Applying the PR-EoS to Asphaltene Precipitation from n-Alkane Diluted Heavy Oils and Bitumens

Abstract

The Peng−Robinson equation of state (EoS) was adapted using group contribution methods to model asphaltene precipitation from solutions of toluene and an n-alkane and from n-alkane diluted bitumens. A liquid−liquid equilibrium was assumed between a primary liquid phase and a second dense asphaltene phase. Bitumen was characterized in terms of solubility fractions: saturates, aromatics, resins, and asphaltenes. Critical properties of the saturates, aromatics, and resins were determined that fit their measured densities and compared well with existing critical property correlations. The saturate and aromatic critical properties were also tuned to fit asphaltene precipitation data from solutions of the saturate and toluene or the aromatic and heptane. Asphaltenes were divided into fractions of different molar masses using a gamma distribution function. EoS parameters for asphaltenes were determined that fit the measured densities, fit precipitation data for mixtures of asphaltenes, toluene, and heptane, and compared well with existing critical property correlations. The model successfully fitted and predicted the onset and amount of precipitation over a broad range of compositions, temperatures from 0 to 100 °C, and pressures up to 7 MPa. The model results were within the error of the measurements except for high dilutions with n-pentane.