Abstract
X-ray Absorption Near Edge Structure (XANES) spectroscopy has been employed to characterize the different chemical structures of sulfur in kerogens, asphaltenes, and coals. Commonalities are found for the sulfur chemistry in these disparate carbonaceous materials. Most of the sulfur is organic, with thiophenic structures typically the most abundant and sulfidic forms also fairly abundant. Oxidized organic sulfur in lesser amounts is found in lowrank coals, in the different fractions of one crude oil, and Type I kerogens. In addition, there is pyrite in the coals and pyrite/elemental sulfur in the kerogens. The sulfur chemistry is shown to reflect the carbon chemistry in kerogens and coals. Type II kerogens have a larger ratio than Type I kerogens of aromatic to saturated carbon. Likewise higher rank coals also have a larger ratio of aromatic to saturated carbon than lower rank coals. Here, it is shown that Type II kerogens and higher rank coals similarly have larger fractions of aromatic sulfur. This important result establishes a relationship between the carbon and sulfur chemistry of these materials. The nitrogen chemistry of the carbonaceous materials was also investigated with XANES. In all of the materials, the nitrogen is almost entirely aromatic with pyrrolic nitrogen being the most abundant.
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Mitra-Kirtley, S., Mullins, O.C. (2007). Sulfur Chemical Moieties in Carbonaceous Materials. In: Mullins, O.C., Sheu, E.Y., Hammami, A., Marshall, A.G. (eds) Asphaltenes, Heavy Oils, and Petroleomics. Springer, New York, NY. https://doi.org/10.1007/0-387-68903-6_6
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