Asphaltene Nanoaggregates Measured in a Live Crude Oil by Centrifugation

• Published in: Energy & fuels Vol. 23; no. 9; pp. 4460 - 4469
• Main Authors: Indo, Kentaro, Ratulowski, John, Dindoruk, Birol, Gao, Jinglin, Zuo, Julian, Mullins, Oliver C
• Format: Journal Article
• Language: English
• Published: American Chemical Society 17.09.2009
• Subjects: Fossil Fuels
• ISSN: 0887-0624; 1520-5029
• DOI: 10.1021/ef900369r

Asphaltene nanoaggregates have recently been observed in live crude oil by observation of gravitationally induced asphaltene gradients in four different reservoir sands with oil columns up to 1000 m vertical. When the liquid phase is invariant, these gradients can be fit using Archimedes buoyancy in the Boltzmann distribution; the only adjustable parameter in data fitting is the size of the asphaltene nanoaggregate; ∼2 nm is obtained in four reservoir sands and is similar to laboratory results for asphaltene nanoaggregates in toluene. Here, a live crude oil (with dissolved gases) has been spun at modest g forces for long times designed to create a large, equilibrium asphaltene gradient for the presumed 2 nm aggregates. Elevated temperatures (∼91 °C) were employed during centrifugation to mimic reservoir conditions for asphaltene aggregation and prevention of a possible wax phase. Elevated pressures were employed on the hot, live crude oil to maintain dissolved gas concentrations. A total of 13 alliquots of crude oil were removed after centrifugation, and the asphaltene concentrations were determined by optical spectroscopy. Indeed, a large asphaltene gradient was observed, and a 2.6 nm diameter nanoaggregate was obtained using Archimedes buoyancy in the Boltzmann distribution. In addition, a solubility model accounting for the gas/oil ratio (GOR) gradient was used to analyze the asphaltene gradient, giving an asphaltene particle size of 2.0 nm, thus, the same as field observations. In addition, the gradient in bulk resins was shown to be quite small, showing the stark contrast of asphaltene versus bulk resin aggregation. The heaviest resins (or lightest asphaltenes) do show some gradient. These observations allow for the determination of the maximum and minimum asphaltene aggregation number; the range is roughly 3−8. Some modest resin association with asphaltenes, one resin molecule in every asphaltene nanoaggregate, is consistent with our data. These results are discussed within the increasingly successful modified Yen model of asphaltenes.