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Energy Conversion and Management 47 (2006) 201210

www.elsevier.com/locate/enconman

Formation and dissociation of HFC134a gas hydrate in nano-copper suspension

Jinping Li
a

a,*

, Deqing Liang b, Kaihua Guo b, Ruzhu Wang c, Shuanshi Fan

College of Fluid Power and Controlling Engineering, Lanzhou University of Technology, Lanzhou, 730050, China b Institute of Refrigeration and Cryogenics, Shanghai Jiaotong University, Shanghai 200030, China c Laboratory of Gas Hydrates, Guangzhou Institute of Energy Conversion, Guangzhou 510640, China Received 21 May 2004; received in revised form 5 October 2004; accepted 30 March 2005 Available online 26 May 2005

Abstract The major technical issue in gas hydrates energy storage systems is how to increase the refrigerants-water mass and heat transfer and how to realize a rapid formation of clathrate hydrate. Borrowing ideas from heat transfer enhancement of the uid with the addition of nano-sized particles, the formation and dissociation of HFC134a (CH2FCF3) hydrate were studied in nano-copper suspensions of dierent mass fractions. The experimental results indicate that the addition of nano-copper enhances the heat and mass transfer process of HFC134a hydrate formation, which was shortened with the increasing mass fraction of nano-copper. Compared with the dissociation pressure at a given temperature below the critical dissociation point, a signicant upward shift of the dissociation pressure of the HFC134a hydrate formed in the nano-uid was observed. The critical dissociation point shifts from the former point (283.15 K, 414.86 kPa) to the latter one (282.65 K, 401.35 kPa), and the dissociation curve does not shift with the change of mass fraction of the nano-copper. 2005 Elsevier Ltd. All rights reserved.
Keywords: Gas hydrate; Energy storage; Nano-uid; Formation process; Dissociation

Corresponding author. Address: College of Fluid Power and Controlling Engineering, Lanzhou University of Technology, Lanzhou, 730050, China. Tel.: +86 931 2973750; fax: +86 931 2756250. E-mail address: lijinping77@lut.cn (J. Li). 0196-8904/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.enconman.2005.03.018

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1. Introduction Clathrate hydrates are ice like crystalline solid compounds composed of hydrogen bonded water molecules (host molecules), of which the lattices are in a cage like structure, and some other species molecules (guest molecules), which are trapped in the cage and stabilize the structure. Most hydrates can be formed at a temperature above the freezing point of water under dierent pressures. The refrigerants gas hydrates, which are formed above 273.15 K at moderate pressure and have formation heats comparable to the fusion heat of ice, can be considered as promising energy storage materials, especially suitable for air conditioning systems [1]. The major technical issue in gas hydrates energy storage systems is how to overcome the potential barrier at the interface between the liquid (or gaseous) refrigerant and the water phase, which are insoluble in general, namely to increase the refrigerants-water mass and heat transfer and to realize a rapid formation of clathrate hydrate, which has been theoretically called a solid solution. Agitation [2,3] and adding surfactants [4,5] and inoculating seeds [6,7] have been applied to reduce the induction time and supercooling degree for crystallization and to promote the growth rate of the gas hydrates. However, there are some limitations in the eective uses of the above methods in practice. Some other means, such as employment of ultrasonic and magnetic elds, have been studied and have shown favorable eects on the formation of gas hydrates [8,9], however, it is hardly practical to use their results. Its well known that the metals in solid form have higher thermal conductivities than uids by orders of magnitude [10]. For example, the thermal conductivity of copper at room temperature is about 700 times greater than that of water and about 3000 times greater than that of engine oil. Even oxides such as alumina (Al2O3), which are good insulators compared to metals such as copper, have thermal conductivities more than an order of magnitude larger than that of water. Therefore, uids containing suspended solid particles are expected to display signicantly enhanced thermal conductivities relative to those of conventional heat transfer uids [11]. Nano-uids, rst presented by Choi [12], refers to a new kind of heat transport uid containing suspended nano-scaled metallic or nonmetallic particles in base uids. Eastman et al. [13] demonstrated that oxide nano-particles, such as Al2O3 and CuO, have excellent dispersion properties in water, oil and ethylene glycol and form stable suspensions (i.e. signicant settling does not occur in static suspensions even after weeks and months). Some experimental investigations have revealed that the nano-uids have remarkably higher thermal conductivities than those of conventional pure uids and have shown that the nano-uids have great potential for heat transfer enhancement. A maximum increase in thermal conductivity of approximately 20% was observed for 4 vol.% CuO nano-particles with average diameter 35 nm dispersed in ethylene glycol [14]. Furthermore, the eective thermal conductivity has been shown to be increased by up to 40% for the nano-uid consisting of ethylene glycol containing approximately 0.3 vol.% Cu nanoparticles of mean diameter less than 10 nm [15], and the eective thermal conductivity of the nano-uid consisting of carbon nano-tubes (1 vol.%) in oil exhibited 160% enhancement [16]. Compared with the base uid, the convective heat transfer coecient is increased about 60% for the nano-uid with 2.0 vol.% Cu nano-particles at the same Reynolds number [17]. Borrowing ideas from heat and mass transfer enhancement of the suspension with the addition of nano-particles, a nano-copper suspension was used to increase the refrigerants-water mass and heat transfer and to realize a rapid formation of the HFC134a hydrate. At the same time, the

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inuence of the nano-copper on the dissociation condition of the HFC134a hydrate was also investigated.

2. Experimental 2.1. Apparatus and agents The experimental apparatus is shown in Fig. 1. A glass cell whose volume is 1.84 104 m3 was made of quartz glass. A magnetic stirrer with three wings (4 102 m3) was placed in the center of the anges. Two platinum resistance thermometers measured the temperature in the cell and the bath with an accuracy of 0.1 K, and a strain gauge type pressure transducer measured the absolute pressure in the cell with an accuracy of 0.06%. The employed water (100 g) was deionized. The grain size distribution of the nano-copper with 25 nm nominal grain size is shown in Fig. 2. The HFC134a samples used were furnished by Solvay Flour und Derivate Gmbh, and their purities was claimed to be 99.9% or higher. The sodium dodecylbenzenesulfonate-6 of 92 wt.% analytical purity was furnished by Shanghai Lingfeng Chemical Reagent Co. Ltd., Shanghai, China. 2.2. Experimental procedures Because of their high surface free energy, ultra-ne particles tend to agglomerate in water. In order to obtain evenly distributed and stabilized suspensions, some auxiliary activators or dispersants are necessary. According to the earlier preliminary experiments, nano-copper can be dispersed evenly and stably in a water solution with the addition of 0.04 wt.% sodium dodecylbenzenesulfonate-6 with the dispersing by an ultrasonic instrument.

Fig. 1. Schematic plan of experimental apparatus: (1) to refrigerant cylinder; (2) to vacuum; (3) pressure transducer; (4) magnetic stirrer; (5) platinum resistance; (6) ange; (7) quartz glass cell; (8) thermostated bath; (9) data collection unit; (10) computer.

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Fig. 2. Grain size distribution of nano-copper.

The test procedure was the same for all rigs. Before the experiment, the cell was evacuated, 120.00 g of nano-copper suspension was charged into the glass cell, ushed with the gaseous refrigerant and re-evacuated. Then, the desired amount (20.00 g) of refrigerant HFC134a was fed into the cell. After the suspension and sample have been charged in the cell, the temperature of the cell immersed in the bath was adjusted to 293.15 K and cooled to 274.15 K until the gas hydrate formed completely while the stirring was 475 rpm, which is the proper speed demonstrated by previous work [18] and near the speed of 500 rpm, which gave a maximum hydrate reaction rate [19]. For the three phase test of liquid water-hydrate-vapor, the temperature was then raised stepwise, allowing at lease 4 h for equilibrium to be reached at each temperature, and the temperature and pressure were logged continuously while the corresponding equilibrium data was recorded. The point at which the slope of the PT curve sharply changed was considered as the hydrate dissociation point. The literature reported, Refs. [20,21], conducting three phase tests of liquid waterhydrate-vapor using the same method as that used in this work.

3. Results and discussion 3.1. The inuence of nano-copper on the formation of HFC134a hydrate In order to clarify the inuence of the nano-copper on the formation of HFC134a, the variations of pressure and temperature in the process of HFC134a hydrate formation in dierent systems, including pure water and HFC134a, a water solution with 0.04 wt.% sodium dodecylbenzenesulfonate-6 and HFC134a and a suspension with nano-copper and HFC134a, were shown in Figs. 3 and 4, respectively, when the speed of the stirrer is 475 rpm. In Figs. 3 and 4, the variations of pressure and temperature in the system of pure water and HFC134a show typical characteristics of the hydrate formation. The pressure and the temperature

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Fig. 3. The inuence of nano-Cu on the formation pressure of HFC134a hydrate when the speed of stirrer is 475 rpm.

Fig. 4. The inuence of nano-Cu on the formation temperature of HFC134a hydrate when the speed of stirrer is 475 rpm.

in the cell decrease with the continuous cooling of the bath. After a period of induction time, the temperature increases suddenly as the formation heat is given o when the HFC134a hydrate nucleates. Meanwhile, the pressure of the system almost keeps steady as the HFC134a is supersaturated and the pressure component of the water vapor is insignicant. As the process continues, the pressure decreases gradually with the consumption of the HFC134a, and the temperature also decreases with the decreasing amount of formation heat given o. Finally, phase equilibrium has been reached.

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Comparing with the curves of the pressure and temperature in the system of pure water and HFC134a, the curves of the pressure and temperature are greatly dierent in the system of the water solution with 0.04 wt.% sodium dodecylbenzenesulfonate-6 and HFC134a, or the suspension with nano-copper and HFC134a. In these three systems, as shown in Figs. 3 and 4, the pressure and temperature change more sharply and intensively. Because of the formation heat, the temperature will rise suddenly and the pressure will uctuate when the hydrate nucleates massively, hence there are peaks in the curve of T versus time or the curves of P versus time. The height and the time length of the peaks depend on the amount of formation heat and the heat and mass transfer rates of the hydrate nucleation. From Figs. 3 and 4, it can be seen that the height and the time length of the peaks of temperature and pressure shrink with the increasing nano-copper mass fraction, which suggests that the addition of nano-copper improves not only the heat transfer but also the mass transfer in the course of hydrate nucleation. The enhanced heat transfer depends on the good conductivity of the nano-copper, while the mass transfer enhancement may be caused by the presence of the large specic surface area, which would not only provide nucleation sites but also adsorb a great amount of gas/liquid HFC134a. From Figs. 3 and 4, it can also be seen that when the speed of the stirrer is 475 rpm, the HFC134a hydrate forms completely in pure water in about 5 h, in the water solution with 0.04 wt.% sodium dodecylbenzenesulfonate-6 in about two and a half hours, in the suspension with 0.1 wt.% nano-copper in about 2 h and in the suspension with 1.0 wt.% nano-copper in only one and a half hours. Hence, the formation process of the HFC134a hydrate is shortened with the increasing mass fraction of nano-copper in the water solution. 3.2. The inuence of nano-copper on the dissociation of HFC134a hydrate Dissociation points for all experiments are presented graphically in Fig. 5, which plots the dissociation temperature versus the logarithm of the dissociation pressure. Best t lines, which rep-

Fig. 5. Experimental hydrate dissociation pressures for HFC134a.

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resent the uid/gas/hydrate equilibrium lines, were drawn through the dissociation points of each uid from 273.15 K to 293.15 K. The saturated vapor points of HFC134a are calculated by the following equation [22]: 1.2 2 3 1 a3 1 T r a4 1 T r c; 1 lnP =P c T r ba1 1 T r a2 1 T r where T r TTc , a1 = 8.07488, a2 = 1.39779, a3 = 0.613357, a4 = 3.60021 and Tc and Pc are the critical pressure and critical temperature, respectively, Tc = 374.30 K, Pc = 4.0640 Mpa. Above the critical dissociation point, Q2, since the pressure component of the water vapor is insignicant, the dissociation pressure of the HFC134 hydrate coincides with the saturated vapor pressure of HFC134. Below Q2, the dissociation pressures of the HFC134a hydrate in pure water and the water solution with 0.04 wt.% sodium dodecylbenzenesulfonate-6 agrees well with that in the work of Liang et al. [21], which demonstrates the accuracy of the temperature and pressure measurements and the reliability of the experimental method and also reveals that the addition of sodium dodecylbenzenesulfonate-6 has no eect on the dissociation condition of the HFC134a hydrate. Comparing with the dissociation pressures of the HFC134a hydrate in pure water, the water solution with 0.04 wt.% sodium dodecylbenzenesulfonate-6 and in the work of Liang et al. [21], at a given temperature, a signicant upward shift of the dissociation pressure of the hydrate formed in the ultra-ne copper suspension was observed. Furthermore, in the 0.1 wt.% nano-copper suspension and in the 1.0 wt.% nano-copper suspension, the best t lines of the dissociation pressure of the HFC134a hydrate coincide with each other. Thus, in this work, the change of the mass fraction of ultra-ne copper in the suspension shows no eect on the dissociation condition of HFC134a. Table 1 shows the experimental data of the dissociation temperature and pressure of the HFC134a hydrate. Table 2 shows the critical dissociation point of HFC134a hydrate in dierent works. In this work, it can be seen that the critical dissociation point shifts from (283.15 K, 414.86 kPa) in the system of pure water and HFC134a or the water solution and HFC134a to (282.65 K, 401.35 kPa) in the system of the suspensions and HFC134a. This phenomenon of the critical dissociation point shift by addition of nano-sized copper has never been reported before. The above experimental results of dissociation of the HFC134a hydrate in a nano-copper suspension are similar to those in porous media [2327], such as sand, loam, bentonite [23], nano-fossil rich claystone [24], porous Vycor glass, various silica gels [25] and so on. Below the critical dissociation point, at a given temperature, a signicant upward shift of the dissociation pressure of the hydrate formed in porous media was investigated. At a given temperature and pressure, phase equilibrium is a reection of the liquid, gas and solid phases compositions. At equilibrium, the chemical potential of water in all three phases (at same T, P) is equal. For small shifts in equilibrium, the gas composition and hydrate composition are essentially unchanged. Any change in the phase equilibrium must be the result of a change in the liquid phase composition. As noted by Handa and Stupin [25], the stability conditions of gas hydrates might depend directly on the activity of the water. The water activity decreases with increasing pressure at a given temperature and increases at lower temperatures at a given pressure. Many investigations [2327] have conrmed that the pore eect on the hydrate equilibrium conditions depends on the pore diameter, and it is predicted by the activity of the water. In this work, the size eect of the ultra-ne copper might be the cause of the upward shift of the dissociation pressure of the hydrate.

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Table 1 The comparison of the dissociation pressure for HFC134a gas hydrate T (K) 273.51 274.15 274.75 274.82 274.95 275.15 275.35 275.55 275.95 276.12 276.15 276.35 276.65 276.85 277.35 277.45 277.75 278.15 278.23 278.25 278.85 279.25 279.35 280.15 280.46 280.55 280.65 281.15 281.45 281.51 281.75 281.95 282.15 282.35 282.45 282.5 282.65 282.85 282.92 283.05 283.13 283.15 The The The The The P (kPa) 56.6 72.58 73.9 91.66 80.23 83.75 103.55 96.3 94.40 103.57 106.47 123.32 122.79 138.56 132.85 145.77 148.4 143.67 185.0 228.96 235.7 266.53 247.54 274.50 318.33 294.0 312.67 321.55 338.91 350.26 363.2 375.55 392.12 397.8 414.68 414.4 414.86 dissociation dissociation dissociation dissociation dissociation pressure pressure pressure pressure pressure of of of of of simple HFC134a hydrate cited from Ref. [21]. simple HFC134a hydrate in this work. HFC134a hydrate in 0.04 wt.% sodium dodecylbenzenesulfonate-6 solution. HFC134a hydrate in the suspension with 0.1 wt.% nano-Cu. HFC134a hydrate in the suspension with 1.0 wt.% nano-Cu. 401.35 401.35 372.35 375.85 350.75 359.39 335.23 227.22 242.67 212.53 251.31 162.58 183.21 144.85 158.32 111.57 110.53 93.73 94.21 61.61 71.54 89.08 P (kPa) P (kPa) P (kPa) P (kPa)

J. Li et al. / Energy Conversion and Management 47 (2006) 201210 Table 2 The critical dissociation point, Q2 T (K) Q2 Q2 Q2 Q2 by Oowa et al. [20] by Liang et al. [21] of hydrate in pure water in this work of hydrate in suspensions in this work 283.20 283.13 283.15 282.65 P (kPa) 415 414.4 414.86 401.35

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According to the analysis of Cha et al. [28], the inuence of the nano-copper, termed the third surface, on the dissociation of the HFC134a hydrate may be caused by the ordered adsorption of water molecules onto some surface as a structure, which approximates a part of a hydrate lattice, and this surface becomes part of the hydrate structure. The hydrate reaction for systems where adsorption of water molecules is possible can then be written as a two step process: water nano-copper ! nano-copper-adsorbed water nano-copper-adsorbed water gas=liquid ! nano-copper-adsorbed HFC134a hydrate:

4. Conclusion This paper has presented an eective method for the heat transfer and mass transfer enhancement of the formation and dissociation of HFC134a (CH2FCF3) hydrate by the addition of ultrane particles. The experimental results indicate that the addition of nano-copper enhances the heat transfer and mass transfer of the formation process of the HFC134a hydrate, the formation process is shortened with the increase of the mass fraction of nano-copper below the critical dissociation point. Compared with the dissociation pressure of the simple HFC134 hydrate at a given temperature, signicant upward shift of the dissociation pressure of the HFC134a hydrate formed in the nano-uid was observed, and the critical dissociation point shifts from the former point (283.15 K, 414.86 kPa) to the latter one (282.65 K, 401.35 kPa). The dissociation curve does not shift with the change of the mass fraction of nano-copper. Acknowledgments This work has been supported by the Natural Science Foundation of China (No. 59836230) and the Major Basic Research Program (G2000026306) and the Natural Science Foundation of Guangdong (No. 036996). References
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