Interactions Between Athabasca Pentane Asphaltenes and n-Alkanes at Low Concentrations

The mass fraction and the properties of asphaltenes vary significantly with the n-alkane used to separate them from their parent oil and with the details of the separation procedure, such as washing steps. Measurement repeatability is challenging, with different error bounds reported within the American Society for Testing and Materials (ASTM) standards for a single operator using the same equipment and procedure vis-a-vis measurements performed by different operators in different laboratories. In this work, reversible interactions between Athabasca pentane asphaltenes and n-alkanes from pentane to hexadecane were observed using cross-polarized and visible light microscopy and were quantified using high-precision density measurements for mixtures ranging from 1000 to 8000 ppmw (from 0.8 to 6.5 g/L) and enthalpy of solution measurements for mixtures comprising from 1000 to 3500 ppmw (from 0.8 to 3 g/L) asphaltenes. The partial specific volumes of Athabasca pentane asphaltenes and the enthalpy of solution values, including a change of sign, were found to vary systematically with n-alkane carbon number. The microscopic observations revealed the formation of liquid crystals followed by isotropic liquid on the surface of the asphaltene particles. The interactions at low concentrations are consistent with n-alkane sorption by asphaltene particles, asphaltene particle swelling, and dissolution of a fraction of the asphaltenes in n-alkanes. The partial specific volume and enthalpy of solution results, simulated using a phenomenological model that includes these effects, explain the sensitivity of the repeatability of asphaltene mass fraction determinations to the details of the washing procedure applied during their preparation. Preparation techniques without washing appear to be preferred because the mass fractions of asphaltenes recovered are expected to be more repeatable and their properties are likely to be more consistent.