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Journal of Supercritical Fluids, Vol.11, No.1, 1-14, 1997
A new apparatus to measure the vapour-liquid equilibria of low-volatility compounds with near-critical carbon dioxide. Experimental and modelling results for carbon dioxide plus n-butanol, plus 2-butanol, plus 2-butyl acetate and plus vinyl acetate systems
A new apparatus has been developed for the experimental determination of vapour-liquid equilibria in systems containing low-volatility compounds and near-critical carbon dioxide. The apparatus combines the advantages of the gas saturation method with those of a circulation method. An air-lift-functioning draft tube is used in the centre of the equilibrium cell to increase contact time between solute and solvent. The apparatus is tested by measuring the vapour-liquid equilibrium (VLE) of the system CO2 + 1-butanol at 313.2 and 333.2 K and at pressures up to 11 MPa. For the systems CO2 + 2-butanol, CO2 + vinyl acetate and CO2 + 2-butyl acetate, VLE data were measured at pressures up to 10 MPa and at the temperatures of 303.2, 313.2 and 333.2 K. The measured mole fractions of the low-volatility compound in carbon dioxide have an accuracy better than 3%. The solubility isotherms were modelled using the PRSV EOS with Wong-Sandler mixing rules and the LCVM model. It is shown that the solubility of the low-volatility compounds in carbon dioxide can be predicted well with the PRSV-WS EOS (NRTL-G(E)-model) using the fit parameters obtained from bubble point measurements. The PRSV-WS predicts the solubilities better than the LCVM model (t-mPR EOS with an adapted UNIFAC-Ge-model).
Keywords:HIGH-PRESSURE;PHASE-EQUILIBRIA;CUBIC EQUATIONS;MIXING RULES;LCVM MODEL;STATE;1-BUTANOL;SOLUBILITIES;PREDICTION;MIXTURES