Fractionation of alkylated carbazoles in petroleum during subsurface migration: Evidence from molecular simulation and application in sandstone reservoirs.

Carbazole (CA) and alkylated carbazoles are common nitrogen-containing heterocyclic aromatic compounds widely found in crude oils and sedimentary rocks extracts. Their geochemical significances in petroleum exploration have been widely investigated in previous studies. Using density functional theory (DFT) and molecular dynamics (MD) simulation, we calculated the polarity of alkylated carbazole isomers/homologues and their adsorption energy with water and α-quartz, respectively. The calculated results show that there are significant differences in migration fractionation effects for alkylated carbazole isomers/homologues. This study confirmed the validity of previously proposed carbazole migration indicators, i.e. 4-/1-MCA (the relative abundance of 4-methylcarbazole to 1-methylcarbazole), 2,5-/1,8-DMCA (2,5-dimethylcarbazole to 1,8-dimethylcarbazole) and 2,4-/1,8-DMCA (2,4-dimethylcarbazole to 1,8-dimethylcarbazole) on the basis of quantum chemistry and molecular simulation. All these three parameters have been successfully applied in a lacustrine sandstone reservoir in the Fushan Depression, Beibuwan Basin (South China Sea). The calculations of Gibbs free energy show that the differences in thermal stability between the isomers of alkylcarbazoles can be negligible. The source input and depositional environment have no significant effect on these indicators for oils from a same oil family. Hence, the values of these parameters are mainly controlled by subsurface petroleum migration processes. Therefore, the molecular parameters relative to alkylated carbazoles can be used as practically effective geochemical markers to trace the oil filling orientation and pathways for subsurface oil migration. • Geochromatography of alkylcarbazoles was calculated by molecular dynamics simulation. • Three indicators were proposed to trace oil migration orientation. • Alkylcarbazoles were successfully applied in lacustrine sandstone reservoirs. • The effect of maturity and depositional environment were discussed. [ABSTRACT FROM AUTHOR]