How grain size influences hydrocarbon generation and expulsion of shale based on Rock-Eval pyrolysis and kinetics?

The differences between the Rock-Eval pyrolysis results of powder and grain samples have attracted wide attentions. Grain samples show lower hydrocarbon yield and different composition of the products. However, the effect of grain size on hydrocarbon generation and expulsion has not yet been quantitatively evaluated. In this study, we prepared each grain into a regular column with precise geometric parameters such as diameter, height, surface area, and volume, which is defined as an independent unit of hydrocarbon generation and expulsion. For comparison, a powder sample corresponding to each grain sample is collected simultaneously during the preparation process. The grain samples are used to simulate the mass of hydrocarbons expelled, while the powder samples are used to simulate the total mass of hydrocarbon generated. Our results show significant differences between the grain samples and the powder samples. All powder samples have a higher expulsion of free hydrocarbons (S1) than grain samples, and almost all grain samples have a higher expulsion of pyrolysis hydrocarbons (S2) than powder samples when the diameter of the grains is smaller than 3 mm. Temperature controls hydrocarbon generation, but grain size retards hydrocarbon expulsion. The influences of the "carry-over" phenomenon, oil adsorption and nanopore confinement are enhanced by grain size, which retards and inhibits hydrocarbon expulsion. Some free hydrocarbons (S1) cannot be expelled from the grain samples at 300 °C. Parts of the retained free hydrocarbons (S1) further cracked into small molecules, which can be expelled and detected as pyrolysis hydrocarbons (S2) at 300–650 °C. Four new parameters were proposed to quantify these influences, namely the S1retained, the S2extra expulsion, the HI difference parameter, and the TOC difference parameter. Diameter is more closely related to hydrocarbon expulsion rather than height. For grain samples, HI increases and TOC decreases with increasing diameter. Activation energies for hydrocarbon generation ranges from 43 to 67 kcal/mol for powder samples, while activation energies for grain samples are almost concentrated in 54–55 kcal/mol, indicating a high expulsion threshold for grain samples. As the grain diameter increases from 1.74 to 5.24 mm, the transformation ratio decreases and the generation rate increases, indicating that the grain size delays the expulsion of hydrocarbon. This laboratory simulation provides some new results to better understand the hydrocarbon generation and expulsion of shale rock under natural conditions.