Structure and Evolution of Clay-Organic Nanocomposites in Three Leading Shales in China

Organic matter(OM)in shales occurs as nanometer-sized intercalations with clay minerals that are termed as clay-organic nanocomposites;however,the OM occurrence in nanocomposites at different stages of maturation is still unclear,and the co-evolution process of OM and clay under burial is not well understood.To reveal the variation of OM occurrence and clarify the relationship between petroleum generation of OM&transformation of clay minerals in nanocomposites as a function of maturity,this study investigates the structure and clay-OM association in 44 samples from three leading shales at different maturity stages from two basins in China.A total of 15 samples of lacustrine shale from upper Triassic Yanchang Formation,15 samples of marine shale from Lower Silurian Longmaxi Formation,and 14 samples of marine shale from Lower Cambrian Niutitang Formation were analyzed based on organic geochemistry,X-ray diffraction(XRD),and field emission-scan electron microscopy(FE-SEM),focused ion beam(FIB)sample preparation and consequent high resolution-transmission electron microscopy(HR-TEM)observations combined with energy dispersive spectroscopy(EDS).The results from this study show that most shale samples are organic-rich,and these three shales represent thermal evolutionary process from oil-window mature to overmature in a sequence of Triassic Yanchang,Silurian Longmaxi,and Cambrian Niutitang formations.Thorough observations indicate that sub-parallel bands of clays and intermingling of detrital minerals(such as quartz)dominate the nanocomposites in the Yanchang samples.While for Longmaxi and Niutitang shales,abundant nanopores and pyrite nanoparticles are observed in nanocomposites with features of layered distributions of OM and clay minerals.The structural investigation of nanocomposites shows that organic carbon between multi-layers dominates the OM occurrence in nanocomposites,which significantly extends the traditional opinion of OM-clay association.At an oil-window mature stage,the fluctuational interlayer spacing and a certain intensity of the carbon peak observed in the EDS spectra for corresponding clays provide a visual evidence of the organic molecules accessing the monolayer spaces of smectite.With the evolutional process of nanocomposites in shale and petroleum generation of OM&mineral transformation(illitization of smectite)running in parallel,it is inferred that the organic molecules migrate from monolayer spaces as gaseous hydrocarbons are generated,and eventually form stable clay-organic nanocomposites at an overmature stage.The results presented here will contribute to an improved understanding of diagenesis and organic-inorganic interactions in OM-rich shales.

Role of the Interlayer Space of Montmorillonite in Hydrocarbon Generation: A Combined Study by TG-FTIR and High Temperature-Pressure Pyrolysis

The interlayer clay-organic complex is an important clay-organic association in sedimentary environments. The interlayer region of clay minerals not only provides storage space for organic matter, but also possesses solid acid sites; and these acid sites were proposed to be involved with the transformation of organic matter into liquid and gaseous hydrocarbons. However, the effect of the organic matter storage in the interlayer space of clay minerals on the hydrocarbons generation has not been made clear. In this study, the interlayer complex of 12-aminolauric acid (ALA) and Na+-montmorillonite (Na+-Mt), labeled as ALAinter-Mt (Na), was synthesized to investigate the role of the interlayer space of montmorillonite in hydrocarbon generation. Simply mixed ALA-Mt complex [ALA-Mt (Na)] was also prepared for comparison. The pyrolysis of ALA and ALA-Mt complexes was studied using thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR) and a high temperature-pressure system (a confined gold capsule-autoclave system).