Shale Pore Characterization Using NMR Cryoporometry with Octamethylcyclotetrasiloxane as the Probe Liquid

Qian Zhang, Yanhui Dong, Shimin Liu, Derek Elsworth, Yixin Zhao

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Fluid flow and chemical transport within shale are determined by the pore size distribution and its connectivity. Because of both low porosity and small (nanometer) pore size, common characterization methods, such as mercury injection capillary pressure (MICP) and the nitrogen adsorption method (NAM), have limited resolution and applicability. Nuclear magnetic resonance cryoporometry (NMR-C) is a novel characterization method that exploits the Gibbs-Thomson effect and provides a complementary method of characterizing aggregate pore structure at fine resolution. We use water and octamethylcyclotetrasiloxane (OMCTS) as probe liquids for NMR-C on controlled porosity samples of SBA, CPG, and shale. The analysis accommodates the influence of melting temperature, KGT, and surface layer thickness, ε, on the pore size distribution (PSD). Calibration experiments permeated with the two fluids demonstrate that OMCTS has a larger KGT and that the PSD for different cryoporometric materials is not subject to different surface curvatures of pores. Furthermore, the PSDs for shale are characterized by MICP, NAM, and NMR-C, which give comparable results. Shale samples have heterogeneous pore distributions with peak pore diameters at ∼3 nm and mesopore diameters of 2-50 nm comprising the main storage volume. Because of its larger molecular size and correspondingly large KGT, NMR-C-OMCTS is able to characterize pores to 2 μm but misses pores smaller than 5 nm. Meanwhile, NMR-C using OMCTS images a broader PSD than that by NMR-C-Water due to the propensity of OMCTS to imbibe into the organic matter relative to that of water. NMR-C-OMCTS shows the superiority and potential due to the higher signal/noise (S/N) ratio and wider measurement range up to 2 μm. With regard to shales, one insight is that 115 K nm is an appropriate KGT value for measurements with the surface layer thickness of 2 nm. Moreover, the applications of NMR-C-OMCTS will come down to other rocks through further research.

Original languageEnglish (US)
Pages (from-to)6951-6959
Number of pages9
JournalEnergy and Fuels
Volume31
Issue number7
DOIs
StatePublished - Jul 20 2017

Fingerprint

Shale
Nuclear magnetic resonance
Pore size
Liquids
Capillarity
Mercury
Water
Nitrogen
Porosity
Adsorption
octamethylcyclotetrasiloxane
Pore structure
Biological materials
Melting point
Flow of fluids
Rocks
Calibration
Fluids

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology

Cite this

@article{880ce30f84294c439bf103a96e6a7195,
title = "Shale Pore Characterization Using NMR Cryoporometry with Octamethylcyclotetrasiloxane as the Probe Liquid",
abstract = "Fluid flow and chemical transport within shale are determined by the pore size distribution and its connectivity. Because of both low porosity and small (nanometer) pore size, common characterization methods, such as mercury injection capillary pressure (MICP) and the nitrogen adsorption method (NAM), have limited resolution and applicability. Nuclear magnetic resonance cryoporometry (NMR-C) is a novel characterization method that exploits the Gibbs-Thomson effect and provides a complementary method of characterizing aggregate pore structure at fine resolution. We use water and octamethylcyclotetrasiloxane (OMCTS) as probe liquids for NMR-C on controlled porosity samples of SBA, CPG, and shale. The analysis accommodates the influence of melting temperature, KGT, and surface layer thickness, ε, on the pore size distribution (PSD). Calibration experiments permeated with the two fluids demonstrate that OMCTS has a larger KGT and that the PSD for different cryoporometric materials is not subject to different surface curvatures of pores. Furthermore, the PSDs for shale are characterized by MICP, NAM, and NMR-C, which give comparable results. Shale samples have heterogeneous pore distributions with peak pore diameters at ∼3 nm and mesopore diameters of 2-50 nm comprising the main storage volume. Because of its larger molecular size and correspondingly large KGT, NMR-C-OMCTS is able to characterize pores to 2 μm but misses pores smaller than 5 nm. Meanwhile, NMR-C using OMCTS images a broader PSD than that by NMR-C-Water due to the propensity of OMCTS to imbibe into the organic matter relative to that of water. NMR-C-OMCTS shows the superiority and potential due to the higher signal/noise (S/N) ratio and wider measurement range up to 2 μm. With regard to shales, one insight is that 115 K nm is an appropriate KGT value for measurements with the surface layer thickness of 2 nm. Moreover, the applications of NMR-C-OMCTS will come down to other rocks through further research.",
author = "Qian Zhang and Yanhui Dong and Shimin Liu and Derek Elsworth and Yixin Zhao",
year = "2017",
month = "7",
day = "20",
doi = "10.1021/acs.energyfuels.7b00880",
language = "English (US)",
volume = "31",
pages = "6951--6959",
journal = "Energy & Fuels",
issn = "0887-0624",
publisher = "American Chemical Society",
number = "7",

}

Shale Pore Characterization Using NMR Cryoporometry with Octamethylcyclotetrasiloxane as the Probe Liquid. / Zhang, Qian; Dong, Yanhui; Liu, Shimin; Elsworth, Derek; Zhao, Yixin.

In: Energy and Fuels, Vol. 31, No. 7, 20.07.2017, p. 6951-6959.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Shale Pore Characterization Using NMR Cryoporometry with Octamethylcyclotetrasiloxane as the Probe Liquid

AU - Zhang, Qian

AU - Dong, Yanhui

AU - Liu, Shimin

AU - Elsworth, Derek

AU - Zhao, Yixin

PY - 2017/7/20

Y1 - 2017/7/20

N2 - Fluid flow and chemical transport within shale are determined by the pore size distribution and its connectivity. Because of both low porosity and small (nanometer) pore size, common characterization methods, such as mercury injection capillary pressure (MICP) and the nitrogen adsorption method (NAM), have limited resolution and applicability. Nuclear magnetic resonance cryoporometry (NMR-C) is a novel characterization method that exploits the Gibbs-Thomson effect and provides a complementary method of characterizing aggregate pore structure at fine resolution. We use water and octamethylcyclotetrasiloxane (OMCTS) as probe liquids for NMR-C on controlled porosity samples of SBA, CPG, and shale. The analysis accommodates the influence of melting temperature, KGT, and surface layer thickness, ε, on the pore size distribution (PSD). Calibration experiments permeated with the two fluids demonstrate that OMCTS has a larger KGT and that the PSD for different cryoporometric materials is not subject to different surface curvatures of pores. Furthermore, the PSDs for shale are characterized by MICP, NAM, and NMR-C, which give comparable results. Shale samples have heterogeneous pore distributions with peak pore diameters at ∼3 nm and mesopore diameters of 2-50 nm comprising the main storage volume. Because of its larger molecular size and correspondingly large KGT, NMR-C-OMCTS is able to characterize pores to 2 μm but misses pores smaller than 5 nm. Meanwhile, NMR-C using OMCTS images a broader PSD than that by NMR-C-Water due to the propensity of OMCTS to imbibe into the organic matter relative to that of water. NMR-C-OMCTS shows the superiority and potential due to the higher signal/noise (S/N) ratio and wider measurement range up to 2 μm. With regard to shales, one insight is that 115 K nm is an appropriate KGT value for measurements with the surface layer thickness of 2 nm. Moreover, the applications of NMR-C-OMCTS will come down to other rocks through further research.

AB - Fluid flow and chemical transport within shale are determined by the pore size distribution and its connectivity. Because of both low porosity and small (nanometer) pore size, common characterization methods, such as mercury injection capillary pressure (MICP) and the nitrogen adsorption method (NAM), have limited resolution and applicability. Nuclear magnetic resonance cryoporometry (NMR-C) is a novel characterization method that exploits the Gibbs-Thomson effect and provides a complementary method of characterizing aggregate pore structure at fine resolution. We use water and octamethylcyclotetrasiloxane (OMCTS) as probe liquids for NMR-C on controlled porosity samples of SBA, CPG, and shale. The analysis accommodates the influence of melting temperature, KGT, and surface layer thickness, ε, on the pore size distribution (PSD). Calibration experiments permeated with the two fluids demonstrate that OMCTS has a larger KGT and that the PSD for different cryoporometric materials is not subject to different surface curvatures of pores. Furthermore, the PSDs for shale are characterized by MICP, NAM, and NMR-C, which give comparable results. Shale samples have heterogeneous pore distributions with peak pore diameters at ∼3 nm and mesopore diameters of 2-50 nm comprising the main storage volume. Because of its larger molecular size and correspondingly large KGT, NMR-C-OMCTS is able to characterize pores to 2 μm but misses pores smaller than 5 nm. Meanwhile, NMR-C using OMCTS images a broader PSD than that by NMR-C-Water due to the propensity of OMCTS to imbibe into the organic matter relative to that of water. NMR-C-OMCTS shows the superiority and potential due to the higher signal/noise (S/N) ratio and wider measurement range up to 2 μm. With regard to shales, one insight is that 115 K nm is an appropriate KGT value for measurements with the surface layer thickness of 2 nm. Moreover, the applications of NMR-C-OMCTS will come down to other rocks through further research.

UR - http://www.scopus.com/inward/record.url?scp=85026230613&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85026230613&partnerID=8YFLogxK

U2 - 10.1021/acs.energyfuels.7b00880

DO - 10.1021/acs.energyfuels.7b00880

M3 - Article

AN - SCOPUS:85026230613

VL - 31

SP - 6951

EP - 6959

JO - Energy & Fuels

JF - Energy & Fuels

SN - 0887-0624

IS - 7

ER -