Surface interaction of crude oil, maltenes, and asphaltenes with calcite: An atomic force microscopy perspective of incipient wettability change

Abstract

Close examination of surface interactions between calcite and crude oil is relevant to better understand the mechanisms that lead to wettability changes in petroleum reservoirs. Mineral surface wettability is a determinant factor in petroleum production and recovery, and the surface-active compounds in crude oil, typically concentrated in its asphaltene fraction, are mainly responsible for these wettability changes. Here, we use atomic force microscopy (AFM) to examine the incipient interactions between calcite {101‾4} surfaces and the Kuwait UG8 crude oil, and its asphaltene and maltene (i.e., crude oil after asphaltene has been extracted) fractions. The resulting adsorbates are interpreted on the basis of coverage, size, shape, and distribution. Adsorbates from crude oil are equally-spaced hemispheroidal droplets occurring predominantly at [4‾41] and [481‾] surface steps with a separation of about 550 nm between centers of adjacent adsorbates. Adsorbates from asphaltenes are irregularly spaced droplets or continuously cover the steps along the edges of dissolution pits. The average and standard deviation of diameter and height of 10–16 representative adsorbates from the selected images highlight the contrast among samples. Crude oil adsorbates average about (240 ± 120) nm in diameter and (60 ± 30) nm in height. Diameters of isolated adsorbates and lateral dimension of elongated adsorbates of asphaltene average (100 ± 20) nm and (150 ± 40) nm, respectively, and about (30 ± 10) nm in height overall. Isolated non-periodic smaller adsorbates (average diameter (20 ± 5) nm and height (7 ± 3) nm) occur from the maltene fraction and are mostly restricted to steps surrounding dissolution pits. Adsorbates from maltenes are most likely produced by resins that remain in this fraction after extracting the asphaltenes. Adsorption from crude oil involves the greatest surface area compared to asphaltenes and maltenes. Based on the sizes and heights of adsorbates reported here, we infer that, unlike resins, asphaltenes in crude oils act as anchors for increased oil adsorption and help enhance the change of an original water-wet surface to an oil-wet one. Differences in average height and architecture between adsorbates from oil and asphaltenes (i.e., isolated vs. continuous) may in part be associated to increased aggregation in toluene, which will intensify colloidal interactions before adsorption. We argue that asphaltenes in crude oil help stabilize larger, almost periodically spaced adsorbates all throughout the calcite surface and not only along the deeper steps that border large dissolution pits. The computational model of a chosen specific asphaltene molecule attached to a calcite surface shows strong interactions between hydroxyl groups and Ca2+ cations on the calcite surface in addition to weaker interactions of the negatively charged π orbitals of the polycyclic aromatic hydrocarbon (PAH) center and the surface cations, which is in agreement with the notion of establishing asphaltene anchors on calcite. Along with basic chemical information, systematic AFM imaging of a variety of crudes may become part of a practical strategy to evaluate surface-active compounds in oil and to predict their likely molecular structure and participating functional groups.