbent S efficiently desorbs water by heating and has a high regeneration capacity.

Therefore, by using the adsorbent of this example, the adsorption core and the evaporative condenser exhibit excellent cooling performance, and it is possible to provide a vehicle air conditioner having excellent cooling performance. In addition, since the crosslinked polymer is supported by a three-dimensional network structure of an inorganic substance, swelling due to water adsorption is small. Therefore, the size of the suction core for containing the adsorbent S can be reduced.

Embodiment 2 Next, the water absorption performance of the adsorbent of the present invention was measured. The adsorbent of the present invention is the same as the adsorbent of the first embodiment.
For comparison, silica gel was produced by reacting with sodium silicate and sulfuric acid and then calcining, and the water absorption performance of this silica gel was also measured.

For the above-mentioned present invention and silica gel, a water adsorption isotherm shown in FIG. 4 was obtained. As is clear from FIG. 4, the adsorbent of the present invention had better water absorption performance than silica gel. In particular, water absorption performance in the region of the relative humidity of the operating environment of the vehicle air conditioner _(P / P 0 = _0.08~0.3) was high.

Embodiment 3 Next, the water absorption performance of the adsorbent of the present invention and a comparative adsorbent was measured. The adsorbent of the present invention is the same as the adsorbent of the first embodiment.

On the other hand, a comparative adsorbent was produced by the following production method. To a methanol solution of N-isopropylacrylamide and 2,2'-isobis (isobutyronitrile) as a polymerization initiator, add tetramethoxysilane and 0.1N hydrochloric acid as an acid catalyst, and at room temperature for about 3 hours. After stirring, a hydrolysis polymerization reaction was performed. continue,
The homogeneous solution thus obtained was left at about 60 ° C. for 7 days to carry out the polymerization reaction of N-isopropylacrylamide and evaporate the solvent to obtain a colorless transparent gel-like solid. The thus obtained inorganic-organic composite was baked at 600 ° C. for about 24 hours.

According to this production method, a comparative adsorbent, that is, a porous composite having an average pore volume of 0.36 cm ³ / g occupied by pores having a pore diameter of 1.0 nm to 1.5 nm (average) (Pore size 1.27 nm). The average pore diameter and pore volume were measured by a nitrogen adsorption method.

The water adsorption isotherm shown in FIG. 5 was obtained for the adsorbents of the present invention and the comparative examples thus obtained. As is clear from FIG. 5, the adsorbent of the present invention had better water absorption performance than the comparative adsorbent.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a sol-gel phase transition point of an organic substance in the present invention.

FIG. 2A is a schematic overall configuration diagram of a vehicle air conditioner according to a first embodiment, and FIG. 2B is a configuration diagram of an adsorption refrigeration cycle.

FIG. 3 is a partially cutaway view (a) of an airtight container, a perspective view of an adsorption core (b), and a state in which an adsorbent is filled between a tube of the adsorption core and a heat transfer fin in the first embodiment. FIG.

FIG. 4 is a diagram showing water adsorption isotherms of the adsorbent of the present invention and silica gel as a conventional example in Embodiment 2.

FIG. 5 is a diagram showing water adsorption isotherms of an adsorbent of the present invention and an adsorbent for comparison in a third embodiment.

[Explanation of symbols]

 1. . . 15. Vehicle air conditioning unit, . . 1. indoor heat exchanger, . . Air conditioning duct, 20. . . First core, 22. . . Condenser, 23. . . Receiver, 24. . . Expansion valve, 25. . . Adsorption core cooler, 30. . . 2nd core, 36-39. . . Four-way valve, 60. . . First steam condenser, 62. . . First adsorption core chamber, 63. . . Second suction core chamber, 66. . . First steam condensing chamber, 67. . . Second vapor condensation chamber, 70. . . Second steam condenser, 86. . . 1st communication part, 87. . . 2nd communication part, 100. . . Adsorption type-refrigeration cycle, 200. . . Vapor pressure refrigeration cycle, 201,301. . . Heat exchange section, 222. . . Tube, 223. . . Heat transfer fins, 601. . . First closed container, 602. . . 2nd closed container, . . Adsorbent, E. . . engine,

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 C09K 3/00 C09K 3/00 N 5/02 5/02 5/04 5 / 04 F25B 17/08 F25B 17/08 Z (72) Inventor Kin Koichi 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside Denso Co., Ltd. (72) Inventor Jun Kosaka 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside Denso, Inc. (72) Inventor Hideaki Sato 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside Indenso, Ltd. (72) Yoshiki Chujo 2-Terminal, Nishita-cho, Sakyo-ku, Kyoto, Kyoto F-term (Reference) 3L093 NN03 PP15 PP18 QQ01 RR03 RR05 4G066 AA20C AA22C AA23C AC02B AC12B AC17B BA09 BA25 CA43 DA03 FA07 FA21 FA26 4J002 AB011 BE001 BG131 CH021 DE096 DE136 DE146 DJ016 FD016 GD02 GN00

Claims (9)

[Claims] 1. An adsorbent for desorbing water by heating and adsorbing water by cooling, the adsorbent comprising an organic substance capable of causing a sol-gel phase transition by a temperature change; An adsorbent, which is a porous composite comprising an inorganic substance having a three-dimensional network structure, wherein the organic substance is dispersed in the inorganic three-dimensional network structure. 2. The adsorbent according to claim 1, wherein the organic substance is a polymer having a hydrophilic group and a hydrophobic group in a molecule. 3. The adsorbent according to claim 1, wherein the organic substance is a crosslinked polymer. 4. The method according to claim 1, wherein:
The organic substance is poly (N-isopropylacrylamide), poly (Nt-butylacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-
Diethylacrylamide), polyethylene glycol,
An adsorbent comprising one or more selected from a polymer comprising cellulose or polymethyl vinyl ether, or a crosslinked polymer obtained by crosslinking at least one of the polymers. 5. The method according to claim 1, wherein:
The inorganic substances are silica (SiO ₂ ), alumina (Al ₂
O ₃ ), titania (TiO ₂ ), or zirconia (Z
rO ₂ ) An adsorbent comprising one or more selected from the group consisting of rO ₂ ). 6. An organic substance capable of causing a sol-gel phase transition by a temperature change in a three-dimensional network structure of an inorganic substance, and an organic substance capable of causing the sol-gel phase transition by causing a solvent-extractable organic substance to be compatible with the organic substance. Obtaining a complex comprising: and a solvent-extractable organic substance;
A step of solvent-extracting the solvent-extractable organic substance from the complex to make the complex a porous body. 7. The method according to claim 6, wherein in the step of obtaining the complex, an uncrosslinked substance which can be an organic substance capable of causing a sol-gel phase transition is crosslinked in the presence of the inorganic substance and the organic substance which can be extracted by a solvent. A method for producing an adsorbent, comprising: 8. An adsorbent core provided with an adsorbent, a temperature control mechanism for controlling the temperature of the adsorbent core, an evaporative condenser, an indoor heat exchanger, and the adsorbent core and the evaporative condenser. A circulating passage for circulating heat between the evaporative condenser and the indoor heat exchanger, wherein the adsorbent desorbs water by being heated The evaporative condenser has a property of adsorbing water by being cooled, and the evaporative condenser evaporates water when the water is adsorbed by the adsorption core, and water evaporates when the water is desorbed by the adsorption core. A heat exchange fluid, wherein the heat exchange fluid is cooled by depriving latent heat of evaporation by evaporation of water in the evaporative condenser, and heat exchanges with vehicle interior air in the indoor heat exchanger. , The adsorbent according to any one of claims 1 to 5, An air conditioner for a vehicle, which is the adsorbent according to any one of the preceding claims. 9. An adsorption core provided with an adsorbent, a temperature control mechanism for controlling the temperature of the adsorption core, an evaporative condenser, an indoor heat exchanger, and a device between the adsorbent core and the evaporative condenser. The adsorbent is composed of a communicating part for circulating water and a flow passage for circulating a heat exchange fluid between the evaporative condenser and the indoor heat exchanger. The adsorbent desorbs water by being heated and is cooled. The evaporating condenser evaporates the water when the water is adsorbed by the adsorption core, and condenses the water when the water is desorbed by the adsorption core; The heat exchange fluid is a vehicle air conditioner that is cooled by depriving latent heat of evaporation by evaporation of water in the evaporative condenser, and performs heat exchange with vehicle interior air in the indoor heat exchanger, wherein the adsorbent is Is described in one of claims 6 and 7. An air conditioner for a vehicle, which is an adsorbent manufactured by a manufacturing method.