Bound hydrocarbons and structure of pyrobitumen rapidly formed by asphaltene cracking: Implications for oil–source correlation

Abstract

The pyrobitumen in conventional petroleum reservoirs is a thermally altered product of ancient oil pools, which may provide valuable source information using its molecular and isotopic signatures. Pyrobitumen formation is often associated with thermal alteration of asphaltene or polar-rich components rather than that of oil as a whole. Although asphaltenes are useful in source correlation of altered oils, the geochemical characteristics of asphaltene-derived pyrobitumen are poorly understood. In this study, artificial pyrobitumen formation through oil asphaltene cracking was performed at different thermal simulation (i.e., pyrolysis) temperatures. Systematic variations in the amounts and distributions of extractable and bound hydrocarbons, released by catalytic hydropyrolysis of the artificially produced pyrobitumen were studied. Pyrobitumen production yield was high at pyrolysis temperatures corresponding to post oil peak maturities, with a maximum yield of ∼70 wt% of asphaltene being reached in the early condensate–wet-gas stage. The molecular structure of pyrobitumen varied only slightly over the high maturity range (EasyRo 1.64–2.51%). Compared with the parent asphaltene, the pyrobitumen had a low biomarker (e.g., regular steranes and terpanes) content, and even the carbon isotopic values of the more stable bound n-alkanes were strongly altered. Thermal cracking of asphaltene alone, rather than whole oil, accelerates cross-linking of aromatic units, and cleavage or condensation of molecules bound in the pyrobitumen. These molecular changes suggest that care is needed when using the geochemical characteristics of bound hydrocarbons in natural pyrobitumen for source determinations. Nevertheless, the carbon isotopic ratios of bulk pyrobitumen hydropyrolysate were similar to those of bulk oil or pyrobitumen, even at very high maturities, suggesting these may be reliable indices for source tracing. A comparison of carbon isotopic compositions between pyrobitumen-bound and solvent-extractable n-alkanes could be useful in determining whether they have the same origin. Furthermore, the compositional and isotopic characteristics of bound hydrocarbons in pyrobitumen may provide information on the stage of maturity under geological conditions. The investigation of free and bound molecules may thus elucidate pyrobitumen genesis as related to its source, thermal maturity, and possible later hydrocarbon charging.