Fluid distribution and gas adsorption behaviors in over-mature shales in southern China

To better understand the mechanism of hydrocarbon accumulation and fluid migration in Chinese shales, several samples from two leading marine shales (Longmaxi and Niutitang) were collected for geochemical and mineral analysis, the characterization of pore structure, preliminary studies on fluid flow, and the distribution and investigation of different methane adsorption behaviors. Firstly, the Longmaxi and Niutitang marine shales were found to be in an over-matured stage and dry gas window. Pore structures and connectivity were characterized by field emission - scanning electron microscopy (FE-SEM). The SEM images showed that the micro-fracture, interparticle pores, and organic pores had better connectivity than intraparticle pores. Results from contact angles indicated that the Longmaxi and Niutitang shales tended to have higher affinities for oil rather than for water. The connectivity of pores, distribution of fluids (water and gas) and fluid flow behaviors in the over-matured shale were analyzed using spontaneous imbibition (SI) and tracer diffusion tests. It was found the tracer fluids flow in the way of network flow inside of shale matrix. The connected pore network may be the main path for fluid migration in shale. Additionally, a gravimetric isothermal adsorption experiment was applied to assess methane adsorption capacity in shale. Shale samples with higher total organic carbon (TOC) contents had higher methane adsorption capacities. Organic matter (including kerogen and bitumen), had much greater adsorption capabilities than inorganic minerals (quartz, clay, and others). Finally, the fluid distribution patterns in over-matured marine shale were studied. Shale gas was originally generated in organic matter and then migrated out through connected pores, under differential pressure, between internal and external organic matter hydrocarbon generation areas. These hydrocarbons replaced the water in the pores. Therefore, shale gas may adsorb in organic pores and is freely stored in connected inorganic pores, with bound water, whereas isolated pores are saturated with water. Two different adsorption patterns on mineral surfaces (organic matters and inorganic minerals) were established to explain the different shale gas adsorption behaviors in organic pores and connected pores, with bound water.