Characterization of kerogen molecular structure and its effect on methane adsorption behavior: A comparative study on outcrop and core samples from Longmaxi shale.

• Microstructures of the outcrop/core kerogen were systematically characterized. • Differences in chemical structure between the outcrop/core kerogen were identified. • Realistic 2D/3D molecular models of the outcrop/core kerogen were constructed. • Validity of the proposed molecular models was verified by gravimetric adsorption. • Effect of the kerogen microstructure on CH 4 adsorption behavior was investigated. It has been known that adsorbed gas, mainly CH 4 , serves as the dominant source of shale gas yield in the middle and later stages of reservoir exploitation. Therefore, it is of great significance to study the microstructure of kerogen (organic matter rich in shale) and its effect on CH 4 adsorption characteristics. In this paper, for the first time, a comparative study was conducted to experimentally characterize the microstructure of both outcrop and core kerogen samples from Longmaxi Shale, Sichuan Basin, SW China, using 13C NMR, FTIR, and XPS. Great differences in the chemical structure such as carbon skeleton (e.g. , aromaticity, aliphatic branch) and heteroatoms (e.g. , distribution and proportion of various types of functional groups) between the two kerogen samples have been identified. Molecular models of the outcrop and core kerogen samples were constructed based on the experimental data, that is, C 237 H 219 O 21 N 5 S 4 for the former and C 239 H 175 O 27 N 5 S 4 for the latter. CH 4 adsorption isotherms obtained from gravimetric adsorption test and molecular simulation using proposed kerogen molecular models are in reasonable agreement with each other, especially at low-pressure range. Interestingly, the adsorption capacity of CH 4 in the core sample is found higher than that in the outcrop sample under the same condition, indicating the effect of kerogen microstructure on CH 4 adsorption behavior. As a result, to precisely evaluate the adsorbed gas content in shale gas reservoirs, it is strongly recommended to use a core sample rather than an outcrop sample. [ABSTRACT FROM AUTHOR]