Experimental study of the effects of thermochemical sulfate reduction on low molecular weight hydrocarbons in confined systems and its geochemical implications

摘要

Experimental studies of the effects of thermochemical sulfate reduction (TSR) on light hydrocarbons were conducted in sealed gold tubes for 72h at 400°C and 50MPa. A variety of pyrolysis experiments were carried out, including anhydrous, hydrous without MgSO_4 (hydrous experiments) and hydrous with MgSO_4 (TSR experiments). Common reservoir minerals including montmorillonite, illite, calcite and quartz were added to various experiments. Measurements of the quantities of n-C_(9+) normal alkanes (high molecular weight, HMW), n-C_(6-8) normal alkanes (low molecular weight, LMW), C_(7-8) isoalkanes, C_(6-7) cycloalkanes and C_(6-9) monoaromatics and compound specific carbon isotope analyses were made. The results indicate that TSR decreases hydrocarbon thermal stability significantly as indicated by chemically lower concentrations and isotopically heavier LMW saturated hydrocarbons in the TSR experiments compared to the hydrous and anhydrous experiments. In the LMW saturated hydrocarbon fraction, cycloalkanes tend to be more resistant to TSR than n-alkanes and isoalkanes. TSR promotes aromatization reactions and favors the generation of monoaromatics, resulting in higher chemical concentrations and isotopically equivalent compositions of monoaromatics in the anhydrous, hydrous and TSR experiments. This indicates that LMW monoaromatics are thermally stable during the pyrolysis experiments. Acid rather than basic catalyzed ionic reactions probably play a major role in TSR. This is suggested by the promotion effects of acid-clay minerals including illite and particularly montmorillonite. The basic mineral calcite retards the destruction of n-C_(9+) normal alkanes within the TSR experiments. Furthermore, clay minerals have a minor influence on the generation of LMW monoaromatics and play a negative role in regulating the concentrations of LMW saturated hydrocarbons; calcite does not favor the generation of LMW monoaromatics and plays a positive role in controlling the concentrations of LMW saturates relative to clay minerals. Quartz has a negligible role in the TSR experiments.Due to their differential responses to TSR, LMW hydrocarbon parameters, such as Schaefer [Schaefer, R.G., Littke, R., 1988. Maturity-related compositional changes in the low-molecular-weight hydrocarbon fraction of Toarcian Shale. Organic Geochemistry 13, 887-892], Thompson [Thompson, K.F.M., 1988. Gas-condensate migration and oil fractionation in deltaic systems. Marine and Petroleum Geology 5, 237-246], Halpern [Halpern, H., 1995. Development and application of light-hydrocarbon-based star diagrams. American Association of Petroleum Geologists Bulletin 79, 801-815] and Mango [Mango, F.D., 1997. The light hydrocarbons in petroleum: a critical review. Organic Geochemistry 26, 417-440] parameters and stable carbon isotopic compositions of individual LMW saturated hydrocarbons in TSR affected oils should be used with caution. In addition, water promotes thermal cracking of n-C_(9+) normal alkanes and favors the generation of LMW cycloalkanes and monoaromatics. The result is lower concentrations of n-C_(9+) HMW normal alkanes and higher concentrations of LMW cycloalkanes and monoaromatics in hydrous experiments relative to anhydrous experiments with or without minerals.This investigation provides a better understanding of the effects of TSR on LMW hydrocarbons and the influence of reservoir minerals on TSR in natural systems. The paper shows how LMW hydrocarbon indicators in TSR altered oils improve understanding of the processes of hydrocarbon generation, migration and secondary alteration in subsurface petroleum reservoirs.