Hydrocarbon evaporative loss from shale core samples as revealed by Rock-Eval and thermal desorption-gas chromatography analysis: Its geochemical and geological implications

摘要

The 51 peak generated by Rock-Eval analysis of source rock and reservoir interval core and cuttings samples has been routinely employed for in-place hydrocarbon resources assessment by petroleum geochemists, geologists and even engineers. Significant evaporative loss of gaseous and light hydrocarbons (up to C-10) can occur during core and cuttings collection and storage, and subsequent sample preparation in the laboratory before instrumental analysis. Consequently a correction to the S1 values is needed in order to obtain a more accurate estimate of the resources. To investigate the effect of evaporative loss on both the amount and the composition of the hydrocarbons retained in shale, a time-series of Rock-Eval and thermal desorption-gas chromatography (TD-GC) analyses have been carried out on an organic-rich Devonian Duvernay Formation shale core sample from the Western Canada Sedimentary Basin (WCSB) and an organic-lean Ordovician Lotbiniere Formation shale core sample from Quebec, Canada. The results suggest that the content of total organic carbon (TOC) may play an important role in retaining and preserving light hydrocarbons in sedimentary rocks. A total loss of gaseous and light liquid hydrocarbons up to C-9 is shown to take place within 21 h of sample preparation for the low TOC (<1%) Ordovician Lotbiniere shale when the powdered sample was left exposed to the open air, accounting for a 38% decrease in its Rock-Eval S1 peak. The Rock-Eval S1 peak can be reduced by 29% even if the powdered sample has been stored in a sealed container for just over a week. In contrast, the volatile loss has been found to occur at a much slower rate for the high TOC (>11%) Devonian Duvernay shale core sample. After 360 h of exposure to the open air, the powdered Duvernay shale sample shows only 15% decline in its Rock-Eval S1 peak, and still contains high relative concentrations of C-7-C-9 hydrocarbons. In addition, the evaporative loss of some isomers of C-5-C-7 hydrocarbons from the organic-rich shale is not fully in agreement with their GC retention/elution behavior, but appears to be partially controlled by their adsorption/desorption on the organic matter and mineral matrix. This suggests that the C-5-C-8 gasoline range hydrocarbon parametefs should be used with caution for oil oil correlation for unconventional shale and tight petroleum systems. While the findings in this study validate the current industrial practice that targets organic-rich and mature shale intervals for unconventional shale gas and oil exploration because of their large hydrocarbon storage capacity, the results also have an important implication that high TOC content may adversely affect the production efficiency of shale and tight hydrocarbon reservoirs due to the strong adsorption of hydrocarbons by the high maturity organic matter. Crown Copyright (C) 2015 Published by Elsevier Ltd. All rights reserved.