Solid–liquid–gas equilibrium of the naphthalene–biphenyl–CO 2 system: Measurement and modeling

Abstract

The first and last melting points (FLMP) method was employed to measure the melting temperature–composition ( T – w ) data at solid–liquid–gas (SLG) equilibrium for the naphthalene–biphenyl–CO 2 system. Results show that the system's phase diagram is simple eutectic under all investigated pressures (0.1, 3.0, 6.0 and 8.0 MPa), and the system's eutectic composition is almost constant. The ( T – w ) data measured with a high-pressure differential scanning calorimetry are in good agreement with these from FLMP. The semi-predictive model using solubility data (SMS) and the calculation model combining with G E models (CMG) for binary systems were extended to this ternary system. For the SMS model, the Peng–Robinson equation of state (PR-EoS) with the van der Waals one-fluid mixing rule was used to correlate the solubility data of the two solutes in CO 2 to obtain the two interaction parameters k 12 and k 13 and calculate the fugacity coefficients of the solutes in the liquid and vapor phases; the UNIFAC method was also applied to the activity coefficient of the solutes in the liquid phase. For the CMG model, the PR-EoS combining respectively the MHV1, LCVM, and modified LCVM (mLCVM) mixing rules was applied to the fugacity coefficients of the solutes. Results show that the CMG model with MHV1 gives the best prediction of the system's SLG equilibrium, while the SMS model and the CMG model with mLCVM provide comparable and acceptable results.