Impact of Liquid-Vapor to Liquid-Liquid-Vapor Phase Transitions on Asphaltene-Rich Nanoaggregate Behavior in Athabasca Vacuum Residue + Pentane Mixtures

Journal Article · Wed Jun 05 00:00:00 EDT 2013 · Energy and Fuels

DOI:https://doi.org/10.1021/ef301475f· OSTI ID:1078046

Long, Bingwen; Chodakowski, Martin; Shaw, John M. ^[1]

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1. Alberta

The bulk phase behavior of heavy oil + alkane mixtures and the behavior of the asphaltenes that they contain are topics of importance for the design and optimization of processes for petroleum production, transport, and refining and for performing routine saturates, aromatics, resins, and asphaltenes (SARA) analyses. In prior studies, partial phase diagrams and phase behavior models for Athabasca vacuum residue (AVR) comprising 32 wt % pentane asphaltenes + n-alkanes were reported. For mixtures with pentane, observed phase behaviors included single-phase liquid as well as liquid–liquid, liquid–liquid–vapor, and liquid–liquid–liquid–vapor regions. Dispersed solids were detected under some conditions as well but not quantified. In this work, small-angle X-ray scattering (SAXS) is used to study nanostructured materials in liquid phases present in AVR + n-pentane mixtures from 50 to 170 °C at mixture bubble pressure. The investigation focuses on the impact of the transition from a single AVR-rich liquid to co-existing pentane-rich and AVR-rich liquids on the nanostructure and the nanostructures most resistant to aggregation as the pentane composition axis is approached. Background scattering subtraction was performed using global mixture composition. The robustness of this assumption with respect to values obtained for coefficients appearing in a two level Beaucage unified equation fit is demonstrated. The nanostructured material is shown to arise at two length scales from 1 to 100 wt % AVR. Smaller nanostructures possess mean radii less than 50 Å, while the larger nanostructures possess mean radii greater than 250 Å. The addition of pentane to the AVR causes an increasingly large fraction of the large and small nanostructures to grow in size. Only nanostructures resistant to aggregation remain in the pentane-rich phase as the 0 wt % AVR axis is approached. Step changes in aggregation identified from changes in average radius of gyration, scattering coefficients, and surface/volume ratios arise at the liquid–vapor to liquid–liquid–vapor transition (~40 wt % pentane) and within the liquid–liquid–vapor region (~90 wt % pentane). The temperature is shown to have a limited effect on the mean size and structure of the nanostructured material present, irrespective of global composition.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
• Sponsoring Organization: FOREIGN
• OSTI ID: 1078046
• Journal Information: Energy and Fuels, Vol. 27, Issue (4) ; 04, 2013; ISSN 0887-0624
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: ENGLISH