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Preparation and Performance Testing of Composite Adsorbents for Solar Adsorption Refrigeration
Lingbao Wang1, Xianbiao Bu1,*, Huashan Li1,2 and Weibin Ma1 (1) Key Laboratory of Renewable
Energy and Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China. (2) University of Chinese Academy of Sciences, Beijing 100049, China. (Received 3 March 2012; revised form accepted 10 June 2013)

ABSTRACT: In order to develop a high-performance adsorbent for solar adsorption refrigeration, a series of composite adsorbents is prepared by impregnating CaCl2 into the pores of silica gel. Seven samples are prepared using various concentrations of CaCl2 aqueous solutions. Sorption properties of the samples are tested with gravimetric method. The test results indicate that both the adsorption amount and adsorption rate of the composite adsorbents increase significantly compared with that of the pure silica gel. The water uptakes of silica gel and composite adsorbent are 1.96 and 8.08 kg/100 kg adsorbents, respectively, with the relative humidity of 20% and adsorption time of 20 minutes. Subsequently, a novel solar adsorption chiller is designed, in which the composite adsorbent is used as an adsorbent and water as a refrigerant. Performance testing of the adsorption chiller shows that the cooling capacity, specific cooling power and coefficient of performance are 1.03 kW, 128.3 W/kg and 0.27, respectively, when hot water temperature, cooling water temperature and circulation time are 90 C, 35 C and 15 minutes.

1. INTRODUCTION The solar-powered adsorption refrigeration technology has rapidly developed in recent years owing to the increasing energy crisis. Adsorption refrigeration systems have the advantages of being environmentally benign, zero ozone depletion potential as well as zero global warming potential with the use of natural refrigerants such as water, ammonia, methanol. Less vibration, simple control, low initial investment and expenditure and less noise are the advantages of adsorption systems over the existing vapour-compression and absorption systems (Wang 2001; Wang and Oliveira 2006). The major drawbacks hindering its competitiveness are its bulkiness and low operating efficiency when compared with the vapour-compression refrigeration system. This is because the physical adsorption working pairs, such silica gelwater, have fewer cycle adsorption quantities, slow adsorption rate and poor thermal conductivity. By contrast, the chemical working pairs (such as CaCl2/NH3 and BaCl 2/NH 3) have better adsorption performance (Wang et al. 2004). However, the phenomenon of salt swelling and agglomeration is critical to heat and mass transfer performance. The design of heat and mass transferenhanced adsorbers as well as the heat and mass recovery circulating system is used to boost the coefficient of performance (COP), which reduces the
*Author to whom all correspondence should be addressed. E-mail: buxb@ms.giec.ac.cn (X.B. Bu).

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amount of adsorbent required (Boelman et al. 1997; Alam et al. 2000; Liu et al. 2005). Another way of increasing the competitiveness would be to use high-performance adsorbent with low regeneration temperature (Wang et al. 2006). The optimization of heat and mass transfer alone will not enhance COP if an adsorbent with poor adsorption capacity is used (Hamamoto et al. 2005; Zhu et al. 2006; Daou et al. 2007). Aristov et al. (2002) indicated that the future progress will be possible only if adsorbents with high-adsorption capacity and innovative performance are used. To develop innovative adsorbents, several types of porous media are used to synthesize composite adsorbents with metal chlorides, such as expanded graphite, activated carbon, activated carbon fibre, vermiculite, MCM-41 (a type of mesoporous molecular sieve). The utilization of expanded graphite can enhance the heat and mass transfer properties of adsorbents (Spinner 1993). In addition, there is no expansion during the adsorption process (Han et al. 1998). Dellero et al. (1999) studied three mixtures of carbon fibres with MnCl2, and found that the samples not only provide a very fast reaction, but also avoid the agglomeration phenomenon. Tokarev et al. (2002) confined CaCl2 in a mesoporous host matrix (MCM-41) to improve the mass-transfer performance. In this paper, the silica gel/CaCl2 composite adsorbent is made by impregnating the silica gel into CaCl2 aqueous solutions. Seven samples are prepared with different concentrations of CaCl2. Subsequently, the sorption properties of these samples are tested with gravimetric method and compared with each other. Finally, an adsorption chiller is produced using the optimal adsorbent.

2. EXPERIMENTAL SECTION 2.1. Materials and Equipment The main raw materials and equipment are shown in Table 1. The parameters of silica gel are listed in Table 2.

TABLE 1. Raw Materials and Equipment No 1 2 3 4 5 Name Silica gel CaCl2 Deionized water Temperature and humidity chamber Electronic balance Specification Spherical granules Analytically pure LY-2150 EJ-200 Manufacturer Qingdao Meigao Group Guangzhou Chemical Reagent Co. Ltd. Self-made Dongguan Liyi Experiment Instrument A&D (Guangzhou ) Co. Ltd

TABLE 2. Characteristics of Silica Gel Particle diameter (mesh) 2028 Pore diameter (nm) 47 Specific surface area (m2/g) 450600 Pore volume (ml/g) 0.500.80

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2.2. Preparation Process The process of impregnation of CaCl2 into the pores of silica gel mainly involves the preparation of the CaCl2 aqueous solution and the immersion of the silica gel into this solution (Gong et al. 2010). The temperature of the CaCl2 aqueous solution is 40 C. The vacuum tank used for impregnation is a flange connection. The detailed preparation process is as follows: 1. Prepare CaCl2 aqueous solution. Keep the solution under ambient temperature for 2 hours, and stir from time to time in order to prevent crystallization. 2. Put dry silica gel into the vacuum tank, and then perform vacuum pumping. 3. Put the vacuum tank into the thermostatic water bath whose temperature is set at 90 C, and then continue vacuum pumping. 4. Inject the prepared CaCl2 aqueous solution into the vacuum tank and keep therein for 2436 hours to allow the salt solution to penetrate and fill into all the pores. 5. Remove the flange, and then filter out the composite adsorbent with a sieve. 6. Lay and scatter the composite adsorbents inside the thermostatic humidistat chamber (THC; temperature 90 C). The THC allows choosing and keeping both the temperature and relative humidity inside constant. During this process, the composite adsorbents are being taken out and weighed from time to time until their weight losses are found to be negligibly small. Using these methods, the silica gels are immersed in different concentrations of CaCl2 aqueous solutions: 0% wt, 10% wt, 20% wt, 30% wt, 40% wt, 50% wt and 56.14% (saturated solution), respectively, and seven composite adsorbent samples are prepared, as shown in Table 3. 2.3. Performance Testing In this paper, the adsorption performance is measured in a THC, with uncertainties of 0.5 C for temperature and 5% for relative humidity. In general, in the adsorption refrigeration system, the adsorption process is slower than desorption process. Therefore, the study on the adsorption process is more meaningful (Akahira et al. 2004). In this experimental study, the adsorption temperature and relative humidity are set as 40 C and 2060%, respectively. The cooling water temperature of the adsorption refrigeration system is generally about 30 C, and therefore, the adsorption temperature of 40 C is appropriate, considering the difference in heat transfer temperature between the adsorption bed and the adsorbents. Desorption is performed in the drier whose temperature is set at 90 C. The weight change is recorded by an electronic balance placed in the THC. The measuring range and precision of the electronic balance are 120 and 0.001 g,
TABLE 3. CaCl2 Loadings of Different Samples Sample S0 S10 S20 S30 S40 S50 Ss Solution concentration (%) 0 10 20 30 40 50 56.14 CaCl2 loadings (%) 0 7.26 15.38 19.87 32.14 37.75 40.30

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respectively. The mass of every adsorbent sample placed in the THC is 50 g. The data-collection interval is 1 second and the testing time of every sample is 2 hours for every fixed relative humidity. The experimental procedure can be summarized as follows: 1. Put the samples in the drier where they are dried at the temperature of 90 C for 2 hours. 2. The temperature and relative humidity of the THC are set to 40 C and 20%, respectively. 3. Put the samples on the electronic balance placed in the THC. The weight change is recorded by the electronic balance. The lasting time is 2 hours. 4. Repeat Step 1. 5. Change the relative humidity of the THC, and then repeat Steps 14.

3. RESULTS AND DISCUSSION 3.1. Adsorption Isotherm The adsorption performance is mainly calculated based on adsorption quantity and adsorption rate. The adsorption quantity can be reflected by the adsorption isotherm. The adsorption isotherms of the samples are shown in Figure 1. The figure shows that the adsorption quantity of every sample increases with the increasing of relative humidity. It is very interesting to note that the increase in the adsorption quantity of composite adsorbents is much larger than that of the pure silica gel. For example, with the increase of the relative humidity from 20% to 60%, the water uptake of S50 rises from 15.70 to 42.32 kg/100 kg, whereas the water uptake of S0 just rises from 2.0 to 8.15 kg/100 kg. In addition, the adsorption quantity and adsorption rate of the composite adsorbents are larger than those of S0 under the same relative humidity. This is likely to due to the fact that the water

45
S0

40

Adsorption temperature 40 C Adsorption time 2 h

Water uptakes (kg/100 kg adsorbents)

S10 S20 S30

35 30 25 20 15 10 5 0

S40 S50 Ss

20%

30%

40%

50%

60%

Relative humidity Figure 1. Adsorption isotherms at T = 40 C.

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adsorption capability of the CaCl2 is superior to those of the silica gel, and the adsorption quantity and adsorption rate of the composite adsorbents are thus larger than the silica gel. 3.2. Adsorption Rate To develop a high-performance adsorbent for solar-powered adsorption refrigeration system, not only the adsorption quantity is demanded largely, but also the adsorption rate should be fast. The curves of adsorption performance of samples S0, S30, S50 and Ss are shown in Figure 2. From the figure, it can be concluded that the adsorption quantities of all samples increase with the test time. In the beginning they increase fast, and then they increase slowly.
Water uptake (kg/100 kg adsorbents) Water uptake (kg/100 kg adsorbents)

14 12 10 8 6 4 2 0 0 20 40 60 80 100 120
20% 30% S0 40% 50% 60%

45 40 35 30 25 20 15 10 5 0 0 20 40 60 80 100 120
20% 30% 40% 50% 60%

S30

Adsorption time (minutes)

Adsorption time (minutes)

Water uptake (kg/100 kg adsorbents)

Water uptake (kg/100 kg adsorbents)

45 40 35 30 25 20 15 10 5 0 0 20 40 60 80 100 120
20% 30% 40% 50% 60%

45 40 35 30 25 20 15 10 5 0 0 20 40 60 80 100 120
20% 30% 40% 50% 60%

S50

Ss

Adsorption time (minutes)

Adsorption time (minutes)

Figure 2. Water uptakes of samples versus time.

At the relative humidity of 20%, the adsorption quantity of S0 is always 1.96 kg/100 kg, when the adsorption time is larger than 30 minutes, that is, S0 reaches adsorption equilibrium when the adsorption time is 30 minutes. With the adsorption time being 20, 40, 60, 80 and 100 minutes and the relative humidity being 20%, the adsorption quantity of S0 is 1.959, 1.959, 1.961, 1.99 and 1.99 kg/100 kg adsorbents, respectively, while the adsorption quantity of S50 is 8.08, 11.72, 13.95, 14.65 and 15.31 kg/100 kg adsorbents, respectively. It can be seen that the adsorption rate of the composite adsorbent is much faster than that of the pure silica gel. During the first 20 and

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60 minutes, S0 reaches 98.4% and 98.5% of the overall water uptake in 100 minutes, while S50 reaches 52.8% and 91.1%. It indicates that the more CaCl2 loading is, the more time it needs to reach the adsorption equilibrium. The likely reasons may be explained as follows: on one hand, due to larger adsorption quantity and poor thermal conductivity of silica gel, the adsorption heat of the composite adsorbents cannot be discharged in time. The adsorption temperature of the composite adsorbents is much higher than the silica gel. Therefore, the composite adsorbents take much longer time to reach adsorption equilibrium. On the other hand, the composite adsorbents are prepared by filling CaCl2 into the pores of the silica gel, which makes the pore volume of the composite adsorbents much smaller than that of the pure silica gel. This thus weakens the mass transfer performance of composite adsorbents, which extends the time to reach the adsorption equilibrium. 3.3. Effect of CaCl2 Content The water uptakes of the samples are shown in Figure 3. It is found that the adsorption quantities increase with the increasing of CaCl2 mass concentration (<50%); however, when the CaCl2 mass concentration is above 50%, the adsorption quantities decrease. The adsorption quantity of Ss is smaller than that of S50 at the same relative humidity. This is because when the CaCl2 mass concentration is too high, it is much easier for the crystallization phenomenon to occur, which jams the pores of the silica gel, making it not easy for the water vapour to penetrate into the pores. Therefore, it can be concluded that the optimal CaCl2 mass concentration is 50% in this study.

45 40 35 30 25 20 15 10 5 0

20% humidity 30% humidity 40% humidity 50% humidity 60% humidity

Adsorption time 2 h

Water uptakes (kg/100 kg adsorbents)

10

20

30

40

50

Mass concentration (%) Figure 3. Water uptakes of samples versus CaCl2 mass concentration.

3.4. Refrigeration Performance The objective of the preparation of composite adsorbents is to develop a high-performance and compact adsorption refrigeration prototype driven by solar energy. The relative humidity and the adsorption time in the typical adsorption refrigeration chiller are 20% and 520 minutes,

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respectively. The curves of the specific cooling power (SCP) of the seven samples are shown in Figure 4. It can be seen that the SCP reaches the maximum in the first 3 minutes and then decreases with time. However, the adsorption time cannot be chosen for 3 minutes, as the adsorption bed is in the process of cold and heat alternation. If the switch between the adsorption operation and the desorption operation is too frequent, then the heat loss of the adsorption bed will be large. In addition, the COP of the adsorption refrigeration will be low.
350 300

S0 S10 S20 S30 S40 S50 Ss

SCP (W/kg)

250 200 150 100 50 0 0 2 4 6 8 10 12 14 16 18 20 22

24

Adsorption time (minutes)

Uptake (kg/100 kg adsorbents)

8 6 4 2 0 0 2 4 6 8 10 12 14 16 18 20 22

S0 S10 S20 S30 S40 S50 Ss

24

Adsorption time (minutes) Figure 4. Water uptakes and SCPs of samples versus time.

Assuming the latent heat of vapourization of water is constant in the adsorption process, the SCP is calculated as follows: Lx tc

SCP =

(1)

where L is latent heat of vapourization, x is adsorption quantity and tc is cycle time. From Figure 4, the SCPs of the composite adsorbents are found to be much higher than those of the corresponding pure silica gels. When the adsorption time is 5, 10, 15 and 20 minutes, the SCP of S50 is 245, 222.7, 189 and 175 W/kg, whereas the SCP of pure silica gel is 113.4, 73.1, 56.3 and 42.6 W/kg. To utilize solar energy, a compact adsorption refrigeration prototype is developed, and the sample S50 is selected as the adsorbent. A schematic diagram of the adsorption chiller is presented

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in Figure 5. Compared with the conventional designs in which vacuum valve is needed, the current system has the advantage of no vacuum valve in the system, which can remarkably improve the reliability of adsorption refrigeration systems. The prototype operates intermittently. A tube-fin heat exchanger is used in this system, and 8-kg S50 is packed between the fins. Based on the aforementioned analysis and previous experiences, the adsorption process and desorption process are set to 10 and 5 minutes, respectively. The prototype is designed with a cooling capacity of

Thermometer P

Pressure sensor Fin Adsorber Adsorbents T Water pump 1 F Hot water

Condenser

Hot water T T Cooling water

Cooling water F Flow meter

Cooling water T

Cooling water F F Chilled water Chilled water

Evaporator

Figure 5. Schematic representation of adsorption chiller.

1 kW, and the dimensions of the prototype are 500 (mm, depth) 600 (mm, width) 500 (mm, height). All the valves used in the prototype are controlled by a programmable logic controller. The COP is defined as the ratio of the cooling output at the evaporator to the energy absorbed by the adsorption bed. As the metal heat capacity is very small, it has been neglected in the calculation of the COP. Therefore, qmc ( tc1 tc 2 ) qmh ( th1 th 2 )

COP =

(2)

where qmc is the mass flow of chilled water, tc1 is the inlet temperature of the chilled water, tc2 is the outlet temperature of the chilled water, qmh is the mass flow of the hot water, th1 is the inlet temperature of the hot water and th2 is the outlet temperature of the hot water. The performance testing of adsorption chiller shows that the cooling capacity, SCP and COP are 1.03 kW, 128.3 W/kg and 0.27, when hot-water temperature, cooling-water temperature and circulation time are 90 C, 35 C and 15 minutes, respectively.

4. CONCLUSIONS In this paper, a series of composite adsorbents is prepared by soaking silica gel into CaCl2 aqueous solutions and their adsorption performances are tested. After that, an adsorption chiller is produced

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using S50 as an adsorbent and the cooling capacity is tested. The following conclusions can be drawn based on the experimental results: 1. The adsorption quantity and adsorption rate of composite adsorbents increase greatly as compared with the pure silica gel. The water uptake of S50 and the pure silica gel are 15.70 kg/100 kg and 2.0 kg/100 kg adsorbents, respectively, at the relative humidity of 20% and adsorption time of 2 hours. 2. The adsorption quantity of samples increases with the increasing concentration of CaCl2 aqueous solution, when the CaCl2 mass concentration is less than 50%, but when the CaCl2 mass concentration is above 50%, the adsorption quantity decreases. 3. For the composite adsorbents, the more the CaCl2 loading is, the more time it needs to reach the adsorption equilibrium, owing to larger adsorption quantity and poor thermal conductivity. 4. The SCP of the sample S50 is largely superior to that of S0, and therefore, S50 is used as the adsorbent in the adsorption prototype. The performance testing of the adsorption chiller shows that the cooling capacity, SCP and COP are 1.03 kW, 128.3 W/kg and 0.27, when hotwater temperature, cooling-water temperature and circulation time are 90 C, 35 C and 15 minutes, respectively.

ACKNOWLEDGEMENTS This work was financially supported by the Innovation Program of Chinese Academy of Sciences (Grant No. y007y51001), the National Natural Science Foundation of China (Grant No. 51106161) and the Guangdong province and Chinese Academy of Science Comprehensive Strategic Cooperation Project (Grant No. 2012B091100263).

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