Abstract
The role of asphaltenes in stabilizing water-in-crude oil emulsions is extremely well established. The mechanism appears to be one in which planar, disk-like asphaltene molecules aggregate through lateral intermolecular forces to form primary aggregates or micelles which are interfacially active. These aggregates — upon adsorbing at the oil-water interface — crosslink through physical interactions to form a viscoelastic network, which has been characterized by some as a “skin” or a “plastic film”. The strength of this film, as gauged by shear and elastic moduli, seems to correlate well with water-in-oil emulsion stability. What is still relatively unknown is the role of chemistry in governing the strength of these lateral inter-asphaltene interactions. The candidate interactions include π-bonding between the delocalized electrons in the fused aromatic ring core, H-bonding between proton donors and acceptors imbedded in the asphaltenic cores, and metal-electron interactions between, for example, heavy metal ions such as vanadium or nickel and electron pairs in pyrrolic or porphyrin functional groups. We have probed these interactions indirectly by studying the destabilization of water-in-oil emulsions by a variety of aromatic solvents. In this paper, we review our previous results on both water-in-crude oil systems, as well as water-in-model oil (heptane-toluene-asphaltene mixtures) systems, in which the emulsions were progressively destabilized by addition of aromatic solvents. We also present new results with fused ring aromatic solvents, specifically methyl-naphthalene, phenanthrene, and phenanthridine. Our results suggest that fused ring aromatic solvents are considerably more effective at destabilizing asphaltene emulsions and proton-accepting fused ring aromatic solvents are most effective. These results indicate that both π-bonding and H-bonding play significant roles in mediating the aggregation of asphaltenes in oil-water interfacial films.