Carbon 44 (2006) 747–752 www.elsevier.com/locate/carbon Performance analysis of an adsorption refrigerator using activated carbon in a compound adsorbent Z.S. Lu, R.Z. Wang *, L.W. Wang, C.J. Chen Institute of Refrigeration and Cryogenics, Shanghai Jiao Tong University, Shanghai 200030, China Received 22 July 2005; accepted 13 September 2005 Available online 2 November 2005 Abstract To improve the performance of the adsorption refrigeration of CaCl2–ammonia adsorption system, activated carbon has been distributed uniformly in the mass of CaCl2, thereby helping to enhance mass transfer and uplift the cooling power density. A multifunctional heat pipe adsorption refrigerator, in which activated carbon-CaCl2 is used as compound adsorbent and ammonia as refrigerant, is designed. Water and acetone are used as working liquids for the heat pipe. This paper presents a study on the adsorption refrigeration performances of this adsorption refrigerator under two different working conditions, ice-maker for fishing boat driven by the waste heat from exhaust gases, and solar ice-maker driven by solar water heating. The obtained average SCP (specific cooling power) and the COP (coefficient of performance) of the refrigerator were measured to be 770.4 W/kg and 0.39 at about 20 °C of evaporating temperature for the former working condition, and they were 161.2 W/kg and 0.12 at about 15 °C of evaporating temperature for the later working condition. Ó 2005 Elsevier Ltd. All rights reserved. Keywords: Activated carbon; Carbon/carbon composites; Mixing; Adsorption; Adsorption properties; Thermodynamic properties 1. Introduction Adsorption refrigeration systems have the advantages of being environmentally benign, having zero ozone depletion potential (ODP) as well as zero global warming potential (GWP) due to the use of natural refrigerants such as ammonia, water, methanol, etc. It is also attractive for the efficient use of solar energy and low-grade waste heat. Less vibration, simple control, low initial investment and expenditure, and less noise are the advantages of adsorption systems over the existing vapor compression and absorption systems [1]. Adsorption working pairs for adsorption refrigeration includes physical adsorption working pairs, chemical adsorption working pairs and compound adsorption working pairs. The typical physical adsorption working pairs are * Corresponding author. Tel.: +86 21 6293 3838; fax: +86 21 6293 2601. E-mail address: [email protected] (R.Z. Wang). 0008-6223/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2005.09.016 mainly silica gel–water [2,3], zeolite–water [4,5], activated carbon–ammonia [6,7], activated carbon–methanol [8]. In addition, activated carbon-R134a has been also considered as the physical adsorption working pair [9,10]; A typical chemical adsorption working pair is CaCl2–ammonia which has a large adsorption capacity although subject to the critical problems of expansion and agglomeration [11]. Compound adsorbents have the advantages of both porous medium and chemical adsorbents. One typical example is the mixture of activated carbon and CaCl2, the well-arranged mixture of which is a good adsorbent on ammonia, yielding long lasting and stable operational performances. This paper presents the performances of an adsorption ice-maker which employs the activated carbon and CaCl2 as compound adsorbent and ammonia as adsorbate. The results show that the consolidated compound adsorbent can greatly improve the refrigeration performance, due to the fact that its composition and physical structure contribute to enhancing significantly heat and mass transfer. 748 Z.S. Lu et al. / Carbon 44 (2006) 747–752 In this paper, compound adsorbent of activated carbon and CaCl2 are used to improve adsorption performance. Also, in order to enhance heat transfer in the adsorbent beds, and perform an efficient heat recovery between the two adsorbers, heat pipes are used in the present system. 2. Compound adsorbent by mixing activated carbon and CaCl2 In comparison with the activated carbon and CaCl2 adsorbents, the compound adsorbent, obtained by mixing activated carbon and CaCl2, has a high volume adsorption capacity while avoiding the problems of agglomeration and performance attenuation. The high adsorption performance stems from the presence of activated carbon with its important network of pores cavities which contribute to enhance significantly the mass transfer. The research group of Shanghai Jiao Tong University has studied the compound adsorbent adsorption properties with various mass ratios of activated carbon and CaCl2 [12]. The result shows that the best mass ratio of activated carbon and CaCl2 is 1:4, as shown in Fig. 1. When the compound adsorbent is consolidated, the adsorption performance var- Fig. 1. Granular compound adsorbent after adsorption (mass ratio of activated carbon and CaCl2 is 1:4). Fig. 2. Consolidated compound adsorbent. ies with the consolidated compound adsorbent density. At the optimal density, a significantly improved adsorption performance is reached. The consolidated adsorbent is shown in Fig. 2. Here, CaCl2 powder, coconut shell activated carbon (14–28 mesh) and a small quantity of highquality cement are mixed and compacted together in a consolidated adsorbent in that mixture, the cement acts as binder. The mass fractions of CaCl2, activated carbon and cement in the consolidated compound, are in the proportion of 16:4:1, respectively. 3. Description of the system The heat pipe-type adsorption refrigeration system, used for the experimental researches, is shown in Fig. 3. It comprises two adsorbers, each of them is heated by a boiler and cooled by a water heat exchanger via the gravity heat pipe working liquid (water or acetone). The switching of the valves, make the adsorber plays alternately the role of condenser or evaporator for the gravity heat pipe. The main idea of the above design is to solve the corrosion problems. Indeed, when the adsorption refrigerator is used as ice-maker for fishing boat powered by the waste heat of the exhaust gases, serious corrosion problems may occur if the steel adsorber is heated by the exhaust gases and cooled by seawater directly. In the laboratory experiment, electric heating was used to simulate both the exhaust gas heating and the solar heating. A thermostat was used to control the cooling water temperature, thus various working conditions with different cooling water temperature could be simulated. The consolidated compound adsorbent was used as the adsorbent, while ammonia was used as the refrigerant. During the experiments, water was used as heat pipe working fluid when the system was powered by waste heat, whereas acetone was for the same when the system was driven by solar energy. The heat pipe-type adsorption system is composed mainly of a liquid pumping boiler, a heating boiler, two coolers, two adsorbers, a condenser, and an evaporator. In each adsorber, there are 1.88 kg of calcium chloride contained in the compound adsorbent filled in between the fins of 19 finned tubes. The operation of the system comprises mainly five working processes: The first working process consists in the pumping of heat pipe working liquid into adsorber (PHPL). The heating of the heat pipe (HHP), which leads to the desorption of ammonia from the desorbing adsorber, constitutes the second working process. As to the third, it is concerned with the cooling of the heat pipe (CHP), and causes adsorption in the adsorbing adsorber. The fourth one is the mass recovery process (MR). It consists in balancing the pressure of ammonia prevailing in the two adsorbers, thereby contributing to enhance adsorption as well as desorption. Finally, the fifth process is represented by the heat pipe heat recovery (HPHR), during which heat is recovered from the high temperature adsorber (end of desorption, about to begin the adsorption) to Z.S. Lu et al. / Carbon 44 (2006) 747–752 749 Fig. 3. Structure of the refrigeration system. (a) schematic diagram, (b) photo of the system. 1. Liquid pumping boiler; 2. tap-hole; 3. electric heater; 4. heating boiler; 5. evaporator; 6. vapour pipeline; 7. liquid pipeline; 8. magnetostriction level sensor; 9. adsorbers; 10. condenser; 11. ammonia inlet; 12. safety valve; 13. vapour pipeline; 14. liquid pipeline; 15. coolers; 16. aspirating hole and heat pipe liquid inlet; 17. cooling water pipeline; 18. water meter; 19. cooling water pump; 20. pressure sensor; 21. temperature sensor; 22. safety valve. heat the low temperature adsorber (end of adsorption, about to begin the desorption). This is realized with a looped heat pipe configuration. In PHPL process, the hot adsorber is connected to the cooler. As result, the pressure prevailing therein is lower than that in the boiler. So, the heat pipe liquid can easily be pumped from the liquid pumping boiler into the adsorber. During the CHP process, the hot adsorber serves as the evaporating side of heat pipe, while the cooler serves as its condensing. The heat pipe liquid evaporates in the hot adsorber, absorbing the heat from it, and then enters the cooler via vapor pipeline, wherein it condenses. The condensed liquid then returns to the adsorber via liquid pipeline. In HHP process, the other adsorber is connected to the boiler. The heating boiler serves as the evaporating side of heat pipe and the adsorber serves as its condensing side. The heat pipe liquid is heated to evaporation by the heating boiler. The generated vapor then enters the adsorber via the vapor pipeline, and is condensed into liquid when it touches the cold surface inside the finned tubes in adsorber to provide desorption heat. At last, the condensed heat pipe liquid returns to the heating boiler via liquid pipeline to be heated again. In MR process, the valve between the hot adsorber and the cold adsorber is opened, and the ammonia vapor in the hot adsorber quickly enters the cold one, because the pressure in the hot adsorber is much higher compared to that in the cold adsorber. This process helps to get more desorp- tion from the hot adsorber and more adsorption in the cold adsorber. In HPHR process, the hot adsorber and the cold adsorber are connected. The hot adsorber serves as the evaporating side of heat pipe while the cold adsorber serves as its condensing side. The heat pipe liquid evaporates in the hot adsorber, then enters the cold adsorber, condensing there and transferring heat from the hot adsorber to the cold adsorber. Afterwards, the heat pipe liquid returns to hot adsorber again. Thus, a looped heat pipe heat recovery circuit is performed. In Fig. 3, the cooler is a coil tube heat exchanger, in which seawater is circulated in the copper tube and the vapor of heat pipe working liquid is condensed onto it. Thus, due to the heat pipe arrangement, the problem of corrosion caused by seawater used in steel made adsorber is avoided. The heat exchanger of the evaporator is just a jacket heat exchanger. 4. Experiments The adsorption quantity is measured by a magnetostriction level sensor, with relative measuring error of less than 0.05%. It is inserted inside the evaporator. The diameter of evaporator is 117 mm. The average SCP is calculated by the formula (1): SCP ¼ 1000 hfg ql V l m t ð1Þ Z.S. Lu et al. / Carbon 44 (2006) 747–752 1500 with heat and mass recovery 1000 500 with mass recovery without heat and mass recovery 0 0 5 10 15 20 25 30 35 t /min Fig. 4. Average SCP variations in half cycle time with mass and heat recovery operations. where SCP is in (W/kg), m is the mass of CaCl2 in compound adsorbent for each adsorber (1.88 kg), hfg is the latent heat of vaporization at evaporation temperature of ammonia (kJ/kg), ql is the density of ammonia liquid at the evaporation temperature (kg/m3), Vl is the volume of the ammonia liquid evaporated during the adsorption phase (m3), and t is the corresponding adsorption time (s). It is seen that the SCP value is an integrated cooling effect divided by the adsorption time and the adsorbent mass. The coefficient of cooling performance (COP) is calculated by the formula (2): hfg V l ql COP ¼ R wh dt ð2Þ where COP is the coefficient of performance, wh is heating power (kW). 4.1. Adsorption ice-maker powered by waste heat from exhausting gases of fishing boats As shown in our previously publication before mass and heat recoveries can improve the adsorption refrigeration performance significantly [13]. So, the adsorption refrigeration performance of the multifunctional heat pipe-type refrigerator with mass and heat recoveries is studied, and the results are compared with those obtained without any heat or mass recovery. The average SCP comparison results are shown in Fig. 4. The working condition was set as follows: The cycle time was 70 min (half cycle time of 35 min). The heating power was 3.6 kW. Water was selected as the heat pipe working liquid. The evaporating temperature was about 20 °C. Fig. 4 shows that the average SCP is improved significantly by mass and heat recovery. When the cycle time is 40 min, the average SCP of the cycle without any heat or mass recovery, with mass recovery only, and with heat and mass recoveries are 514.3 W/ kg, 797.5 W/kg and 1026.2 W/kg, respectively. The mass and heat recovery processes have achieved a SCP increase of 28.7% and 70.8%, respectively, in comparison with cycle with no recovery process. The normal fishing period, in China, is from January to June and from September to November, and the corresponding seawater temperature ranges from 15 °C to 30 °C. So the refrigeration performance variation with cooling water temperature has been studied. The selected working conditions was water as heat pipe working liquid, 70 min of cycle time, 40 s of mass recovery time, 2 min of heat recovery time and approximately 20 °C of evaporating temperature. The performance of adsorption refrigeration is shown in Table 1. Table 1 shows that the average SCP and COP increase as the temperature of cooling water decreases. Even at the highest temperature of cooling water, that is at 30 °C, the average SCP and COP are still as high as 528 W/kg and 0.26, respectively. 4.2. Adsorption ice-maker powered by solar energy In the second experiment, the refrigeration performance of solar ice-maker with different heating power, simulated by different electric heating power, was studied. Acetone is a good choice for the reason of faster heating process and the working condition was: 40 s of mass recovery, 24 min of cycle time, approximately 30 °C of cooling water temperature, and approximately 15 °C of evaporating temperature. The adsorber temperature represented versus time is shown in Fig. 5. As it can be seen, the desorption temperature increases with heating power. Likewise, the performance of adsorption refrigeration performance represented in Table 2 shows the average SCP as an increasing function of heating power. The ascending dependency between the system performance and the heating power can be explained by the fact that high desorption temperature leads to a good 90 2.42kW 80 2.05kW 70 T / ºC Average SCP/(W/kg) 750 60 50 1.69kW 40 30 0 6 12 t /min 18 24 Fig. 5. Adsorption bed temperature versus time. Table 1 Adsorption refrigerator performance variation with different cooling water temperature Cooling water temp. (°C) Desorption temp. (°C) Evaporation temp. (°C) Heating power (kW) Average SCP (W/kg) COP 16 20 25 30 110.1 114.7 114.0 113.7 19.1 21.3 18.1 19.4 3.64 3.64 3.64 3.64 865.8 770.4 676.8 528.0 0.43 0.39 0.34 0.26 Z.S. Lu et al. / Carbon 44 (2006) 747–752 751 Table 2 Adsorption solar ice-maker performance variation with different heating power Heating power (kW) Desorption temp. (°C) Evaporation temp. (°C) Cooling water temp. (°C) Average SCP (W/kg) COP 1.69 2.05 2.42 76.5 79.2 82.4 15.1 13.8 15.2 33.5 33.7 31.2 111.2 113.8 161.2 0.12 0.10 0.12 Table 3 Comparison of several typical studies Evaporating temp. (°C) Working pair Cooling water temp. (°C) Average SCP (W/kg) COP Research status Ref. 10 25 10 8 (solar ice-maker) SrCl2–NH3 MnCl2/NiCl2–NH3 Metal hydride–hydrogen Activated carbon–methanol 40 40 35 32 250 140 50 45.1 0.3 0.4 0.4 0.1 Test Simulation Test Test [14] [14] [15] [16] 19 21 15 (solar ice-maker) Activated carbon and CaCl2–NH3 30 20 30 528.0 770.4 161.2 0.3 0.4 0.12 Test desorption, which is conducive to improving the adsorption refrigeration performance. The maximum average SCP is 161.2 W/kg, with the corresponding average COP of 0.12. The performances could be further improved if the desorption temperature is increased, in which case high temperature solar heating will be required. It should be pointed that the measured COP is the refrigeration effect divided by the total heat input, which is not the solar COP, the solar COP would be about 40% that of the measured COP due to the solar heating efficiency. 5. Results and discussion Refrigeration performances are influenced by heat and mass recovery operations. The average SCP obtained for the cycle without any heat or mass recovery process, with mass recovery only, and with heat and mass recoveries are 514.3 W/kg, 797.5 W/kg and 1026.2 W/kg, respectively, at the condition of 40 min of cycle time and about 20 °C of evaporating temperature, about 114 °C of desorption temperature and about 30 °C of condensing temperature. In normal fishing period, refrigeration performances of ice-maker on fishing boats varies with different temperatures of seawater. The average SCP and COP increase as the temperature of cooling water decreases. At the highest temperature of cooling water of 30 °C, the lowest average of SCP and COP are still as high as 528 W/kg and 0.26, respectively. For the solar ice-maker refrigeration modes, the average SCP increases with heating power and the highest average SCP is 161.2 W/kg, and the corresponding COP is 0.12 when powered by 80 °C hot water. The values could still be improved if high temperature solar collector was used. In summary, we have designed a high effective adsorption ice-maker. This work has adopted two new concepts, mixture of activated carbon and CaCl2 as adsorbent and heat pipe for heat transfer, which are really very effective This paper to improve the performance of adsorption refrigeration systems. The achieved average SCP and COP are far higher than those obtained in other experimental systems. A comparison between the study reported in this paper and other studies is shown in Table 3. Acknowledgements This work was supported by National Science Fund for Distinguished Young Scholars of China under the contract No. 50225621, Shanghai Shuguang Training Program for the Talents under the contract No. 02GG03, the State Key Fundamental Research Program under the contract No. G2000026309. The authors thank Mr. Z.Z. Xia, Mr. Y.X. Xu for helping to install the experimental setup. The contributions from Mr. Daou is also appreciated. References [1] Wang RZ, Wu JY, Dai YJ, Wang W, Jiangzhou S. Adsorption refrigeration. China Machine Press; 2002, p. 1–3 [in Chinese]. [2] Wang DC, Wu JY, Xia ZZ, Wang RZ, Zhai H, Dou WD. Study of a novel silica gel–water adsorption chiller: Part I. Design and performance prediction. Int J Refrig 2005;28:1073–83. [3] Saha BB, Akisawa A, Kashiwagi T. Solar/waste heat driven two-stage adsorption chiller: the prototype. Renew Energy 2001;23:93–101. [4] Lai HM. An enhanced adsorption cycle operated by periodic reversal forced convection. 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