ELSEVIER hui Phase Bgilibia 131 (1997) 243-258 Densities and P-x-y diagrams for carbon dioxide dissolution in methanol, ethanol, and acetone mixtures Chiehming J. Chang **, Chany-Yih Day °, Ching-Ming Ko *, Kou-Lung Chiu * * Deparment of Chemical Engineering, National Chung-Hsing University, #250, KuoKuang Road, Taichung, Taiwan 402, People's Republic of China Department of Environmental Engineering, National Chung-Hsing University, #250, KuoKuang Road, Taichung, Taiwan 402, People’s Republic of China Received 20 May 1996; accepted 19 October 1996 Abstract Densities and P-x-y diagrams for carbon dioxide + methanol, carbon dioxide + ethanol, and carbon dioxide + acetone were determined by a novel technique of density measurement at 291, 298, 303, 308, 313 K, and pressures up to 8 MPa. Solubilities of carbon dioxide in methanol, ethanol, and acetone were found to increase with applied pressure, but to decrease with increasing temperature, Carbon dioxide has the highest solubility in acetone for the whole pressure range. The Patel-Teja and Peng-Robinson equations of state with the van der Waals one-fluid mixing rules were able to correlate successfully equilibrium data for these three systems. © 1997 Elsevier Science B.V. Keywords: Experiments; Data; Density: VLE high pressure: Computer simulation 1. Introduction A small amount of products can remain within the stream of wastewater during pharmaceutical and food manufacturing processes. Considering the effects on economics, extraction efficiency, and post-treatment, supercritical fluid extraction could be a separation process for handling wastewater which contains few but valuable organics (Chang and Huang, 1994). Vapor-liquid equilibria of carbon dioxide with hydrocarbons at elevated pressures are commonly used in the design and operation of separation equipment in the petroleum industry. However, limited data are available for carbon dioxide + alcohol and carbon dioxide + other liquid solvent mixtures at elevated pressures. * Conresponding author. (03783812 /97 /817.00 © 1997 Elevier Sclence B.V. All ihts reserved, PI S0378-3812(96)03208-6as 1 Chang eal / Fluid Phave Equibra 131 (1997) 243-258 Staby and Mollerup (1993) reviewed the mutual solubilities of carbon dioxide and mono-alcohols. Jennings et al. (1991) measured VLE data in the carbon dioxide + ethanol and carbon dioxide + 1- butanol systems. Leu et al. (1991) measured the equilibrium phase properties of carbon dioxide + methanol. Panagiotopoulos and Reid (1987), Shibata and Sandler (1989), and Kato et al. (1991) recently measured the density of high pressure systems using vibrating-tube densimeters with circulation in their vapor-liquid equilibrium apparatus. Kato and Tanaka (1995) used the new density apparatus to measure the high pressure phase compositions of carbon dioxide + ethanol mixtures at 308.15 K. The authors (Chang, 1992; Chang et al., 1995) recently proposed volume expansion coefficients and activity coefficients of carbon dioxide + organic liquids at 298 K, and the solubilities of carbon dioxide and nitrous oxide in three liquid solvents were measured under phase equilibria at several temperatures and elevated pressures. An equation of state in the cubic volume form is suitable for the correlation of equilibrium data of the binary mixture at high pressure, and a few mixing rules are commonly used to take into account the interactional force between unlike molecules (McHugh and Krukonis, 1986; Prausnitz et al., 1986) 2, Experiment and correlation Methanol (Merck, 99.8 + %), ethanol (Merck, 99.8 + %), acetone (Merck, 99.5 + %), carbon dioxide (Air Product local branch, 99.5 + %), and nitrogen (Air Product local branch, 99.5 + %), were purchased without further purification. The density measurement for any binary mixture and calculation of the pressure related constant for the densimeter can be found elsewhere in the literature (Chang et al., 1995). ‘The experimental system is illustrated schematically in Fig. 1. The liquid in the equilibrium cell ‘was recirculated from bottom to top using a magnetic micropump (Micropump, 1805R-346). The vapor inside the vapor-phase densimeter was flushed at each pressure increment. Equilibrium was achieved for 30 min, the recirculation stopped and the periods of vibration recorded in both densitometers. Through a calibration between period of vibration and density, the vapor and liquid compositions (y and x) at fixed temperature and pressure can be evaluated by combining a set of Table | Physical properties of carbon dioxide, methanol, ethanol, and acetone in this study Carbon dioxide (CO,) Methanol (CH,OH) Ethanol (C,H,OH) Acetone (CH),C=O) Mw 010 32,082 76.069 ‘38080 TAK) 308.10 512.60 51392 508.10 P. (bar) 738 B09 oa 470 Ve (ml mol") 93.9 1180 167.1 2090 iW 194.65 3317 ash 3292 « 07278 1.1708 1.2559 08231 & 0309 0278 0292 0.283, y 0.207727 0.965347 Lins 0701112 o 0239 0.356 0.644 0.304 Dipole moment 0.0 7 Ww 29CA. Chang eta, Fuid Phase Equilibria 131 (1997) 243-258 245 1. gaseylinder 102 check valve 2 filter 11. ireulation pump 3 metering pump 12. digital thermometer 4. reffigerator 13. digital pressure transducer 5. pressure gauge 14. wet gas meter G.reliefvalve 15. line printer Ta, needle valve 16. densitometer(a:DMA6O, 8. air bath biDMASI2.:DMASI2P) 9. equilibrium cell 17. high precision thermometer Fig. [. Experimental apparatus used in VLE composition measurements for CO, dissolution in liguid solvents. density data, based on overall mass balances and the phase rule, which were used in the studies of Kato et al. (1991), Chang (1992), Chang et al. (1995), and Kato and Tanaka (1995). The Patel~Teja equation of state (PT-EOS) with the one-fluid, two-parameter van der Waals mixing rule is written as follows: Rr a vob uetbytee Q LE, @) b= LL aaby rc) pe “