Fractionation of Asphaltenes in Understanding Their Role in Petroleum Emulsion Stability and Fouling

SARA fractionation separates crude oil into fractions of saturates (S), aromatics (A), resins (R), and asphaltenes (A) based on the differences in their polarizability and polarity. Defined as a solubility class, asphaltenes are normally considered as a nuisance in the petroleum industry mainly as a result of their problematic precipitation and adsorption at oil–water and oil–solid interfaces. Because a broad range of molecules fall within the group of asphaltenes with distinct sizes and structures, considering the asphaltenes as a whole was noted to limit the deep understanding of governing mechanisms in asphaltene-induced problems. Extended-SARA (E-SARA) is proposed as a concept of asphaltene fractionation according to their interfacial activities and adsorption characteristics, providing critical information to correlate specific functional groups with certain characteristics of asphaltene aggregation, precipitation, and adsorption. Such knowledge is essential to addressing asphaltene-related problems by targeting specific subfractions of asphaltenes

Demulsification mechanism of asphaltene-stabilized water-in-oil emulsions by a polymeric ethylene oxide-propylene oxide demulsifier

The demulsification mechanism of asphaltene-stabilized water-in-toluene emulsions by an ethylene-oxide-propylene oxide (EO-PO) based polymeric demulsifier was studied. Demulsification efficiency was determined by bottle tests and correlated to the physicochemical properties of asphaltene interfacial films after demulsifier addition. From bottle tests and droplet coalescence experiments, the demulsifier showed an optimal performance at 2.3 ppm (mass basis) in toluene. At high concentrations, the demulsification performance deteriorated due to the intrinsic stabilizing capacity of the demulsifier, which was attributed to steric repulsion between water droplets. Addition of demulsifier was shown to soften the asphaltene film (i.e., reduce the viscoelastic moduli of asphaltene films) under both shear and compressional interfacial deformations. Study of the macrostructures and the chemical composition of asphaltene film at the toluene-water interface after demulsifier addition demonstrated gradual penetration of the demulsifier into the asphaltene film. Demulsifier penetration in the asphaltene film changed the asphaltene interfacial mobility and morphology, as probed with Brewster angle and atomic force microscopy

Electrohydrodynamic Instabilities in Free Emulsion Films

Electrohydrodynamic instabilities were induced in thin water-in-oil emulsion films by application of external DC electric field. The dominant wavelengths of instabilities were measured for constant electric fields of various strengths. The dominant wavelengths agreed reasonably well with theoretical predictions based on a linear stability model. The linear stability model used in this study took into account experimentally measured repulsive disjoining pressure and calculated Maxwell stress. The observation of such instabilities can help to understand the rupture mechanism of emulsion films under the influence of electric field

Asphaltene Subfractions Responsible for Stabilizing Water-in-Crude Oil Emulsions. Part 2: Molecular Representations and Molecular Dynamics Simulations

After successful isolation of the most interfacially active subfraction of asphaltenes (IAAs) reported in the first part of this series of publications, comprehensive chemical analyses including ES-MS, elemental analysis, Fourier transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR) spectrometry were used to determine how the molecular fingerprint features of IAAs are different from those of the remaining asphaltenes (RAs). Compared with the RAs, the IAA molecules were shown to have higher molecular weight and higher contents of heteroatoms (e.g., three times higher oxygen content). The analysis on the elemental content and FTIR spectroscopy suggested that IAAs contained higher contents of high-polarity sulfoxide groups than the RAs. The results of ES-MS, NMR, FTIR, and elemental analyses were used to construct average molecular representations of IAA and RA molecules. These structures were used in molecular dynamics (MD) simulation to study interfacial and aggregation behaviors of the proposed molecules. The MD simulation study showed little affinity of representative RA molecules to the oil/water interface, while the representative IAA molecules had much higher interfacial activity, reflecting the extraction method. The aggregation of IAA molecules in the bulk oil phase and their adsorption at oil/water interface were not directly related to the ring system, but rather to the associations between or including sulfoxide groups. During the simulation, the IAA molecules were found to be self-assembled in solvent, forming supramolecular structures and a porous network at the oil/water interface, as suggested in our previous work. The results obtained in this study provide a better understanding of the role of asphaltenes in stabilizing petroleum emulsions

Interfacial Layer Properties of a Polyaromatic Compound and its Role in Stabilizing Water-in-Oil Emulsions

Physical properties of interfacial layers formed at the xylene–water interface by the adsorption of a polyaromatic organic compound, N-(1-hexylheptyl)-N′-(5-carbonylicpentyl) perylene-3,4,9,10-tetracarboxylic bisimide (in brief, C5Pe), were studied systematically. The deprotonation of the carboxylic group of C5Pe at alkaline pH made it highly interfacially active, significantly reducing the xylene–water interfacial tension. Thin liquid film experiments showed a continuous buildup of heterogeneous C5Pe interfacial layers at the xylene–water interfaces, which contributed to the formation of stable W/O emulsions. Continual accumulation and rearrangement of C5Pe aggregates at the xylene–water interface to form a thick layer was confirmed by in situ Brewster angle microscopy (BAM) and atomic force microscopy (AFM). The rheology measurement of the interfacial layer by double-wall ring interfacial rheometry under oscillatory shear showed that the interfacial layers formed from C5Pe solutions of high concentrations were substantially more elastic and rigid. The presence of elastically dominant interfacial layers of C5Pe led to the formation of stable water-in-xylene emulsions