Heavy Oil Hydrocarbons and Kerogen Destruction of Carbonate–Siliceous Domanic Shale Rock in Sub- and Supercritical Water

Abstract

This paper discusses the results of the influences of subcritical (T = 320 °C; P = 17 MPa) and supercritical water (T = 374 °C; P = 24.6 MPa) on the yield and composition of oil hydrocarbons generated from carbonaceous–siliceous Domanic shale rocks with total organic content (Corg) of 7.07%. It was revealed that the treatment of the given shale rock in sub- and supercritical water environments resulted in the decrease of oil content due to the intensive gas formation. The content of light hydrocarbon fractions (saturated and aromatic hydrocarbons) increased at 320 °C from 33.98 to 39.63%, while at 374 °C to 48.24%. Moreover, the content of resins decreased by almost twice. Insoluble coke-like compounds such as carbene–carboids were formed due to decomposition of kerogen after supercritical water treatment. Analysis of oil hydrocarbons with FTIR method revealed a significant number of oxygen-containing compounds, which are the hydrogenolysis products of structural fragments formed after destruction of kerogen and high-molecular components of oil. The gas chromatography–mass spectroscopy (GC–MS) method was applied to present the changes in the composition of mono- and dibenzothiophenes, which indicate conversion of heavy components into lighter aromatic hydrocarbons. The specific features of transforming trace elements in rock samples, asphaltenes, and carbene–carboids were observed by using the isotopic mass-spectrometry method.