Michael P. Hoepfner

The fractal aggregation of asphaltenes.

This paper discusses time-resolved small-angle neutron scattering results that were used to investigate asphaltene structure and stability with and without a precipitant added in both crude oil and model oil. A novel approach was used to isolate the scattering from asphaltenes that are insoluble and in the process of aggregating from those that are soluble. It was found that both soluble and insoluble asphaltenes form fractal clusters in crude oil and the fractal dimension of the insoluble asphaltene clusters is higher than that of the soluble clusters. Adding heptane also increases the size of soluble asphaltene clusters without modifying the fractal dimension. Understanding the process of insoluble asphaltenes forming fractals with higher fractal dimensions will potentially reveal the microscopic asphaltene destabilization mechanism (i.e., how a precipitant modifies asphaltene-asphaltene interactions). It was concluded that because of the polydisperse nature of asphaltenes, no well-defined asphaltene phase stability envelope exists and small amounts of asphaltenes precipitated even at dilute precipitant concentrations. Asphaltenes that are stable in a crude oil-precipitant mixture are dispersed on the nanometer length scale. An asphaltene precipitation mechanism is proposed that is consistent with the experimental findings. Additionally, it was found that the heptane-insoluble asphaltene fraction is the dominant source of small-angle scattering in crude oil and the previously unobtainable asphaltene solubility at low heptane concentrations was measured.

Multiscale scattering investigations of asphaltene cluster breakup, nanoaggregate dissociation, and molecular ordering

Small-angle X-ray and neutron scattering (SAXS/SANS) by asphaltenes in various solvents (toluene, tetrahydrofuran, and 1-methylnaphthalene) at dilute concentrations of asphaltenes are presented and discussed. As asphaltenes are diluted, it was found that the cluster size decreases and follows a fractal scaling law. This observation reveals that asphaltene clusters persist to dilute concentrations and maintain fractal characteristics, regardless of concentration. For the first time, the fraction of asphaltenes that exist in nanoaggregates compared to those molecularly dispersed was estimated from the scattering intensity. Significant dissociation was detected at concentrations similar to the previously reported critical nanoaggregate concentration (CNAC); however, the dissociation was observed to occur gradually as the asphaltene concentration was lowered. Complete dissociation was not detected, and aggregates persisted down to asphaltene concentrations as low as 15 mg/L (0.00125 vol. %). A simplified thermodynamic aggregation model was applied to the measurements, and the free energy change of association per asphaltene-asphaltene interaction was calculated to be approximately -31 kJ/mol. Finally, novel solvent-corrected WAXS results of asphaltene in a liquid environment are presented and reveal three distinct separation distances, in contrast to the two separation distances observed in diffraction studies of solid phase asphaltenes. Significant differences in the WAXS peak positions and shapes between aromatic and nonaromatic solvents suggests that there may be large differences between the solvation shell or conformation of the asphaltene alkyl shell depending on the surrounding liquid environment.

Revisiting the flocculation kinetics of destabilized asphaltenes

A comprehensive review of the recently published work on asphaltene destabilization and flocculation kinetics is presented. Four different experimental techniques were used to study asphaltenes undergoing flocculation process in crude oils and model oils. The asphaltenes were destabilized by different n-alkanes and a geometric population balance with the Smoluchowski collision kernel was used to model the asphaltene aggregation process. Additionally, by postulating a relation between the aggregation collision efficiency and the solubility parameter of asphaltenes and the solution, a unified model of asphaltene aggregation model was developed. When the aggregation model is applied to the experimental data obtained from several different crude oil and model oils, the detection time curves collapsed onto a universal single line, indicating that the model successfully captures the underlying physics of the observed process.

Structure of Asphaltenes during Precipitation Investigated by Ultra-Small-Angle X-ray Scattering

Time-resolved size and structure measurements of asphaltenes while in the process of precipitating were monitored for the first time using ultra-small-angle X-ray scattering. The results revealed that asphaltenes precipitating from a heptane-toluene mixture demonstrate a hierarchical structure of an asphaltene-rich phase (e.g., droplet) that further agglomerates into fractal flocs. The fractal flocs that form by the agglomeration of the asphaltene-rich phase are what is commonly detected by optical microscopy above the precipitation detection point. The surface of the asphaltene-rich phase is initially rough and transitions to a smooth interface, as would be expected for a highly viscous liquid. Simultaneous small-angle X-ray scattering measurements were also performed to investigate the structure of soluble asphaltenes, providing comprehensive structural characterization from the nanometer- to micrometer-length scales as a function of time. Further, the results demonstrate that the size and concentration of asphaltenes remaining in solution (e.g., soluble asphaltenes) do not change during precipitation, whereas the structure of insoluble asphaltenes varies. The ability to measure the properties of asphaltenes as they undergo precipitation opens new opportunities for understanding the fundamental mechanisms of asphaltene deposition and aggregation and the impact of chemical inhibitors to alter these processes. The universality of these conclusions and how specific properties vary as a function of asphaltene source and solution properties can provide valuable insight into asphaltene behavior.