JP2001048673A - Inorganic porous body and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an inorganic porous body excellent in pore characteristics and having high adsorption efficiency at low humidity, to obtain an adsorbent and to provide an air conditioner for a vehicle using the adsorbent. SOLUTION: An organic monomer having polymerizability and crosslinkability, a polymerization initiator, a crosslinking agent, a crosslinking initiator and a metal alkoxide capable of forming a three-dimensional network structure are made compatible with one another in the presence of a solvent in a step (a). A metal oxide having a three-dimensional network structure is formed from the metal alkoxide in a step (b). The organic monomer is polymerized to form a polymer and this polymer is crosslinked to form a crosslinked body in the network of the metal oxide in a step (c). The solvent is evaporated to make the metal oxide gel in steps (d) and (e). The organic crosslinked body is removed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, silica gel and zeolite have been generally used as adsorbents. In the case of silica gel, the pore diameter is uniformly distributed over a wide range, the pore volume occupied by a small pore diameter (for example, 2 nm or less) is small, and the water absorption efficiency at low humidity is poor.

[0003] In the case of zeolite, the pore diameter is relatively small and uniform, but the interaction between the pore wall and water is large, so that a large amount of heat is required for dehydration. For these reasons, these adsorbents have a very low efficiency of adsorbing and desorbing water at a low humidity required in an air conditioner using water as a refrigerant. Therefore, in order to use zeolite as an adsorbent for an air conditioner, a large volume is required. Therefore, miniaturization of the air conditioner is hindered, and it is not suitable for a vehicle air conditioner accommodated in a small space.

Japanese Patent Laid-Open Publication No. 5-85860 discloses that
It discloses that an organic-inorganic composite is used as an adsorbent. This organic-inorganic composite is obtained by dispersing a polymer having a urethane bond in a matrix of an inorganic oxide. This complex becomes porous by eluting and removing the polymer. However, such a porous inorganic adsorbent cannot be said to have sufficient control of the pore diameter, and cannot be said to have sufficient performance for use as an adsorbent for an air conditioner.

[0005]

SUMMARY OF THE INVENTION In view of the above problems, the present invention is directed to an inorganic porous material having excellent pore characteristics and high adsorption efficiency at low humidity, a method for producing the same, an adsorbent, and a vehicle air conditioner using the same. It is intended to provide a device.

[0006]

According to the present invention, as set forth in claim 1,
A step of making a polymerizable and crosslinkable organic monomer, a polymerization initiator, a crosslinker, a crosslinker, and a metal alkoxide capable of forming a three-dimensional network structure compatible with each other in the presence of a solvent; Forming a metal oxide having a three-dimensional network structure from the alkoxide, polymerizing the organic monomer to form a polymer, and crosslinking the polymers to form a cross-link in the three-dimensional network structure of the metal oxide; A porous body, a step of volatilizing the solvent to gel the metal oxide, and a step of removing the crosslinked body from the gelled metal oxide. It is a method of manufacturing the body.

The most remarkable point in the present production method is to form a three-dimensional network structure of a metal oxide and polymerize an organic monomer and crosslink the formed polymer in the network. As a result, the polymers are cross-linked to each other, so that they do not agglomerate with each other but are uniformly dispersed.

Therefore, when the metal oxide is gelled,
A gel is formed while surrounding the uniformly distributed crosslinked product.
For this reason, when the organic crosslinked body is subsequently removed from the gelled metal oxide, an inorganic porous body having uniformly distributed pores can be obtained in its place. Further, the obtained inorganic porous material has a small pore diameter, and thus has excellent adsorption performance at low humidity.

Further, according to the above production method, the pore volume occupied by pores having a pore diameter of 1.0 nm to 1.5 nm is 0.1 mm.
An inorganic porous material having a density of 20 cm ³ / g or more can be obtained. Furthermore, an inorganic porous material having a pore volume of 0.30 cm ³ / g or more occupied by pores having a pore diameter of 1.0 nm to 1.5 nm can be obtained. The obtained inorganic porous material is
Has excellent performance as an adsorbent. As described above, according to the present production method, an inorganic porous body having excellent pore characteristics and high adsorption efficiency at low humidity can be produced.

The organic monomer is an organic monomer having polymerizability and crosslinkability. As in the third aspect of the present invention, the organic monomer is preferably composed of one or more selected from amide compounds containing a carbon-carbon multiple bond.

[0011] The polymerization initiator initiates the polymerization reaction of the organic monomer. As in the invention of claim 5, the polymerization initiator is 2,2'-azobis (isobutyronitrile),
2'-azobis (2,4-dimethylvaleronitrile),
It is preferable to be composed of one or more selected from the group of organic peroxides. Some polymerization initiators also serve as crosslinking initiators. For example, 2,
2'-Azobis (isobutyronitrile) acts both as a polymerization initiator and as a crosslinking initiator.

The crosslinking agent crosslinks the produced polymers. As in the invention of claim 6, it is preferable that the cross-linking agent is one or more selected from the group consisting of methylene bisacrylamide, isocyanate compound and ethylene urea.

[0013] The crosslinking initiator initiates a crosslinking reaction between polymers formed by polymerization of the organic monomer. As in the invention of claim 7, the crosslinking initiator is 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), an organic peroxide,
It is preferable to be composed of one or more members selected from the group consisting of Bronsted acids and Bronsted bases.

The metal alkoxide can form a three-dimensional network structure by a condensation reaction or the like. As in the invention of claim 8, the metal alkoxide is preferably composed of one or more selected from the group consisting of silicon alkoxide, aluminum alkoxide, titanium alkoxide, and zirconium alkoxide.

The organic monomer, the polymerization initiator, the cross-linking agent, the cross-linking initiator and the metal alkoxide are compatible with each other by a solvent. Solvents include methanol, ethanol, isopropanol, 1,4-dioxane, tetrahydrofuran, dimethylsulfoxide, N, N-dimethylformamide, 1-
Methyl-2-pyrrolidone or the like can be used.

Next, a condensation reaction is performed between the metal alkoxides to form a three-dimensional network structure of the metal oxide. The three-dimensional network structure refers to a state in which metals of a metal oxide are three-dimensionally connected via oxygen.

As for the means for forming the three-dimensional network structure of the metal oxide, it is preferable that the pH of the reaction solution is 1 to 7. Thereby, a dehydration condensation reaction of the metal alkoxide occurs, and a three-dimensional network structure can be easily formed. On the other hand, when the pH of the metal alkoxide is lower than 1, the organic monomer and the organic polymer may be decomposed. When the pH is higher than 7, pores other than those obtained by removing the organic polymer are removed. Many may occur.

Next, the polymerization and crosslinking of the organic monomer are started by heating. When the polymerization and the crosslinked product of the organic monomer are formed by heating, the solvent is volatilized, and the gelation of the metal oxide proceeds.

Next, the solvent is volatilized to gel the metal oxide. The solvent can be volatilized by standing naturally, heating, or reducing the pressure. Next, the crosslinked body is removed from the metal oxide. The removal can be performed by burning out.

Further, in the above production method, a crosslinked body was formed using an organic monomer as a starting material. However, an inorganic porous material having uniform pore characteristics can be similarly produced using an organic polymer as a starting material. That is, as in the invention of claim 2, an organic polymer having a crosslinking property, a crosslinking agent, a crosslinking initiator,
A step of dissolving a metal alkoxide capable of forming a three-dimensional network structure in the presence of a solvent, a step of forming a metal oxide having a three-dimensional network structure from the metal alkoxide, and cross-linking the polymers. A step of forming a crosslinked body in the three-dimensional network structure of the metal oxide, a step of volatilizing the solvent to gel the metal oxide, and a step of forming the crosslinked body from the gelled metal oxide. And a step of removing the inorganic porous body.

The organic polymer used in the present production method is, for example, one or two selected from the group consisting of amide bond-containing polymers, polyethers and polyvinyl alcohol.
Preferably, it consists of more than one species. Others are the same as the above-mentioned production method using an organic monomer as a starting material.

Further, according to the tenth aspect of the present invention, an inorganic porous body can be obtained by the above manufacturing method. Further, as in the twelfth aspect, the obtained inorganic porous material can be used as an adsorbent.

[0023] Next, according to the invention of claim 11, the pore volume occupied by pores having a pore diameter of 1.0 nm to 1.5 nm is 0.20 cm ³ / g or more. There is a body.

Since the above-mentioned inorganic porous material has the above-mentioned pore characteristics, it has excellent adsorption efficiency at low humidity. On the other hand, when the pore diameter is less than 1.0 nm, water is adsorbed on the inorganic porous body even when the relative humidity near the inorganic porous body is lower than 0.08. Therefore, when such an inorganic porous material is used as an adsorbent, regeneration of the adsorbent requires a large amount of heat. On the other hand, when the pore diameter is larger than 1.5 nm, the object to be adsorbed is hardly adsorbed when the relative humidity near the inorganic porous body is 0.30, and it is difficult to obtain a sufficient amount of adsorption. .

In order to obtain a sufficient amount of adsorption, it is more preferable that the pore volume occupied by pores having a pore diameter of 1.0 nm or more and 1.5 nm or less is 0.30 cm ³ / g or more. Further, the inorganic porous material can be used as an adsorbent.

Next, as a vehicle air conditioner using the adsorbent, an adsorbent core provided with an adsorbent and a temperature control mechanism for controlling the temperature of the adsorbent core are provided. , An evaporating condenser, an indoor heat exchanger, a communicating portion for circulating water between the adsorption core and the evaporating condenser, and a flow passage for circulating a heat exchange fluid between the evaporating condenser and the indoor heat exchanger. The adsorbent has a property of desorbing water by heating and adsorbing water by cooling. The evaporative condenser is capable of absorbing water by the adsorption core. Water is condensed when the water is desorbed by the adsorption core, and the heat exchange fluid is cooled by depriving latent heat of evaporation by evaporation of the water in the evaporative condenser, thereby cooling the indoor heat. Heat exchange with the cabin air in the heat exchanger Cormorant a vehicle air conditioner, the adsorbent may vehicle air conditioner which is a adsorbent of claim 12.

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 is configured to repeat a temperature cycle of the adsorbent in the adsorption core between a temperature lower than 40 ° C. and a temperature higher than 90 ° C. every predetermined time. Is preferred. 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.

The adsorbent can be used not only for the air conditioner for vehicles but also for a ventilation air purifier, a dehumidifier and the like. When the adsorbent is used in a vehicle air conditioner, the operating range of relative humidity is set to 0.1.
It is preferably set to 08 to 0.30. Thereby, the cooling in the vehicle air conditioner can be performed more efficiently.

[0035]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 An adsorbent of the present invention and an air conditioner for a vehicle 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 made of silicon oxide and has a three-dimensional network structure in which fine pores are uniformly dispersed.

Next, a method for producing the adsorbent will be described. First, as shown in FIG. 1 (a), in a 50 ml capacity reaction vessel (eg, beaker, flask, etc.), a polymerizable and crosslinkable organic monomer, a polymerization initiator, a crosslinker, And the agent in the presence of a solvent. N-isopropylacrylamide (1.8 g) was used as the organic monomer. Methylene bisacrylamide (0.2 g) was used as a crosslinking agent. As a polymerization initiator and a crosslinking initiator, 2,2′-azobis (isobutyronitrile) (AIBN, 30 mg) was used. These are methanol (MeOH, 20m) as a solvent.
l). Next, tetramethoxysilane (2.0 g) as a metal alkoxide capable of forming a three-dimensional network structure was added to this solution.

Next, as shown in FIG. 1 (b), 0.1N hydrochloric acid (0.5 ml) was added to the solution and stirred at room temperature for 24 hours. Thereby, as shown in FIG. 1C, a three-dimensional network structure (metal oxide network) 91 of silicon oxide was formed.

Next, as shown in FIG. 1D, the solution was allowed to stand at 60 ° C. for one week to evaporate the solvent. As a result, the organic monomer 92 was polymerized to form a polymer, and the formed polymer was crosslinked in a network by a crosslinking agent to form a crosslinked body 97. At the same time, a silicon oxide having a three-dimensional network structure is gelled to form a transparent organic-inorganic hybrid gel (hereinafter abbreviated as gel) 9.
3 was obtained.

Next, as shown in FIG. 2 (f), the transparent gel was pulverized to obtain a pulverized product 94 which was particles of an organic-inorganic hybrid gel. As shown in FIG.
4 was fired at 600 ° C. for 24 hours to obtain inorganic porous particles 95 having a large number of pores 96.

The obtained inorganic porous particles 95 have an average pore diameter of 1.2 nm and a pore diameter of 1.0 nm to 1.5 n.
The pore volume occupied by m pores was 0.31 cm ³ / g or more.

FIG. 3 shows a water adsorption isotherm of the obtained inorganic porous particles. According to FIG.
It can be seen that when the value is as low as 0.3, especially about 0.2, the adsorption isotherm sharply increases the adsorption rate and reaches saturation immediately.
This indicates that the inorganic porous particles exhibit excellent adsorption characteristics at low humidity, and can be said to be suitable for use as an adsorbent.

The obtained inorganic porous particles are shown in FIG.
As shown in the figure, uniformly distributed pores were formed.
The reason why the pores are uniformly dispersed is considered as follows.
As shown in FIG. 4A, the crosslinked body 97 of the organic polymer formed in the silicon oxide network structure 91 is
Disperse uniformly without agglomeration. For this reason,
As shown in FIGS. 1 (e) and 4 (a), when the silicon oxide gels, a gel 93 is formed while surrounding the uniformly dispersed crosslinked body 97. Then, FIGS. 2 (g) and 4 (b)
As shown in (1), when the crushed product of the gel is fired, the crosslinked body 97 in the gel 93 is burned off, and the inorganic porous material particles 95 having uniformly dispersed pores 96 are obtained in the trace.

On the other hand, when only the polymerization of the organic monomer is carried out without adding the crosslinking agent, methylenebisacrylamide, and the crosslinking reaction is not carried out, as shown in FIG. Aggregated. Thereafter, when a three-dimensional network structure of the metal alkoxide was formed and gelled, relatively large pores 969 were formed in the traces of the aggregated portions 979 of the polymer as shown in FIG.
Was formed. The pore distribution was not as uniform as when the crosslinking agent was added.

Embodiment 2 In this embodiment, an embodiment in which the inorganic porous particles obtained in Embodiment 1 are used as an adsorbent and applied to a vehicle air conditioner will be described. The adsorbent was fixed to the heat exchange fins in the adsorption core of the vehicle air conditioner through a binder using water as a refrigerant. In FIG. 6, 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. Inlets 4,5
Are switched by the inside / outside air switching door 6.

Reference numeral 3 denotes a blower, which blows air into the air conditioning duct 2 by driving the 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 type 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 the first and second evaporative condensers 60. , 70
And first and second evaporating and condensing 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. 7A to 7C, 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. 7B 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. 6, the engine E, the heat exchange part 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 / evaporating condenser cooler (hereinafter, abbreviated as an adsorbing core cooler) 25, which 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.

An 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.

In the middle of the fluid circulation paths b and d, four-way valves 38 and 39 are provided, and by these four-way valves 38 and 39, heat exchange flowing out of the first and second water condensation evaporators 60 and 70 is performed. 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. .

Further, 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. 6B. .

In the first step, the engine cooling water (about 90 ° C.) of the engine E is circulated to the heat exchange section 301 of the second adsorption core 30 through 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. 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. In addition, the adsorbent S efficiently desorbs water by heating and has a high regeneration ability. 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.

[Brief description of the drawings]

FIGS. 1A to 1E are diagrams illustrating a method for producing inorganic porous material particles according to a first embodiment.

FIG. 2 is an explanatory view (f) to (g) showing a method for producing the inorganic porous material particles, following FIG. 1;

FIG. 3 is a diagram showing an adsorption isotherm of inorganic porous material particles in the first embodiment.

FIGS. 4A and 4B are cross-sectional explanatory views of inorganic porous particles before burning out of a crosslinked body and cross-sectional explanatory views of inorganic porous particles after burning out of a crosslinked body in Example 1. FIG.

5A and 5B are cross-sectional explanatory views of inorganic porous particles before burning of a crosslinked body and cross-sectional explanatory views of inorganic porous particles after burning of a crosslinked body in a comparative example.

6A is a schematic overall configuration diagram of a vehicle air conditioner according to a second embodiment, and FIG. 6B is a configuration diagram of an adsorption refrigeration cycle.

FIG. 7 is a partially cutaway view (a), 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 of the sealed container in the second embodiment. FIG.

[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 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, 91. . . Network structure, 92. . . Organic monomer, 93. . . Gel (organic-inorganic hybrid gel), 94. . . Crushed product, 95. . . 96. inorganic porous particles, . . Pores, 97. . . Crosslinked product, 969. . . Relatively large pores, 979. . . Polymer agglomeration,

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Jun Kosaka 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside Denso Corporation (72) Inventor Hideaki Sato 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Denso Corporation F-term (reference) 4G019 GA04

Claims (13)

[Claims] An organic monomer having polymerizability and crosslinkability, a polymerization initiator, a crosslinker, a crosslinker, and a metal alkoxide capable of forming a three-dimensional network structure are compatible in the presence of a solvent. A step of forming a metal oxide having a three-dimensional network structure from the metal alkoxide; and forming a polymer by polymerizing the organic monomer and crosslinking the polymers to form a three-dimensional network of the metal oxide. A step of forming a crosslinked body in the structure, a step of volatilizing the solvent to gel the metal oxide, and a step of removing the crosslinked body from the gelled metal oxide. A method for producing an inorganic porous material. 2. A process in which a crosslinkable organic polymer, a crosslinker, a crosslinker, and a metal alkoxide capable of forming a three-dimensional network structure are compatible with each other in the presence of a solvent. Forming a metal oxide having a three-dimensional network structure, cross-linking the organic polymers to form a cross-linked body in the three-dimensional network structure of the metal oxide, and evaporating the solvent to form a metal. A method for producing an inorganic porous body, comprising: a step of gelling an oxide; and a step of removing a crosslinked body from the gelled metal oxide. 3. The method for producing an inorganic porous material according to claim 1, wherein the organic monomer comprises one or more selected from amide compounds containing a carbon-carbon multiple bond. 4. The method for producing an inorganic porous material according to claim 2, wherein the organic polymer is at least one selected from the group consisting of an amide bond-containing polymer, polyethers, and polyvinyl alcohol. . 5. The method according to claim 1, wherein the polymerization initiator is 2,2′-azobis (isobutyronitrile),
One or two selected from the group consisting of 2,2′-azobis (2,4-dimethylvaleronitrile) and organic peroxides
A method for producing an inorganic porous material comprising at least one species. 6. The method according to claim 1, wherein:
The method for producing an inorganic porous material, wherein the crosslinking agent is at least one member selected from the group consisting of methylenebisacrylamide, isocyanate compound, and ethylene urea. 7. The method according to claim 1, wherein:
The crosslinking initiator is selected from the group consisting of 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), organic peroxide, Bronsted acid, and Bronsted base. A method for producing an inorganic porous material, comprising one or more selected ones. 8. The method according to claim 1, wherein:
The method for producing an inorganic porous material, wherein the metal alkoxide is at least one selected from the group consisting of silicon alkoxide, aluminum alkoxide, titanium alkoxide, and zirconium alkoxide. 9. The method according to claim 1, wherein:
The means for forming the three-dimensional network structure of the metal oxide comprises adjusting the pH of the reaction solution to 1 to 7 in a method for producing an inorganic porous material. 10. An inorganic porous material produced from any one of claims 1 to 9. 11. An inorganic porous material, wherein a pore volume occupied by pores having a pore diameter of 1.0 nm to 1.5 nm is 0.20 cm ³ / g or more. 12. An adsorbent comprising the inorganic porous material according to claim 10. 13. 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 heat exchanger 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 Claim 12
An air conditioner for a vehicle, characterized in that the air conditioner is an adsorbent.