Hydrocarbon retention in lacustrine shales during thermal maturation: Insights from semi-open system pyrolysis

Abstract Evaporative loss of light hydrocarbons during shale core collection and sample preparation makes it challenging to characterize hydrocarbon retention and accurately evaluate petroleum resources in a shale layer with high thermal maturity. Here, semi-open system pyrolysis experiment was applied to investigate the evolution of hydrocarbon in shales during thermal maturation, using an immature lacustrine shale with total organic carbon (TOC) of 2.13 wt% from the Es3 Member in Dongpu Depression, Bohai Bay Basin, China. Moreover, Ro measurement, solvent extraction, kinetic study, open-system pyrolysis, thermovaporization-gas chromatography (Tvap-GC) and pyrolysis-gas chromatography (Py-GC) were also conducted on the products from semi-open system pyrolysis experiments. Retained oil in shales consists of free oil (pyrolysis S1) and sorbed oil (involved in pyrolysis S2). A preponderance of sorbed oil retained in the studied lacustrine shale is observed, with its content reaching to more than 4 times larger than that of free oil at a given thermal maturity. As thermal maturity increases, molecular weights of n-alkanes in free oil show a more obvious reduction than sorbed oil. In addition, compared to sorbed oil, free oil is more likely to be retained at higher thermal maturity. Despite of the larger oil generation potential than gas of the immature shale sample, residual hydrocarbon generation potential of heated lacustrine shales is dominated by gaseous hydrocarbon, and consists of >90% of the potential losses before entering into gas window. Change of TOC in lacustrine shales, which roughly characterizes hydrocarbon generation process, is attributed to both the loss of hydrocarbon generation potential and the formation of pyrobitumen. Although hydrocarbon retention in shales is affected by many complex processes and is controlled by various factors, it can be virtually considered as a status when hydrocarbon generation, expulsion and retention during thermal maturation come to a balance. A “retention ratio (RR)” index is thus suggested in this study, based on experimental results from semi-open system and open-system pyrolysis. Application of RR in resource evaluation in a shale play is reasonable especially in high-mature shales, because evaporative loss of light hydrocarbon is considered in this method.