Energy & Fuels 2007, 21, 1169-1172

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Evaluation of Adsorption Equilibrium and Thermodynamic Performance of R-123 (2,2-Dichloro-1,1,1-trifluoroethane)-Activated Carbon Working Pair
Maiga A. Siddeye, Qin Wang, and Guangming Chen*
Institute of Cryogenics and Refrigeration, Zhejiang UniVersity, Hangzhou 310027, China ReceiVed August 5, 2006. ReVised Manuscript ReceiVed December 13, 2006

In adsorption refrigeration, one of the key factors is the choice of the working pair. Therefore, the adsorption and desorption equilibrium data are very useful for designers and also for the analysis of the thermodynamic performance. In this paper, R-123 (2,2-dichloro-1,1,1-trifluoroethane) refrigerant with activated carbon adsorption cooling working pair is investigated. The adsorption is carried out with a thermogravimetric balance, and the equilibrium data are obtained. The Dubinin-Astakhov modified model is used to calculate the adsorption equilibrium parameters. The maximum adsorption capacity is obtained. The standard estimate error (SEE) between the experiment and the model result is evaluated. The results give a good agreement with the experiment data. The influence of the heterogeneity coefficient n to the adsorption capacity is presented. Desorption also is carried out to calculate the thermodynamic performance (refrigeration capacity) at different regeneration temperatures.

1. Introduction The impacts of air conditioning and refrigeration systems on stratospheric ozone are primarily linked to the release of ozone depleting refrigerants, and their contributions to global warming stem from both release of refrigerants and emissions of greenhouse gases for associated energy use. Ozone depletion and global warming are major environmental concerns with serious implications for the future development of refrigerationbased industries. Under this background, adsorption refrigeration and heat pump systems have attracted increasing attention because they are environmental friendly and allow usage of a huge amount of industrial waste heat and renewable energies. Gas adsorption phenomena are strictly correlated to energy transfer and transformation, and they are regulated by temperature and pressure. Taking into account these properties and combining endothermic desorption with exothermic adsorption processes in closed cycles, it is possible to realize adsorption refrigeration whose external effect is equal to that obtained with vapor compression machines using an inverse Carnot cycle. Choosing the most appropriate adsorbent-adsorbate pair is one of the key factors determining the efficiency of the adsorption refrigeration and heat pumps. A suitable adsorbent to be employed in the adsorbate should be able to adsorb a high quantity of adsorbate and also to be easily regenerated regarding the pressure and temperature ranges of the operation, whereas a proper adsorbate should have a high latent heat of vaporization and a suitable boiling point. The lower the temperature at which adsorption occurs relative to the boiling point of the adsorbate, the larger will be the amount adsorbed. Since the desirable lowest adsorption temperature for a heat pump, for example, is room temperature, the boiling point should be preferentially higher than 20 C. There have been many adsorbate-adsorbents suggested for adsorption refrigeration and heat pump systems.
* Corresponding author. Tel.: +86 571 8795 1680. Fax: +86 571 8795 2464. E-mail: gmchen@zju.edu.cn.

Historically, Faraday in 1848 observed the cooling effect obtained by adsorbing ammonia into silver chloride, and in the 1920s, sulfur dioxide and silica gel were used for the air conditioning of railway carriages in the U.S.A.1 In recent times, the pairs used include water-zeolite,2 methanol-activated carbon,3 ethanol-activated carbon,4 ammonia-carbon,5,6 ammonia-salts,7,8 butane-carbon and R32-carbon,9 and R141bactivated carbon fiber.10 In this paper, R-123 (2,2-dichloro-1,1,1-trifluoroethane) has been chosen as a refrigerant and activated carbon has been chosen as its adsorbent in the adsorption system. The adsorption equilibrium has been investigated experimentally. At last, the refrigeration capacity per unit mass of adsorbent is given out. 2. Experimental Setup The gravimetric method consists of exposing a clean adsorbent sample to a pure gas at constant temperature. The change
(1) Hulse, G. E. Freight car refrigeration by an adsorption system employing silica gel. Refrig. Eng. 1924, 17, 2. (2) Cacciola, G.; Fichera, A.; Fichera, A. Advances on innovative heat exchangers in adsorption heat pumps. Presented at Proc. symp. le froid a sorption solide, Paris, 1992. (3) Douss, N.; Meunier, F. Experimental study of cascading adsorption cycles. Chem. Eng. Sci. 1989, 44, 225-235. (4) Cui, Q.; Tao, G.; Chen, H.; Guo, X.; Yao, H. Environmental benign working pairs for adsorption refrigeration. Energy 2005, 30, 261-271. (5) Critoph, R. E. Forced convection enhancement of adsorption cycles. Heat RecoVery Syst. CHP 1994, 14, 343-350. (6) Shelton, S. V.; Wepfer, W. J.; Miles, D. J. Ramp wave analysis of the solid-vapor heat pump. J. Energy Resour. Technol. 1990, 112, 6977. (7) Spinner, B. Les transformations thermochimiques an ammoniac. Presented at Proc. Symp. le froid a sorption solide, Paris, 1992. (8) Rockenfeller, U.; Kirol, P.; Sarkisian et al. Advanced heat pump staging for complex compound chemisorptions system. Presented at Proc. Symp. le froid a sorption solide, Paris, 1992. (9) Critoph, R. E. Evaluation, of alternative refrigerant-adsorbent pairs for refrigeration cycles. Appl. Therm. Eng. 1996, 16, 891-900. (10) Lin, S. H.; Chen, Y. W. Gas-phase adsorption isotherms and mass transfer characteristics of 1,1,-dichloro-1-fluoroethane (R-141b) by various adsorbents. J. Hazard. Mater. 1998, 57, 193-207.

10.1021/ef060361l CCC: $37.00 2007 American Chemical Society Published on Web 02/02/2007

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vacuum pump is kept open until the absorbent temperature reaches 200 C, and then the vacuum pumps are turned on to remove formed vapor for 1 h. After that, the equilibrium adsorption is carried out. At each adsorption process, the sample is heated at the regeneration temperature, which is 300 C for activated carbon, under vacuum conditions for 1 h to see if the drying weight changes.
Figure 1. Experimental setup of the thermogravimetric balance system: (1) U-tube manometer; (2) thermostatic bottle + refrigerant vessel; (3) valve; (4) valve; (5) vacuum pump; (6) thermobalance; (7) data acquisition; and (8) computer.

3. Working Pairs Selected The adsorbent tested in this experiment is coconut shell activated carbon, a commercial product from Shanghai Tangxin Active Carbon Co. Ltd. Its physical properties are mainly dependent on the pore structure. The specific surface area is 1230 m2/g with an average diameter of 0.5 mm. Commercial activated carbon is commonly produced from coal and coconut shell by chemical activation or physical activation processes. The refrigerant used is R-123. Its operating pressure is near to atmospheric pressure. It has a great latent heat, a high molecular weight, and a high critical temperature with a boiling point of 27 C. Although R-123 is a chemical of hydrochlorofluorocarbons (HFCs), which might be phased out in the future because of their nonzero ozone depletion potential (ODP), it shows better from the environmental view than many HFCs because its atmospheric lifetime is only as short as 1.3 years. The ODP is 0.012, and the GWP is only 76; meanwhile, R134a, for example, has a lifetime of 14 years and a very high GWP of 1320.11 So R-123 has a favorable overall impact on the environment that is attributable to some factors such as a short atmospheric lifetime, very low GWP, low ODP, low emissions of current design for R-123 chillers, and also exceptionally high efficiency. It is a safer refrigerant and its toxicity is very low, classified as a B1 refrigerant.12 While long-term alternatives have been identified for most refrigerant needs, the search is going on for R-123s replacement. For perspective, R-134a has largely replaced R-12 in appliances, commercial and transport refrigeration, mobile air conditioners, chillers, and other uses. These uses and the elusive R-123 replacement are the plums of the refrigerant market. Despite all the activity for the plums, niche applications, and service fluids, the important successor to replace R-123 has not emerged.13 R-123 has been employed in a vapor compression chiller. If using it with activated carbon as the working pair for refrigeration and heat pump systems, the compressor and its associated problems such as lubricant and electric power consumption are eliminated. Adsorption refrigeration has no moving parts and also has the potential of a long life. In addition, the pair R-123-activated carbon can use natural gas-fired heat, waste heat, or renewable energy such as solar energy, which all are environmentally friendly. The production cost of adsorption refrigeration is also lower than that of the traditional compressor one, since the activated carbon and the standard materials for the adsorber construction can be found at a lower price. Activated carbon has the advantage to be regenerated more easily than other adsorbents, making it an excellent adsorbent.
(11) Calm, J. M. Comparative Efficiencies and Implications for Greenhouse Gas Emissions of Chiller Refrigerants. Proceedings of Fourth International Symposium on Non-CO2 Greenhouse Gases; July 2005; pp 671-680. (12) ASHRAE. Addendum to Number Designation and Safety Classification of Refrigerants; ANSI/ASHRAE Standard 34a-1993 (Addendum to ANSI/ASHRAE 34-1992); American Society of Heating Refrigerating and Air-Conditioning Engineers (ASHRAE): Atlanta, GA, 1993. (13) Calm, J. M.; Wuebbles, D. J.; Jain, A. Impacts on global ozone and climate from 2,2-dichloro-1,1,1-trifluoroethane (R-123) emissions. J. Clim. Change 1999, 42 (2), 439-474.

in the weight of the adsorbent sample as well as pressure and temperature are measured when equilibrium is reached. Unlike other methods, this method allows the direct measurement of the amount adsorbed. It is considered as a well-established and accurate technique. The experiment setup shown in Figure 1 consists of a thermogravimetric balance type PCT-IA, calibrated from Beijing Optical Instrument Factory, with an accuracy of 0.01 mg, when the sample mass is in the range between the maximum weight of 200 mg and the minimum of 1 mg at a working room temperature varying between 10 and 35 C. The maximum pressure of the system is atmospheric pressure. The temperature fluctuation in the balance can be controlled within about 1 C. A thermostatic bottle with an adsorbate vessel containing refrigerant is submerged in a thermostatically controlled bath of liquid water; thus, the pressure within the system is kept at the saturation pressure corresponding to the bath temperature. The temperature of the bath is measured by a Pt 100 thermometer with an accuracy of (0.02 K after calibration from Yunnan Instrument Company. A glass tube of 10 mm diameter is used for the connection between the balance, the adsorbate vessel contained in the thermostatic vessel, and two glass vacuum valves and the vacuum pump. In order to obtain temperature and mass adsorbed data, a data-acquisition system model Hewlett-Packard Agilent 34970A and a remote microcomputer were used. A U-tube Hg manometer is used to monitor the vacuum of the system. The room temperature is also controlled so that there is no danger of any condensed liquid in any part of the glass tube, which might give an erroneous adsorption capacity measurement. In the thermogravimetric balance, the weight of the sample is measured as a function of the samples temperature and the saturated pressure of the refrigerant. Isobar and isotherm measurement can be carried out to obtain the entire field of the equilibrium state of the system. Isobaric desorption measurements can also be carried out. In an isobaric desorption procedure, the pressure of the vapor is fixed by setting the working fluid at a fixed temperature. The sample temperature is decreased from high to low temperature, and the temperature of the working fluid is fixed at 0, 5, and 10 C; for each adsorption temperature step, one equilibrium point consisting of temperature, saturated pressure, and adsorbed amount is obtained. To calculate the adsorbed amount, the dry mass is needed. In the thermogravimetric balance, the temperature and the mass of the adsorbent is given in millivolts (mv) so that we standardize with standard weight to find the relation between the milligram and millivolt for an eventual conversion. The temperature can be converted by the catalog given by the thermogravimetric balance manufacturer. To obtain the dry weight, the activated carbon is first weighed by an electronic balance with high accuracy (0.001 mg) and then put into the thermogravimetric balance. After that, the regeneration of the activated carbon is carried out at 250 C. In this phase, the valve connected to the thermogravimetric balance via the

Performance of R-123-ActiVated Carbon Working Pair

Table 1. Results of the Dubinin-Astakhov Equation Parameters adsorbent activated carbon refrigerant R-123 x0 0.58 K 1.9 n 1.37

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Table 2. Comparison of the Limiting Concentration of Different Refrigerants on the Activated Carbon refrigerant limiting concentration x0 R-717 0.2909 R-32 0.4769 R-600 0.2599 R-744 0.32411 R-123 0.580

Table 3. Comparison Between the Experiment Results and the Model adsorption temperature (C) 50 65 75 100 120 150 200 adsorption capacity (exp) (kg/kg) 0.48 0.44 0.42 0.36 0.31 0.25 0.168 adsorption capacity (DA model) (kg/kg) 0.4817 0.444 0.419 0.359 0.313 0.251 0.169 standard estimate of error 0.0043 0.009 0.0024 0.0028 0.0095 0.004 0.0059

Figure 2. Adsorption temperature vs adsorbed amount.

4. Test Results The following combination was tested: R-123-activated carbon. The adsorption capacity of the adsorbent was normally measured between the room temperature and 250 C under the pressure of 32.9 kPa for R-123 because of the safety of the balance. A modified Dubinin-Astakhov (DA) equation is adopted to describe the adsorption at equilibrium status, which is expressed as14

x ) x0 exp -k

[ ( )]
T -1 Ts
n

(1)
Figure 3. Desorption temperature vs desorbed amount.

where the adsorption capacity x represents the concentration of refrigerant adsorbed in adsorbent at temperature T and pressure p, x0 is the saturated adsorption capacity, Ts is the saturated temperature at adsorbent pressure p, and both k and n are the adsorption parameters depending on the material of adsorbentadsorbate pair. In order to calculate the Dubinin-Astakhov equations parameter, the least-squares method was used. According to the obtained equilibrium data, the results are given in Table 1From the obtained values of Dubinin-Astakhov parameters, some comparisons between our limiting concentration x0 and those of other authors using other refrigerants with the same adsorbent are made in Table 2. It can be seen in Table 2 that R-123 has the highest limiting concentration of all the refrigerants. After finding the parameters of Dubinin-Astakhov, a comparison is made between the experimental data and the model, and a standard estimate error is calculated as shown in Table 3. Figure 2 shows the relation between the adsorption temperature and the adsorbed amount, while Figure 3 shows the relation between the desorption temperature and the desorbed amount. From Figure 4, it can be observed that, from 1 to 3, the n has a great influence on the adsorption capacity, and after n > 3, the adsorption is almost stable. This can be explained, as said in many papers such as ref 15, that the n is varied between 1 and 3 for activated carbon and zeolite.
(14) Wang, R. Z.; Wang, Q. B. Adsorption mechanism and improvements of adsorption equation for adsorption refrigeration pairs. Int. J. Energy Res. 1999, 23 (10), 887-898. (15) Rudzinski, W.; Everett, D. H. Adsorption of gases on heterogeneous surfaces; Academic Press Inc.: San Diego, CA, 1992.

Figure 4. Influence of the heterogeneity coefficient (n) on the adsorption capacity.

The experiment of desorption is also carried out at different regeneration temperatures. For adsorption cooling, the refrigeration capacity is an important parameter. We used a simple method to calculate the refrigeration capacity. The sensible heat is considered as equal to zero, and only the desorption capacity is used to calculate the desorption refrigeration capacity. The following equation is used:

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Table 4. Results of Desorption and Refrigeration Capacity at Different Regeneration Temperatures desorption temperature (C) 80 100 130 160 200 230 250 desorption capacity (kg/kg) 0.153 0.21 0.307 0.42 0.543 0.639 0.686 refrigeration capacity (kJ/kg) 27.05 37.128 54.278 74.256 96 113 121.3

refrigeration capacity ) (desorption capacity) (latent heat of vaporization of the adsorbent at corresponding temperature)
In this study, the regeneration temperature starts from 80 to 250 C and the evaporator temperature is taken at 10 C. The calculated results can be seen in Table 4. From Table 4, it can be seen that R-123-activated carbon has a high desorption capacity at all regeneration temperatures. By comparing our results with those of the activated carbon-ethanol found by Cui et al.,4 one can see that R-123 desorption capacity is higher than that of ethanol at the same desorption temperature. Therefore, it can be used as a working pair for adsorption refrigeration by low quality of heat energy such as solar energy. 5. Conclusions In adsorption refrigeration, one of the key factors that influences the characteristics of the system is the working pair. Therefore, the adsorption and desorption equilibrium data of a working pair are very useful for designers and also for the analysis of thermodynamic performance. The adsorption and desorption equilibriums for R-123 were measured with activated

carbon at low pressures. The results show that R-123 gives a high adsorption capacity with activated carbon and also can be desorbed at a low regeneration temperature. The tested results also showed that R-123 with activated carbon can be described accurately with the modified Dubinin-Astakhov model, with which the standard estimated error between the experiment and the model is varied from 0.24% to 0.95%. The refrigeration capacity reaches 121.3 kJ/kg at 250 C. From this study, it can be seen that R-123 can be used as a refrigerant in the adsorption cooling system, even though the driving force is low-grade heat energy if activated carbon is used as its adsorbent.
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