Structural Characteristics of Low-Aromaticity Marine and Lacustrine Oil Shales and their NaOH-HCl Kerogens Determined Using 13C NMR and XPS

Abstract

Few comparisons have been made between low-aromaticity marine and lacustrine oil shales and their kerogens, because the reliability of structural analyses has been limited by a reliance on only one method of kerogen isolation, HCl-HF. Therefore, a detailed analysis by 13C NMR and X-ray photoelectron spectroscopy (XPS) was made for Attrat marine oil shale (Jordan) and Colorado (Green River) lacustrine oil shale (USA) and their NaOH-HCl kerogens. Some differences between oil shales and their kerogens were noted, but many structural features were considered to be true characteristics of the organic matter. The results emphasise the importance of comparing the analyses of kerogens isolated by different methods to ensure that features of the organic matter are not an artefact of the method of kerogen isolation. For both oil shales, the predominantly aliphatic character of the organic part was confirmed and the long average chain length of the aliphatic hydrocarbons was established. All shales and their kerogens showed a small cluster size for the aromatic rings. The elemental analysis obtained by XPS, compared with the bulk elemental analysis, indicated major differences between the near-surface region sampled by XPS and the bulk. The organic S was determined to be aliphatic and aromatic S with possibly small amounts of sulfoxide. Most of the N was pyrrolic with smaller amounts in pyridinic or quaternary form. Nearly all of the surface organic C in both kerogens was bonded to C and H. Two major forms of organic O were distinguishable. A good correlation between the proportion of aliphatic S and pyrolysis reactivity is suggested.