Characteristics of molecular nitrogen generation from overmature black shales in South China: Preliminary implications from pyrolysis experiments

Abstract

High content of molecular nitrogen (N2) is one of the natural gas exploration risks in petroliferous basins where black shales act as source rocks of either hydrocarbon gas or molecular nitrogen. In this study, two overmature and one low-maturity shale samples and their kerogens were investigated to determine the generation characteristics of molecular nitrogen as well as methane and the differences in the release processes of inorganic nitrogen fixed in ammonium-bearing minerals and organic nitrogen bound in kerogen. The results illustrate that with increasing pyrolysis temperature, the yield of methane first increases and then decreases with an inflection temperature of 650 °C (EqVRo = 3.4%), whereas the yield of molecular nitrogen shows a continuous increase throughout the pyrolysis experiment. The molecular nitrogen during the stage of methane generation (i.e., EqVRo < 3.4%) is more preferentially derived from the inorganic nitrogen in ammonium-bearing minerals, whereas the significant generation of molecular nitrogen from organic nitrogen in kerogen commences only after the methane generation potential is exhausted (EqVRo > 3.4%). The results also reveal that at the experimental maxima of thermal maturity (EqVRo = 4.9%), the generation potential of inorganic molecular nitrogen (mg/g Ninorg) is much lower than that of organic molecular nitrogen (mg/g Norg), indicating that in our experiments the organic nitrogen in kerogen is more easily to be converted into molecular nitrogen than the inorganic nitrogen in ammonium-bearing minerals. All these results indicate that molecular nitrogen content in shale gas may change dramatically during thermal evolution, and source rocks with exceptionally high maturity and high abundance of organic nitrogen likely lead to a high molecular nitrogen risk, particularly in regions of poor preservation conditions of shale gas, which may be the main reasons for the high molecular nitrogen content in the Lower Cambrian shale gas in South China.