This study examined the occlusion of two polynucleararomatic hydrocarbons (PAHs) (pyrene and phenanthrene) in asphaltene precipitates. To test for occlusion inside the nanoaggregates, a toluene solution of asphaltene and each of these aromatic compounds was allowed to equilibrate and mix for two days to enable penetration into the asphaltene nanoaggregates, then the asphaltenes were precipitated with n-pentane, filtered washed and dried. To test for trapping and adsorption outside the nanoaggregates during precipitation, a solution of asphaltene in toluene was mixed with a solution of aromatic compound in toluene and n-pentane giving immediate precipitation, then allowed to equilibrate overnight, then filtered, washed, and dried. The PAHs in the asphaltene precipitates were determined quantitatively by gas chromatography using a high-temperature simulated distillation instrument. Pyrene and phenanthrene, which are normally soluble in the toluene-n-pentane solutions, were detected in the asphaltene precipitates at up to 6 wt% concentration. Trapping of PAHs outside of the nanoaggregates during precipitation gave 7-14 times less of the PAHs in the solid precipitate. This study shows that asphaltene aggregates can interact significantly with PAHs. The results are consistentwith the presence open porous asphaltene nanoaggregates in solutions such as toluene.

Asphaltenes exist in the form of a colloidal dispersion in crude oils and solvents. Even in a good solvent such as toluene, asphaltene aggregates persist at the nanoscale. In this study, the impact of Rayleigh scattering on the apparent absorption of visible radiation by asphaltene aggregates in solution was assessed. Recent work with a stirred diaphragm diffusion cell indicates that membranes with pore sizes less than 5 nm are capable of removing the species responsible for the absorption of visible light with wavelengths >550 nm. A further analysis of the spectra of the whole asphaltene samples in toluene indicates that the absorbance of visible light with wavelengths >600 nm follows a λ–4 dependence for asphaltenes from a range of sources over a wide range of concentration. This functional dependence is consistent with Rayleigh scattering, rather than a mixture of colored components or chromophores. Rayleigh scattering equations were combined with experimental visible spectra to estimate the average nanoaggregate sizes, which were in a very good agreement with the sizes reported in the literature by other methods. Various additives, solvents, and ultrasound and heat treatments were employed in an attempt to completely disaggregate the asphaltene nanoaggregates in solution at room temperature. None of the treatments eliminated nanoaggregration, but some treatments increased absorption due to formation of larger aggregates, as confirmed by acoustic spectroscopy.

We examined the fouling and corrosion that took place when 316 stainless steel and pure iron wires were electrically heated to 540À680°C in a liquid bath of the atmospheric bottoms fraction of a crude oil. The foulant was determined to be heterogeneous, with a thick macroscale outer layer of pitch, covering a microscale sheath of coke, which was in turn both covering and interspersed with a microscale layer of iron sulfide. This foulant was observed to delaminate from the wire surface, presumably as a result of both the generation of growth stresses and the action of gas bubbles that were evolved during the fouling process. Unexpectedly but conclusively, we observed that the underlying wire surface was heavily corroded. In the case of the stainless steel, we observed a microscale chromium oxide layer that separated the foulant from the underlying metal. This layer presumably reduced the rate of metal dissolution. The degree of corrosion was much higher in the pure iron samples, where such a layer did not exist. Our hypothesis is that there is a synergy between the measured macroscopic fouling and the underlying microscopic corrosion, where the iron from the wire reacts with the sulfur in the oil to build up the thick sulfide.

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