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The phase behaviors of toluene/polycyclic aromatic hydrocarbon mixture systems were investigated with a continuous-flow typeapparatus at 573.2, 598.2, 623.2 and 648.2 K, while the pressure changed from I to 5MPa. The pseudo-binary phase behaviors were predictedwith the Peng-Robinson equation of state with interaction parameters between toluene and pseudo-components considered. The phase diagramsof the system have been classified following the category of phase boundary diagram models. The extraction selectivity and efficiency of tolue-ne as a solvent was discussed by comparing with that of hexane. The prediction model for selectivity was also suggest, ed.