Experimental Investigation of the Dependence of Accessible Porosity and Methane Sorption Capacity of Carbonaceous Shales on Particle Size

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...

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Main Authors: Garri Gaus, Anton Kalmykov, Bernhard M. Krooss, Reinhard Fink
Format: Article
Language:English
Published: Wiley 2020-01-01
Series:Geofluids
Online Access:http://dx.doi.org/10.1155/2020/2382153
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author Garri Gaus
Anton Kalmykov
Bernhard M. Krooss
Reinhard Fink
author_facet Garri Gaus
Anton Kalmykov
Bernhard M. Krooss
Reinhard Fink
author_sort Garri Gaus
collection DOAJ
description 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.
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spelling doaj-art-2c5a47badc204551b72e83ef414e792f2025-02-03T01:32:23ZengWileyGeofluids1468-81151468-81232020-01-01202010.1155/2020/23821532382153Experimental Investigation of the Dependence of Accessible Porosity and Methane Sorption Capacity of Carbonaceous Shales on Particle SizeGarri Gaus0Anton Kalmykov1Bernhard M. Krooss2Reinhard Fink3Institute of Geology and Geochemistry of Petroleum and Coal, Energy and Mineral Resources Group (EMR), Lochnerstr. 4-20, RWTH Aachen University, D-52062 Aachen, GermanyFaculty of Geology and Geochemistry of Combustibles, Lomonosov Moscow State University, Leninskie Gory 1, 119234 Moscow, RussiaInstitute of Geology and Geochemistry of Petroleum and Coal, Energy and Mineral Resources Group (EMR), Lochnerstr. 4-20, RWTH Aachen University, D-52062 Aachen, GermanyInstitute of Geology and Geochemistry of Petroleum and Coal, Energy and Mineral Resources Group (EMR), Lochnerstr. 4-20, RWTH Aachen University, D-52062 Aachen, GermanyCrushing 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.http://dx.doi.org/10.1155/2020/2382153
spellingShingle Garri Gaus
Anton Kalmykov
Bernhard M. Krooss
Reinhard Fink
Experimental Investigation of the Dependence of Accessible Porosity and Methane Sorption Capacity of Carbonaceous Shales on Particle Size
Geofluids
title Experimental Investigation of the Dependence of Accessible Porosity and Methane Sorption Capacity of Carbonaceous Shales on Particle Size
title_full Experimental Investigation of the Dependence of Accessible Porosity and Methane Sorption Capacity of Carbonaceous Shales on Particle Size
title_fullStr Experimental Investigation of the Dependence of Accessible Porosity and Methane Sorption Capacity of Carbonaceous Shales on Particle Size
title_full_unstemmed Experimental Investigation of the Dependence of Accessible Porosity and Methane Sorption Capacity of Carbonaceous Shales on Particle Size
title_short Experimental Investigation of the Dependence of Accessible Porosity and Methane Sorption Capacity of Carbonaceous Shales on Particle Size
title_sort experimental investigation of the dependence of accessible porosity and methane sorption capacity of carbonaceous shales on particle size
url http://dx.doi.org/10.1155/2020/2382153
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AT bernhardmkrooss experimentalinvestigationofthedependenceofaccessibleporosityandmethanesorptioncapacityofcarbonaceousshalesonparticlesize
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