Direct Characterization of Kerogen by X-ray and Solid-State 13C Nuclear Magnetic Resonance Methods

• Published in: Energy & fuels Vol. 21; no. 3; pp. 1548 - 1561
• Main Authors: Kelemen, S. R, Afeworki, M, Gorbaty, M. L, Sansone, M, Kwiatek, P. J, Walters, C. C, Freund, H, Siskin, M, Bence, A. E, Curry, D. J, Solum, M, Pugmire, R. J, Vandenbroucke, M, Leblond, M, Behar, F
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 16.05.2007
• Subjects: Applied sciences; Constitution and properties of crude oils, shale oils, natural gas and bitumens. Analysis and characteristics; Crude oil, natural gas and petroleum products; Energy; Exact sciences and technology; Fuels; Petroleum fraction; X ray absorption spectrometry; XANES spectrometry; Chemical structure; X ray spectrometry; Photoelectron spectrometry; NMR spectrometry; Nuclear magnetic resonance; Kerogen
• ISSN: 0887-0624; 1520-5029
• DOI: 10.1021/ef060321h

A combination of solid-state 13C NMR, X-ray photoelectron spectroscopy (XPS) and sulfur X-ray absorption near edge structure (S-XANES) techniques are used to characterize organic oxygen, nitrogen, and sulfur species and carbon chemical/structural features in kerogens. The kerogens studied represent a wide range of organic matter types and maturities. A van Krevelen plot based on elemental H/C data and XPS derived O/C data shows the well established pattern for type I, type II, and type III kerogens. The anticipated relationship between the Rock−Eval hydrogen index and H/C is independent of organic matter type. Carbon structural and lattice parameters are derived from solid-state 13C NMR analysis. As expected, the amount of aromatic carbon, measured by both 13C NMR and XPS, increases with decreasing H/C. The correlation between aromatic carbon and Rock−Eval T max, an indicator of maturity, is linear for types II and IIIC kerogens, but each organic matter type follows a different relationship. The average aliphatic carbon chain length (Cn‘) decreases with an increasing amount of aromatic carbon in a similar manner across all organic matter types. The fraction of aromatic carbons with attachments (FAA) decreases, while the average number of aromatic carbons per cluster (C) increases with an increasing amount of aromatic carbon. FAA values range from 0.2 to 0.4, and C values range from 12 to 20 indicating that kerogens possess on average 2- to 5-ring aromatic carbon units that are highly substituted. There is basic agreement between XPS and 13C NMR results for the amount and speciation of organic oxygen. XPS results show that the amount of carbon oxygen single bonded species increases and carbonyl−carboxyl species decrease with an increasing amount of aromatic carbon. Patterns for the relative abundances of nitrogen and sulfur species exist regardless of the large differences in the total amount of organic nitrogen and sulfur seen in the kerogens. XPS and S-XANES results indicate that the relative level of aromatic sulfur increases with an increasing amount of aromatic carbon for all kerogens. XPS show that the majority of nitrogen exists as pyrrolic forms in comparable relative abundances in all kerogens studied. The direct characterization results using X-ray and NMR methods for nitrogen, sulfur, oxygen, and carbon chemical structures provide a basis for developing both specific and general average chemical structural models for different organic matter type kerogens.