Molecular composition of low-temperature oxidation products in a simulated crude oil In-situ combustion

Abstract

In-situ combustion (ISC) is a thermal enhanced oil recovery process in which energy is generated by the combustion of a portion of the oil within the reservoir. Low temperature oxidation (LTO) is one of the dominant mechanisms controlling fuel availability in ISC and affects the physical properties of the crude oil, thus the characterization of the crude oil and its LTO products are essential for a better understanding of the ISC process. In this study, a thermal oxidation experiment of a heavy crude oil was carried out to investigate the molecular changes associated to coke formation during ISC. More than half of the component was depleted by combustion or thermal pyrolyzed out, leaving a coke-like solid in the reactor with a yield of a quarter by weight of the crude oil. More than 90% of the coke-like solid is toluene soluble. Condensate oil expelled from the reactor was collected with a yield of about 15 wt% of the crude oil. Small-molecule oxidation products, such as ketones, fatty acids, phenolic compounds were identified in the condensate by GC–MS. High-resolution mass spectrometry results showed that the molecular composition of oxygen- and sulfur-containing compounds changed largely, with the generation of highly oxygenated compounds and sulfoxides. A substantial portion of large-molecule hydrocarbons were survived and enriched in the residue. The main components in the toluene insoluble substance, namely oxidation coke, are methanol soluble and composed of highly oxygenated compounds. The results indicate that oxidation and thermal cracking are both the important reaction in the simulated ISC, the molecular composition is instructive for the understanding of pyrolysis and oxidation behavior of coke formation from the crude oil.