Small-angle Neutron Scattering (SANS) Characterization of Clay- and Carbonate-rich Shale at Elevated Pressures
Abstract
Unconventional oil and gas from shale formations have emerged as some of the fastest growing energy resources in the United States, providing both cleaner energy to consumers and reducing the nation’s reliance on energy imports. To properly harness these important natural resources, the nanopore structure of associated shales must be fully understood, particularly under hydraulic fracturing conditions, where they are exposed to both overburden compressive and hydrostatic fluid pressures. The current study uses small-angle neutron scattering (SANS) to characterize pore structure, including porosity, pore accessibility, and pore size distribution, in the 1–100 nm regime at elevated pressures for mineralogically distinct clay- and carbonate-rich shales from the Permian Basin. Unlike typical porosity measurement techniques, SANS is uniquely capable of characterizing both open and closed porosity, allowing measurement of how pore accessibility changes with pressure and determination of the size range of accessible versus inaccessible pores. The porosity of the clay-rich shale was 7.7%, compared to 0.51% for the carbonate-rich shale. However, only 2.6% of the nanopores in the carbonate-rich shale were inaccessible to water at 8 kPSI (55.1 MPa) compared to 7.8% for the clay-rich shale. Furthermore, our analyses indicated that the closed pores fall within distinct size ranges, likely correspondingmore »
- Authors:
-
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Washington State Univ., Pullman, WA (United States)
- Washington State Univ., Pullman, WA (United States)
- National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
- Chevron Energy Technology Co., Houston, TX (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
- OSTI Identifier:
- 1726178
- Report Number(s):
- LA-UR-19-30857
Journal ID: ISSN 0887-0624
- Grant/Contract Number:
- 89233218CNA000001; DMR-1508249
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy and Fuels
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 7; Journal ID: ISSN 0887-0624
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Scattering; shale; porosity; clay
Citation Formats
Neil, Chelsea W., Hjelm, Rex P., Hawley, Marilyn E., Watkins, Erik B., Cockreham, Cody, Wu, Di, Mao, Yimin, Fischer, Timothy B., Stokes, M. Rebecca, and Xu, Hongwu. Small-angle Neutron Scattering (SANS) Characterization of Clay- and Carbonate-rich Shale at Elevated Pressures. United States: N. p., 2020.
Web. doi:10.1021/acs.energyfuels.0c01009.
Neil, Chelsea W., Hjelm, Rex P., Hawley, Marilyn E., Watkins, Erik B., Cockreham, Cody, Wu, Di, Mao, Yimin, Fischer, Timothy B., Stokes, M. Rebecca, & Xu, Hongwu. Small-angle Neutron Scattering (SANS) Characterization of Clay- and Carbonate-rich Shale at Elevated Pressures. United States. https://doi.org/10.1021/acs.energyfuels.0c01009
Neil, Chelsea W., Hjelm, Rex P., Hawley, Marilyn E., Watkins, Erik B., Cockreham, Cody, Wu, Di, Mao, Yimin, Fischer, Timothy B., Stokes, M. Rebecca, and Xu, Hongwu. Fri .
"Small-angle Neutron Scattering (SANS) Characterization of Clay- and Carbonate-rich Shale at Elevated Pressures". United States. https://doi.org/10.1021/acs.energyfuels.0c01009. https://www.osti.gov/servlets/purl/1726178.
@article{osti_1726178,
title = {Small-angle Neutron Scattering (SANS) Characterization of Clay- and Carbonate-rich Shale at Elevated Pressures},
author = {Neil, Chelsea W. and Hjelm, Rex P. and Hawley, Marilyn E. and Watkins, Erik B. and Cockreham, Cody and Wu, Di and Mao, Yimin and Fischer, Timothy B. and Stokes, M. Rebecca and Xu, Hongwu},
abstractNote = {Unconventional oil and gas from shale formations have emerged as some of the fastest growing energy resources in the United States, providing both cleaner energy to consumers and reducing the nation’s reliance on energy imports. To properly harness these important natural resources, the nanopore structure of associated shales must be fully understood, particularly under hydraulic fracturing conditions, where they are exposed to both overburden compressive and hydrostatic fluid pressures. The current study uses small-angle neutron scattering (SANS) to characterize pore structure, including porosity, pore accessibility, and pore size distribution, in the 1–100 nm regime at elevated pressures for mineralogically distinct clay- and carbonate-rich shales from the Permian Basin. Unlike typical porosity measurement techniques, SANS is uniquely capable of characterizing both open and closed porosity, allowing measurement of how pore accessibility changes with pressure and determination of the size range of accessible versus inaccessible pores. The porosity of the clay-rich shale was 7.7%, compared to 0.51% for the carbonate-rich shale. However, only 2.6% of the nanopores in the carbonate-rich shale were inaccessible to water at 8 kPSI (55.1 MPa) compared to 7.8% for the clay-rich shale. Furthermore, our analyses indicated that the closed pores fall within distinct size ranges, likely corresponding with the chemical nature of the pore host material. These results provide valuable insight into the effects of shale petrophysical properties on hydrocarbon extraction from unconventional reservoirs.},
doi = {10.1021/acs.energyfuels.0c01009},
journal = {Energy and Fuels},
number = 7,
volume = 34,
place = {United States},
year = {2020},
month = {6}
}
Works referenced in this record:
The future of U.S. natural gas production, use, and trade
journal, September 2011
- Paltsev, Sergey; Jacoby, Henry D.; Reilly, John M.
- Energy Policy, Vol. 39, Issue 9
The Impact of the Shale Oil Revolution on U.S. Oil and Gasoline Prices
journal, July 2016
- Kilian, Lutz
- Review of Environmental Economics and Policy, Vol. 10, Issue 2
The Mechanics of Design and Interpretation of Hydraulic Fracture Treatments
journal, October 1959
- Crittendon, Bob C.
- Journal of Petroleum Technology, Vol. 11, Issue 10
Experimental study on fracture initiation and propagation in shale using supercritical carbon dioxide fracturing
journal, February 2017
- Zhang, Xinwei; Lu, Yiyu; Tang, Jiren
- Fuel, Vol. 190
Hydraulic fracture monitoring in hard rock at 410 m depth with an advanced fluid-injection protocol and extensive sensor array
journal, November 2016
- Zang, Arno; Stephansson, Ove; Stenberg, Leif
- Geophysical Journal International, Vol. 208, Issue 2
2D-numerical analysis of hydraulic fracturing in heterogeneous geo-materials
journal, June 2009
- Wang, S. Y.; Sun, L.; Au, A. S. K.
- Construction and Building Materials, Vol. 23, Issue 6
A USANS/SANS Study of the Accessibility of Pores in the Barnett Shale to Methane and Water
journal, February 2013
- Ruppert, Leslie F.; Sakurovs, Richard; Blach, Tomasz P.
- Energy & Fuels, Vol. 27, Issue 2
Accessibility of pores in coal to methane and carbon dioxide
journal, January 2012
- Melnichenko, Yuri B.; He, Lilin; Sakurovs, Richard
- Fuel, Vol. 91, Issue 1
SANS investigations of CO2 adsorption in microporous carbon
journal, December 2015
- Bahadur, J.; Melnichenko, Y. B.; He, L.
- Carbon, Vol. 95
Estimation and modeling of coal pore accessibility using small angle neutron scattering
journal, December 2015
- Zhang, Rui; Liu, Shimin; Bahadur, Jitendra
- Fuel, Vol. 161
Probing nanopore structure and confined fluid behavior in shale matrix: A review on small-angle neutron scattering studies
journal, January 2020
- Xu, Hongwu
- International Journal of Coal Geology, Vol. 217
Application of small-angle neutron scattering to the study of porosity in energetic materials
journal, May 2000
- Mang, Joseph T.; Skidmore, Cary B.; Hjelm, Rex P.
- Journal of Materials Research, Vol. 15, Issue 5
Flow-through compression cell for small-angle and ultra-small-angle neutron scattering measurements
journal, May 2018
- Hjelm, Rex P.; Taylor, Mark A.; Frash, Luke P.
- Review of Scientific Instruments, Vol. 89, Issue 5
In situ neutron diffraction study of deuterated portlandite Ca(OD)2 at high pressure and temperature
journal, February 2007
- Xu, Hongwu; Zhao, Yusheng; Zhang, Jianzhong
- Physics and Chemistry of Minerals, Vol. 34, Issue 4
High-pressure/low-temperature neutron scattering of gas inclusion compounds: Progress and prospects
journal, March 2007
- Zhao, Y.; Xu, H.; Daemen, L. L.
- Proceedings of the National Academy of Sciences, Vol. 104, Issue 14
Pore structure characterization of North American shale gas reservoirs using USANS/SANS, gas adsorption, and mercury intrusion
journal, January 2013
- Clarkson, C. R.; Solano, N.; Bustin, R. M.
- Fuel, Vol. 103
Pore Architecture and Connectivity in Gas Shale
journal, February 2015
- King, Hubert E.; Eberle, Aaron P. R.; Walters, Clifford C.
- Energy & Fuels, Vol. 29, Issue 3
Porosity of Coal and Shale: Insights from Gas Adsorption and SANS/USANS Techniques
journal, July 2012
- Mastalerz, Maria; He, Lilin; Melnichenko, Yuri B.
- Energy & Fuels, Vol. 26, Issue 8
Quantitative X-Ray Diffraction Analysis of Clay-Bearing Rocks from Random Preparations
journal, January 2001
- Środoń, Jan
- Clays and Clay Minerals, Vol. 49, Issue 6
Some successful approaches to quantitative mineral analysis as revealed by the 3rd Reynolds Cup contest
journal, December 2006
- Omotoso, Oladipo; McCarty, Douglas K.; Hillier, Stephen
- Clays and Clay Minerals, Vol. 54, Issue 6
Quantitative interpretation of X-ray diffraction patterns of mixtures. I. Matrix-flushing method for quantitative multicomponent analysis
journal, December 1974
- Chung, F. H.
- Journal of Applied Crystallography, Vol. 7, Issue 6
Enthalpies of formation of polyhalite: A mineral relevant to salt repository
journal, November 2017
- Guo, Xiaofeng; Xu, Hongwu
- The Journal of Chemical Thermodynamics, Vol. 114
Thermochemistry of microporous silicotitanate phases in the Na 2 O–Cs 2 O–SiO 2 –TiO 2 –H 2 O system
journal, March 2000
- Xu, Hongwu; Navrotsky, Alexandra; Nyman, May D.
- Journal of Materials Research, Vol. 15, Issue 3
Enthalpies of formation of microporous titanosilicates ETS-4 and ETS-10
journal, October 2001
- Xu, Hongwu; Zhang, Yiping; Navrotsky, Alexandra
- Microporous and Mesoporous Materials, Vol. 47, Issue 2-3
Characterization of slip zone associated with the 1999 Taiwan Chi-Chi earthquake: X-ray CT image analyses and microstructural observations of the Taiwan Chelungpu fault
journal, March 2008
- Hirono, Tetsuro; Sakaguchi, Masumi; Otsuki, Kenshiro
- Tectonophysics, Vol. 449, Issue 1-4
Anisotropic thermal expansion and hydrogen bonding behavior of portlandite: A high-temperature neutron diffraction study
journal, April 2007
- Xu, H.; Zhao, Y.; Vogel, S. C.
- Journal of Solid State Chemistry, Vol. 180, Issue 4
High-temperature neutron diffraction study of deuterated brucite
journal, July 2013
- Xu, Hongwu; Zhao, Yusheng; Hickmott, Donald D.
- Physics and Chemistry of Minerals, Vol. 40, Issue 10
Small-angle scattering in materials science - a short review of applications in alloys, ceramics and composite materials
journal, April 2003
- Fratzl, Peter
- Journal of Applied Crystallography, Vol. 36, Issue 3
The 30 m Small-Angle Neutron Scattering Instruments at the National Institute of Standards and Technology
journal, June 1998
- Glinka, C. J.; Barker, J. G.; Hammouda, B.
- Journal of Applied Crystallography, Vol. 31, Issue 3, p. 430-445
Reduction and analysis of SANS and USANS data using IGOR Pro
journal, November 2006
- Kline, Steven R.
- Journal of Applied Crystallography, Vol. 39, Issue 6, p. 895-900
Pore structure characterization of organic-rich Niutitang shale from China: Small angle neutron scattering (SANS) study
journal, February 2018
- Sun, Mengdi; Yu, Bingsong; Hu, Qinhong
- International Journal of Coal Geology, Vol. 186
Pores in Marcellus Shale: A Neutron Scattering and FIB-SEM Study
journal, February 2015
- Gu, Xin; Cole, David R.; Rother, Gernot
- Energy & Fuels, Vol. 29, Issue 3
Quantification of Organic Porosity and Water Accessibility in Marcellus Shale Using Neutron Scattering
journal, May 2016
- Gu, Xin; Mildner, David F. R.; Cole, David R.
- Energy & Fuels, Vol. 30, Issue 6
Characterization of tight gas reservoir pore structure using USANS/SANS and gas adsorption analysis
journal, May 2012
- Clarkson, C. R.; Freeman, M.; He, L.
- Fuel, Vol. 95
Mechanisms of shale gas generation and accumulation in the Ordovician Wufeng-Longmaxi Formation, Sichuan Basin, SW China
journal, February 2017
- Borjigin, Tenger; Shen, Baojian; Yu, Lingjie
- Petroleum Exploration and Development, Vol. 44, Issue 1
Shale gas enrichment pattern and exploration significance of Well WuXi-2 in northeast Chongqing, NE Sichuan Basin
journal, June 2016
- Liang, Feng; Bai, Wenhua; Zou, Caineng
- Petroleum Exploration and Development, Vol. 43, Issue 3
Reservoir characteristics and controlling factor of shale gas in Lower Cambrian Niutitang Formation, South China
journal, September 2018
- Wang, Pengfei; Jiang, Zhenxue; Han, Bo
- Petroleum Research, Vol. 3, Issue 3