Abstract
Crushing and grinding of carbonaceous shale samples is likely to enhance the accessibility of pores and embedded organic matter as compared to the intact rock. This may lead to an overestimation of the total (volume and sorptive) gas storage capacity. In order to investigate the importance of these effects we have measured unconfined apparent grain densities (helium pycnometry) and methane sorption capacities (high-pressure methane excess sorption) of four carbonaceous shales (Cambro-Ordovician Alum Shale, Jurassic Kimmeridge Clay, Jurassic/Cretaceous Bazhenov Shale, and Late Cretaceous Eagle Ford Shale) as a function of particle size. Measurements were first conducted on 38 mm diameter core plugs, which then were crushed and milled to successively smaller particle sizes (<10 mm, <2 mm, <64 μm, and <1 μm). Apparent grain densities of the smallest particle fractions of the Alum, Bazhenov and Kimmeridge samples were consistently higher by 0.5 to 1% than apparent grain densities of the original sample plugs. Methane excess sorption capacity increased significantly for particle sizes <64 μm for the Alum and <1 μm for the Bazhenov and Kimmeridge samples while no significant changes upon grinding were observed for the Eagle Ford Shale. For the Bazhenov Shale, the apparent grain density increased slightly from 2.446 g/cm3 to 2.450 g/cm3 upon particle size reduction from <64 μm to <1 μm while the maximum sorption capacity (“Langmuir volume”) increased substantially from 0.11 mmol/g to 0.19 mmol/g. Similarly, for the Kimmeridge Clay and Alum Shale, a slight increase of the apparent grain density from 1.546 g/cm3 to 1.552 g/cm3 and from 2.362 g/cm3 to 2.385 g/cm3, respectively, was accompanied by increases in sorption capacity from 0.37 mmol/g to 0.45 mmol/g and from 0.14 mmol/g to 0.185 mmol/g, respectively. The increase in sorption capacity indicates an opening of a considerable amount of micropores with large internal surface area upon physical disruption of the rock fabric and/or removal of included fluids. It may also be due to increased swelling abilities of clay minerals and organic matter upon destruction of the stabilizing rock fabric with decreasing particle size. Grain density and sorption isotherms measured on small particle sizes are likely to overestimate the gas storage capacities and the amounts of producible gas-in-place since under field conditions (largely undisrupted rock fabric), significant portions of this storage capacity are essentially inaccessible. Poor interconnectivity of the pore system and slow, diffusion-controlled transport will massively retard gas production. Based on these findings, particle sizes >64 μm should be used for porosity and sorption measurements because they are more likely to retain the properties of the rock fabric in terms of accessible pore volume and sorptive storage capacity.
Highlights
The characterization of the pore systems of shales still constitutes a major challenge substantial effort has been dedicated to this research (e.g. [1,2,3,4,5,6,7,8]), and some progress has been made in recent years
Pore volumes and grain densities measured in the laboratory depend on the method used and on the particle size of the samples
The main aim of this study was to investigate whether successive reduction of the particle size from plug (~38 mm diameter) to
Summary
The characterization of the pore systems of shales still constitutes a major challenge substantial effort has been dedicated to this research (e.g. [1,2,3,4,5,6,7,8]), and some progress has been made in recent years. Apparent grain and apparent pore volume, are not intrinsic properties and can change upon particle size reduction. They may vary depending on equilibration time, utilization of different gases, and sample pretreatment (e.g. drying procedure and solvent extraction). The “true grain volume” is an intrinsic rock property and is defined as the volume (of the mineral and organic matter) after removal of all enclosed pores and fluids. This is typically achieved by grinding to very small particle sizes
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.