KR101544721B1 - A fabrication method of material for adsorption and desorption of moisture using freeze drying, and the material for adsorption and desorption of moisture fabricated by this method. - Google Patents
A fabrication method of material for adsorption and desorption of moisture using freeze drying, and the material for adsorption and desorption of moisture fabricated by this method. Download PDFInfo
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- KR101544721B1 KR101544721B1 KR1020130114371A KR20130114371A KR101544721B1 KR 101544721 B1 KR101544721 B1 KR 101544721B1 KR 1020130114371 A KR1020130114371 A KR 1020130114371A KR 20130114371 A KR20130114371 A KR 20130114371A KR 101544721 B1 KR101544721 B1 KR 101544721B1
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Abstract
A method for producing a moisture absorbing / desorbing material, comprising the steps of preparing silica, salt and distilled water, preparing an impregnation solution by dissolving the salt in distilled water, mixing the silica with the impregnation solution, And freeze-drying the mixture to prepare a moisture absorbing / desorbing material. The silica is Fumed silica, and the salt is selected from calcium chloride (CaCl 2 ) and magnesium chloride (MgCl 2 ).
The present invention relates to a technique for manufacturing a water-absorbing material having excellent performance by impregnating commercially available silica particles with CaCl 2 and freeze-drying, and has a simple manufacturing process and a low operating cost (P / P o = 0.1 To 0.2) of 0.21 g-water / g-sorbent or higher in the adsorbent of the present invention.
In order to realize this, CaCl 2 is dissolved in water and mixed with the silica particles, and in the step of removing water used in the mixing, vacuum drying and freeze drying, which are general drying methods, are possible, and when the freeze drying method is used, .
In the case of wet silica, the performance of the adsorbent produced by vacuum drying exhibits the ability to adsorb moisture above 0.17 g-water / g-sorbent within the driving pressure (P / P o = 0.1 to 0.2). In the case of fumed silica, the water desorption material prepared by freeze-drying showed a great improvement in the maximum adsorption amount within the driving pressure range (P / P o = 0.1 to 0.2) to 0.21 g-water / g-sorbent.
Thus, mass production can be achieved by impregnating CaCl 2 without using a carrier which is difficult to synthesize as mesoporous silica and expensive, by the method of manufacturing the water desorption material of the present invention.
Description
The present invention relates to a moisture absorbing and desorbing material applicable to a water-absorbing refrigerator and its application, and a method of manufacturing a porous material by impregnating salt, freeze-drying, and a moisture absorbing and desorbing material using the same.
In the early 1980s, adsorption systems such as silica gel, zeolite, and activated charcoal were used as natural refrigerants such as water, alcohol, and ammonia. In 1986, 17kW adsorption type refrigerators using silica gel / water were commercialized in Japan. At present, Nishiyodo and Mayekawa in Japan are commercializing 70 to 500 kW absorption chillers and SorTech in Germany has 7.5 kW and 15 kW solar heating systems. Developed and sold.
At present, efficient utilization of energy is becoming a big issue in the world, and researches on the application technology of various industrial waste heat generated in industrial sites are actively being actively carried out. The industrial waste heat is mostly in the range of 70 to 90 ℃ in various forms such as medium and low temperature water and saturated water vapor, but is mostly discarded without being reused.
Adsorption - type refrigeration systems have attracted great interest as a way to effectively utilize these waste heat energy.
The adsorption refrigeration system can use waste heat from each process as a driving source and it is an environmentally friendly system that is not related to ozone layer destruction by using water as a refrigerant.
In the conventional commercialized adsorption refrigeration system, silica gel and water are used, but silica gel has a tendency to start adsorption at a low water vapor partial pressure due to strong hydrophilicity. In addition, the adsorption rate is low at the driving pressure range (P / P o = 0.1 to 0.2) on the adsorption refrigeration system, the desorption is not easy, and the amount of water adsorbed per unit adsorbent is as low as about 0.1 g-water / g-sorbent. That is, in order to improve the performance of the absorption type refrigeration system and to reduce the equipment cost, a new moisture absorbing and desorbing material having a higher water adsorption amount within the driving pressure range is required. Recent researches on mesoporous materials using SBA-15 and CaCl 2 have been published (Microporous and Mesoporous Materials 129 (2010) 243-250).
In this paper, the porous SBA-15 was synthesized and mixed with CaCl 2 -dried aqueous solution to evaporate the water, so that CaCl 2 was impregnated in the pores of SBA-15, and the adsorption characteristics of water were examined.
The maximum moisture adsorption within the driving pressure range (P / P o = 0.1 to 0.2) of the material produced in the above paper was measured to be 0.16 g-water / g-sorbent.
This is higher than the general silica gel, but the dynamic adsorption rate is slow and the maximum moisture adsorption amount is also unsatisfactory. In addition, mesoporous silica such as SBA-15 has a disadvantage in that it is difficult to mass-produce as well as difficult to manufacture.
In order to solve the above problems, the present invention provides a method of exhibiting a significantly higher moisture adsorption amount than a general high-temperature low-pressure drying process, in which salt is highly dispersed in a silica structure using a freeze- do.
A method for producing a moisture absorbing / desorbing material, comprising the steps of preparing silica, salt and distilled water, preparing an impregnation solution by dissolving the salt in distilled water, mixing the silica with the impregnation solution, And freeze-drying the mixture to prepare a moisture absorbing / desorbing material. The silica is Fumed silica, and the salt is selected from calcium chloride (CaCl 2 ) and magnesium chloride (MgCl 2 ).
The present invention relates to a technology for manufacturing a water-absorbing material having excellent performance by impregnating a commercially available silica particle with a salt such as CaCl 2 and freeze-drying, and has a simple manufacturing process and a low manufacturing cost, (CSPM) type adsorbent that adsorbs water at a concentration of 0.21 g-water / g-sorbent or more in a range of 0.1 to 0.2 ( o = 0.1 to 0.2).
In order to realize this, in the step of dissolving salts such as CaCl 2 in water and mixing with the silica particles and removing the water used for mixing, vacuum drying and freeze drying, which are general drying methods, are possible, and when freeze- Can be greatly improved.
That is, it is intended to provide a method for exhibiting a significantly higher moisture adsorption amount than a general high-temperature low-pressure drying process because the salt is highly dispersed in the silica structure using the freeze-drying process to reduce the particle size of the salt.
Also, in the case of wet silica, the performance of the adsorbent produced by vacuum drying exhibits the ability to adsorb moisture of 0.17 g-water / g-sorbent or higher in the driving pressure (P / P o = 0.1 to 0.2). In the case of fumed silica, the water desorption material prepared by freeze-drying showed a great improvement in the maximum adsorption amount within the driving pressure range (P / P o = 0.1 to 0.2) to 0.21 g-water / g-sorbent.
The silica-CaCl 2 composite adsorbent material having a higher water adsorption capacity than the high-temperature vacuum drying process without using a carrier which is difficult to synthesize as mesoporous silica and is expensive by the method of manufacturing the water desorption material of the present invention, Can be produced.
1 shows a drying method of a moisture absorbing / desorbing material according to an embodiment of the present invention.
2 shows a method of manufacturing a moisture absorbing / desorbing material according to an embodiment of the present invention.
FIG. 3 is a graph showing the amount of moisture adsorbed by the moisture absorbing / desorbing material produced according to the embodiment of the present invention.
4 is a graph showing moisture adsorption amount of a moisture absorbing and desorbing material produced according to another embodiment of the present invention.
FIG. 5 is a graph showing the moisture adsorption amount of the moisture absorbing / desorbing material produced according to another embodiment of the present invention.
A drying method of a moisture absorbing and desorbing material includes the steps of producing a mixture of silica impregnated with a salt and drying the mixture by Freeze Drying method.
Fumed silica is used as the silica in the step of producing the mixture impregnated with the salt in the silica.
The step of forming a mixture in which the silica is impregnated with a salt is preferably a salt containing at least one of calcium chloride (CaCl 2 ) and magnesium chloride (MgCl 2 ), most preferably calcium chloride (CaCl 2 ) to be.
In addition, the step of freeze drying the mixture is freeze-dried at a vacuum of 0.1 to 1 mmHg at -10 to -30 캜.
A method for producing a moisture absorbing / desorbing material, comprising the steps of preparing silica, salt and distilled water, preparing an impregnation solution by dissolving the salt in distilled water, mixing the silica with the impregnation solution, And a step of freeze-drying the mixture to prepare a moisture absorbing / desorbing material.
In the step of preparing the silica, the salt and the distilled water, the silica is fumed silica.
In preparing the silica, the salt and the distilled water, the salt preferably contains at least one of calcium chloride (CaCl 2 ) and magnesium chloride (MgCl 2 ), and most preferably calcium chloride (CaCl 2 ) to be.
In the step of mixing and stirring the silica with the impregnation solution to prepare a mixture, the mixture has a ratio of the salt: the silica in a weight ratio of 1: 1.5 to 1: 2.5.
In the step of preparing the moisture absorbing and desorbing material by freeze drying, the mixture is freeze-dried at a vacuum of 0.1 to 1 mmHg at -10 to -30 ° C.
It is obvious that the most preferable vacuum drying temperature can be varied depending on other factors such as the temperature of about -20 DEG C or the amount of the moisture absorbing and deicing material to be produced.
A water absorbing / desorbing material having a water adsorption amount of 0.1 to 0.5 g-water / g-sorbent at a relative pressure (P / P 0 ) of 0.1 to 0.3 and a temperature of 20 to 40 ° C, It is possible to manufacture the material.
As described above, the salt is most preferably calcium chloride (CaCl 2 ).
Further, the ratio of the salt: the silica of the moisture absorbing / desorbing material is
Most preferably, the weight ratio is 1: 2.
It is also possible to manufacture a moisture adsorber / desorber capable of adsorbing moisture at 20 to 40 ° C and desorbing moisture at 70 to 90 ° C, including the moisture absorbing / desorbing material of the present invention.
SS that are commercially available - SIL 230 (eseukem Tech), SS - SIL 52 (eseukem Tech) and AEROSIL 200 (Degussa) was impregnated with CaCl 2 to the silica particles with a high-performance CSPM (Composites Salt in Porous Matrix) Type of water A desorbent is prepared.
The SS-SIL 230 (Eschemtech) and SS-SIL 52 (Eschemtech) are gel type wet silica and the AEROSIL 200 is a fumed silica type.
250 g of CaCl 2 is completely dissolved in 500 mL of water, and this solution is put into a container containing 500 g of AEROSIL 200 and mixed well.
If the amount of water is insufficient, mix a small amount of water.
When fully mixed, half of the mixture is vacuum dried at 150 ° C in a vacuum oven. The other half is frozen in a refrigerator at -20 ° C, then placed in a freeze dryer and freeze-dried under vacuum.
Adsorbents were prepared by the same procedure for SS - SIL 230 and SS - SIL 52.
Each dried material was recovered and analyzed for nitrogen and moisture adsorption characteristics.
The types and characteristics of the silica used in the above Examples are shown in Table 1.
Sample
Kinds
Granularity
Surface Area (m 2 / g)
Pore Volume (cm 3 / g)
Pore Size (nm)
Fumed Silica
-
182
0.71
15.6
SS-SIL-52
Silica Gel (A)
3.5 μm
574
0.62
4.3
SS-SIL-230
Silica Gel (B)
3.5 μm
265
1.23
18.6
Table 2 shows the types and characteristics of the moisture absorbing and desorbing materials prepared in the above Examples.
Materials
Drying Condition
Surface Area (m 2 / g)
Pore Volume (cm 3 / g)
Pore Size (nm)
+ CaCl 2
Air & Vacuum (100 ℃)
113
0.44
150
Freeze Drying
117
0.49
166
SS-SIL-52
+ CaCl 2
Air & Vacuum (100 ℃)
134
0.23
6.9
Freeze Drying
132
0.24
7.1
SS-SIL-230
+ CaCl 2
Air & Vacuum (100 ℃)
174
0.72
16.5
Freeze Drying
156
0.7
17.9
The moisture adsorption amount of the moisture absorbing and desorbing material produced in the above embodiment is as shown in FIG. 3 to FIG.
As can be seen from FIG. 3, the moisture absorbing and desorbing material produced by
Also, it can be confirmed that the adsorption rate of water is fast because the curve indicating the amount of water adsorption is expressed in S (S) shape within the range of relative pressure P / P o = 0.1 to 0.2.
In comparison with this, it can be confirmed that the moisture absorbing and desorbing material produced by
In addition, the moisture adsorption / desorption using SS - SIL 230 and SS - SIL 52 showed similar adsorption amount of about 170g by using freeze drying or vacuum drying method.
That is, the performance of the adsorbent prepared by vacuum drying, which is a general drying method in the case of SS-SIL230 and SS-SIL52, is higher than 0.17 g-water / g-sorbent within the driving pressure (P / P o = Adsorption performance.
In comparison with the
These results indicate that the moisture absorbing and desorbing material prepared from
The silica-CaCl 2 composite material having a higher water adsorption capacity than that of the high-temperature vacuum drying process can be produced by using the method of the present invention for producing a water desorption material, without using a carrier which is difficult to synthesize, such as mesoporous silica, .
While the present invention has been described in conjunction with the accompanying drawings, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. It is to be understood that the present invention is not limited to the above-described embodiments. Accordingly, the scope of protection of the present invention should be construed according to the following claims, and all technical ideas which fall within the scope of equivalence by alteration, substitution, substitution, Range. In addition, it should be clarified that some configurations of the drawings are intended to explain the configuration more clearly and are provided in an exaggerated or reduced size than the actual configuration.
Claims (13)
(I) preparing fumed silica, salt and distilled water;
(Ii) dissolving the salt in distilled water to prepare an impregnation solution;
(Iii) mixing the fumed silica with the impregnation solution and stirring to prepare a mixture; And
(Iv) lyophilizing the mixture to prepare a composite salt-in-porous matrix (CSPM) type silica-CaCl 2 composite material by coalescing the salt into the pores of the fumed silica
, ≪ / RTI &
The salt contains at least one of calcium chloride (CaCl 2 ) and magnesium chloride (MgCl 2 )
The moisture absorbing / desorbing material
The relative pressure (P / P 0 ) is 0.1 to 0.3, and the temperature is 20 to 40 ° C
The water adsorption amount is 0.1 to 0.5 g-water / g-sorbent,
And water is desorbed under the condition of 70 to 90 占 폚.
In the step (iii)
The mixture
The salt: the ratio of silica
Those having a weight ratio of 1: 1.5 to 1: 2.5
Wherein the water-absorbing / desorbing material is a water-absorbing / desorbing material.
The lyophilization of step (iv)
Temperature -10 to -30 < 0 > C,
Performed under vacuum conditions of 0.1 to 1 mmHg
Wherein the water-absorbing / desorbing material is a water-absorbing / desorbing material.
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