Multi-scale multi-dimensional imaging and characterization of oil shale pyrolysis

In recent years, oil shale has attracted renewed attention as an unconventional energy resource, with vast and largely untapped reserves. Oil shale is a fine-grained sedimentary rock containing a sufficiently high content of immature organic matter from which shale oil and combustible gas can be extracted through pyrolysis. Several complex physical and chemical changes occur during the pyrolysis of oil shale where macromolecular network structures of kerogen are thermally decomposed. The pyrolysis of oil shale leads to the formation of a microscopic pore network in which the oil and gas products flow. The pore structure and the connectivity are significant characteristics which determine fluid flow and ultimate hydrocarbon recovery. In this thesis, a state-of-the-art multi-scale multi-dimensional workflow was applied to image and quantify the Lacustrine Eocene Green River (Mahogany Zone) formation, the world’s largest oil shale deposit. Samples were imaged before, during and after pyrolysis using laboratory and synchrotron-based X-ray Micro-tomography (µCT), Optical Microscopy, Automated Ultra-High Resolution Scanning Electron Microscopy (SEM), MAPS Mineralogy (Modular Automated Processing System) and Focused Ion Beam Scanning Electron Microscopy (FIB-SEM). Results of image analysis using optical (2-D), SEM (2-D), and µCT (3-D) reveal a complex fine-grained microstructure dominated by organic-rich parallel laminations in a tightly bound heterogeneous mineral matrix. MAPS Mineralogy combined with ultrafast measurements highlighted mineralogic textures dominated by dolomite, calcite, K-feldspar, quartz, pyrite and illitic clays. From high resolution backscattered electron (BSE) images, intra-organic, inter-organic-mineral, intra and inter-mineral pores were characterised with varying sizes and geometries. A detailed X-ray µCT study with increasing pyrolysis temperature (300-500°C) at 12 µm, 2 µm and 0.8 µm voxel sizes illuminated the evolution of pore structure, which is shown to be a strong function of the spatial distribution of organic content. In addition, FIB-SEM 3-D visualisations showed an unconnected pore space of 0.5% with pores sizes between 15 nm and 22 nm for the un-pyrolysed sample and a well-connected pore space of 18.2% largely with pores of equivalent radius between 1.6 µm and 2.0 µm for the pyrolysed sample. Synchrotron 4-D results at a time resolution of 160 seconds and a voxel size of 2 µm revealed a dramatic change in porosity accompanying pyrolysis between 390-400°C with the formation of micron-scale heterogeneous pores followed by interconnected fracture networks predominantly along the organic-rich laminations. Combining these techniques provides a powerful tool for quantifying petrophysical properties before, during and after oil shale pyrolysis. Quantitative 2-D, 3-D and 4-D imaging datasets across nm-µm-mm length scales are of great value to better understand, predict and model dynamics of pore structure change and hydrocarbon transport and production during oil shale pyrolysis. Open Access