Modeling of Asphaltene Precipitation from Crude Oil with the Cubic Plus Association Equation of State

In this study, different modeling approaches using the Cubic Plus Association (CPA) equation of state (EoS) are developed to calculate the asphaltene precipitation onset condition and asphaltene yield from degassed crude oil during the addition of n-paraffin. A single model parameter is fitted to calculate the asphaltene onset condition during the addition of different n-paraffin precipitants (n-pentane to n-hexadecane). Three parameters per precipitant are fitted to calculate the asphaltene yield during the addition of the precipitant. The results obtained from the model are compared with the experimental data for eight different crude oils. Results were also obtained for seven crudes using the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) EoS based approach described in the literature. The CPA EoS based approaches treat the asphaltene fraction as an associating component whereas the PC-SAFT EoS based approach does not. A comparison between the approaches shows that the CPA EoS based approaches, developed in this work, give more reliable results. The predictions from the PC-SAFT EoS based approach result in behavior that is unphysical: the mole fraction of n-paraffin (at the precipitation onset) and the asphaltene yield do not decrease with the carbon number of n-paraffin. Furthermore, it is shown that the approach, developed in this work, can predict the onset conditions of asphaltene precipitation resulting from a blend of two or more crudes.