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Title: Tetrahydrofuran Hydrate in Clayey Sediments—Laboratory Formation, Morphology, and Wave Characterization

Abstract

Abstract Fine‐grained sediments host more than 90% of gas hydrates on Earth. However, the fundamental properties of hydrate‐bearing silty and clayey sediments are much less understood than those of hydrate‐bearing sands, mainly due to the experimental challenges in synthesizing gas hydrate in fine‐grained sediments in the laboratory as the way they form in nature. This study forms tetrahydrofuran (THF) hydrate in kaolinite, visualizes the hydrate distribution and morphology using X‐ray computed tomography, and uses P and S waves to characterize the formed hydrate‐bearing clayey sediments. The results show that THF hydrate formed in clay is innately segregated and heterogeneous, no longer as a pore constituent as in sandy sediments. Hydrate nucleation, growth, and distribution in clays are dominated by the thermal condition and constrained by water activity and mass transport, which can result in low stoichiometric‐solution‐to‐hydrate conversion ratios of approximately 0.4–0.7. Thus, the estimation of hydrate volume in clays based on the mass of stoichiometric solution can be erroneous. The heterogeneity in hydrate‐bearing clays imposes challenges in wave velocity based characterization. The bulk elastic properties of hydrate‐bearing clays can be well predicted using the self‐consistent model. Specimens with higher hydrate volume fraction VF h show higher wave attenuations Q −1more » , highlighting the dominant role of THF hydrate in the wave attenuation of hydrate‐bearing clays. The results suggest that Q p −1  = 0.08 + 0.4 VF h  = 2 Q s −1 , which underlines the potential of using wave attenuation based methods to quantify the hydrate volume fraction in clayey sediments.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]
  1. China Univ. of Geosciences Wuhan (China); Georgia Inst. of Technology, Atlanta, GA (United States). School of Civil and Environmental Engineering
  2. Georgia Inst. of Technology, Atlanta, GA (United States). School of Civil and Environmental Engineering
  3. Georgia Inst. of Technology, Atlanta, GA (United States). School of Civil and Environmental Engineering ; National Energy Technology Lab. (NETL), Albany, OR (United States)
  4. China Univ. of Geosciences Wuhan (China)
Publication Date:
Research Org.:
National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1569831
Alternate Identifier(s):
OSTI ID: 1507239
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Geophysical Research. Solid Earth
Additional Journal Information:
Journal Volume: 124; Journal Issue: 4; Journal ID: ISSN 2169-9313
Publisher:
American Geophysical Union
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES

Citation Formats

Liu, Zhichao, Kim, Jongchan, Lei, Liang, Ning, Fulong, and Dai, Sheng. Tetrahydrofuran Hydrate in Clayey Sediments—Laboratory Formation, Morphology, and Wave Characterization. United States: N. p., 2019. Web. doi:10.1029/2018JB017156.
Liu, Zhichao, Kim, Jongchan, Lei, Liang, Ning, Fulong, & Dai, Sheng. Tetrahydrofuran Hydrate in Clayey Sediments—Laboratory Formation, Morphology, and Wave Characterization. United States. https://doi.org/10.1029/2018JB017156
Liu, Zhichao, Kim, Jongchan, Lei, Liang, Ning, Fulong, and Dai, Sheng. Thu . "Tetrahydrofuran Hydrate in Clayey Sediments—Laboratory Formation, Morphology, and Wave Characterization". United States. https://doi.org/10.1029/2018JB017156. https://www.osti.gov/servlets/purl/1569831.
@article{osti_1569831,
title = {Tetrahydrofuran Hydrate in Clayey Sediments—Laboratory Formation, Morphology, and Wave Characterization},
author = {Liu, Zhichao and Kim, Jongchan and Lei, Liang and Ning, Fulong and Dai, Sheng},
abstractNote = {Abstract Fine‐grained sediments host more than 90% of gas hydrates on Earth. However, the fundamental properties of hydrate‐bearing silty and clayey sediments are much less understood than those of hydrate‐bearing sands, mainly due to the experimental challenges in synthesizing gas hydrate in fine‐grained sediments in the laboratory as the way they form in nature. This study forms tetrahydrofuran (THF) hydrate in kaolinite, visualizes the hydrate distribution and morphology using X‐ray computed tomography, and uses P and S waves to characterize the formed hydrate‐bearing clayey sediments. The results show that THF hydrate formed in clay is innately segregated and heterogeneous, no longer as a pore constituent as in sandy sediments. Hydrate nucleation, growth, and distribution in clays are dominated by the thermal condition and constrained by water activity and mass transport, which can result in low stoichiometric‐solution‐to‐hydrate conversion ratios of approximately 0.4–0.7. Thus, the estimation of hydrate volume in clays based on the mass of stoichiometric solution can be erroneous. The heterogeneity in hydrate‐bearing clays imposes challenges in wave velocity based characterization. The bulk elastic properties of hydrate‐bearing clays can be well predicted using the self‐consistent model. Specimens with higher hydrate volume fraction VF h show higher wave attenuations Q −1 , highlighting the dominant role of THF hydrate in the wave attenuation of hydrate‐bearing clays. The results suggest that Q p −1  = 0.08 + 0.4 VF h  = 2 Q s −1 , which underlines the potential of using wave attenuation based methods to quantify the hydrate volume fraction in clayey sediments.},
doi = {10.1029/2018JB017156},
journal = {Journal of Geophysical Research. Solid Earth},
number = 4,
volume = 124,
place = {United States},
year = {Thu Mar 28 00:00:00 EDT 2019},
month = {Thu Mar 28 00:00:00 EDT 2019}
}

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Cited by: 48 works
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Figures / Tables:

Figure 1 Figure 1: Temperature signatures of two specimens with identical (stoichiometric THF-water) solution-kaolinite mass ratio ($R$m = 0.7:1, in this case) during the whole course of the tests. The environment chamber is initially set at -10ºC. Stochastic hydrate nucleation occurs randomly at different subcooling temperatures $T$sc. X-ray computed tomography is takenmore » approximately 10 hours after hydrate nucleation. Then the chamber temperature is raised back to room temperature to cause hydrate dissociation.« less

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Works referenced in this record:

Hydrate morphology: Physical properties of sands with patchy hydrate saturation: PATCHY HYDRATE SATURATION
journal, November 2012

  • Dai, S.; Santamarina, J. C.; Waite, W. F.
  • Journal of Geophysical Research: Solid Earth, Vol. 117, Issue B11
  • DOI: 10.1029/2012JB009667

Attenuation of seismic waves in dry and saturated rocks: I. Laboratory measurements
journal, April 1979

  • Toksöz, M. N.; Johnston, D. H.; Timur, A.
  • GEOPHYSICS, Vol. 44, Issue 4
  • DOI: 10.1190/1.1440969

Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field
journal, January 2004

  • Cygan, Randall T.; Liang, Jian-Jie; Kalinichev, Andrey G.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 4
  • DOI: 10.1021/jp0363287

Thermodynamic properties and dissociation characteristics of methane and propane hydrates in 70-.ANG.-radius silica gel pores
journal, October 1992

  • Handa, Y. Paul; Stupin, D. Yu.
  • The Journal of Physical Chemistry, Vol. 96, Issue 21
  • DOI: 10.1021/j100200a071

Attenuation of seismic waves in methane gas hydrate-bearing sand
journal, January 2006


Surface geochemistry of the clay minerals
journal, March 1999

  • Sposito, G.; Skipper, N. T.; Sutton, R.
  • Proceedings of the National Academy of Sciences, Vol. 96, Issue 7
  • DOI: 10.1073/pnas.96.7.3358

Mechanical properties of sand, silt, and clay containing tetrahydrofuran hydrate: MECHANICAL BEHAVIOR OF HYDRATE-BEARING SEDIMENTS
journal, April 2007

  • Yun, T. S.; Santamarina, J. C.; Ruppel, C.
  • Journal of Geophysical Research: Solid Earth, Vol. 112, Issue B4
  • DOI: 10.1029/2006JB004484

Laboratory Strategies for Hydrate Formation in Fine‐Grained Sediments
journal, April 2018

  • Lei, L.; Santamarina, J. C.
  • Journal of Geophysical Research: Solid Earth, Vol. 123, Issue 4
  • DOI: 10.1002/2017JB014624

Do Montmorillonite Surfaces Promote Methane Hydrate Formation? Monte Carlo and Molecular Dynamics Simulations
journal, March 2003

  • Park, Sung-Ho; Sposito, Garrison
  • The Journal of Physical Chemistry B, Vol. 107, Issue 10
  • DOI: 10.1021/jp021427q

Pressure coring, logging and subsampling with the HYACINTH system
journal, January 2006

  • Schultheiss, P. J.; Francis, T. J. G.; Holland, M.
  • Geological Society, London, Special Publications, Vol. 267, Issue 1
  • DOI: 10.1144/GSL.SP.2006.267.01.11

Parametric study of the physical properties of hydrate-bearing sand, silt, and clay sediments: 1. Electromagnetic properties
journal, January 2010

  • Lee, J. Y.; Santamarina, J. C.; Ruppel, C.
  • Journal of Geophysical Research, Vol. 115, Issue B11
  • DOI: 10.1029/2009JB006669

A third-surface effect on hydrate formation
journal, November 1988

  • Cha, S. B.; Ouar, H.; Wildeman, T. R.
  • The Journal of Physical Chemistry, Vol. 92, Issue 23
  • DOI: 10.1021/j100334a006

Sonic waveform attenuation in gas hydrate-bearing sediments from the Mallik 2L-38 research well, Mackenzie Delta, Canada
journal, January 2002


Shear wave measurements of the elasticity of the ground
journal, March 1981


On the compressibility and shear strength of natural clays
journal, September 1990


Formation of natural gas hydrates in marine sediments: 1. Conceptual model of gas hydrate growth conditioned by host sediment properties
journal, October 1999

  • Clennell, M. Ben; Hovland, Martin; Booth, James S.
  • Journal of Geophysical Research: Solid Earth, Vol. 104, Issue B10
  • DOI: 10.1029/1999JB900175

Wave attenuation in partially saturated rocks
journal, February 1979


Influence of vertical cylindrical tetrahydrofuran hydrate veins on fine-grained soil behaviour
journal, December 2018

  • Smith, William E.; Priest, Jeffrey A.; Hayley, Jocelyn L. H.
  • Canadian Geotechnical Journal, Vol. 55, Issue 12
  • DOI: 10.1139/cgj-2017-0399

Electrical anisotropy due to gas hydrate-filled fractures
journal, November 2010

  • Cook, Ann E.; Anderson, Barbara I.; Malinverno, Alberto
  • GEOPHYSICS, Vol. 75, Issue 6
  • DOI: 10.1190/1.3506530

Ultrasonic attenuation of pure tetrahydrofuran hydrate: Ultrasonic attenuation of pure tetrahydrofuran hydrate
journal, June 2018

  • Pohl, Mathias; Prasad, Manika; Batzle, Michael L.
  • Geophysical Prospecting, Vol. 66, Issue 7
  • DOI: 10.1111/1365-2478.12534

Is Gas Hydrate Energy Within Reach?
journal, August 2009


Seismic imaging of a fractured gas hydrate system in the Krishna–Godavari Basin offshore India
journal, August 2010


Hydrate nucleation in quiescent and dynamic conditions
journal, September 2014


Parametric study of the physical properties of hydrate-bearing sand, silt, and clay sediments: 2. Small-strain mechanical properties
journal, January 2010

  • Lee, J. Y.; Francisca, F. M.; Santamarina, J. C.
  • Journal of Geophysical Research, Vol. 115, Issue B11
  • DOI: 10.1029/2009JB006670

Measured temperature and pressure dependence of V p and V s in compacted, polycrystalline sI methane and sII methane–ethane hydrate
journal, January 2003

  • Helgerud, M. B.; Waite, W. F.; Kirby, S. H.
  • Canadian Journal of Physics, Vol. 81, Issue 1-2
  • DOI: 10.1139/p03-016

Attenuation and Dispersion of Elastic Waves in a Cylindrical Bar
journal, October 1961

  • Zemanek, Joseph; Rudnick, Isadore
  • The Journal of the Acoustical Society of America, Vol. 33, Issue 10
  • DOI: 10.1121/1.1908417

Gas hydrate saturations estimated from fractured reservoir at Site NGHP-01-10, Krishna-Godavari Basin, India
journal, January 2009

  • Lee, M. W.; Collett, T. S.
  • Journal of Geophysical Research, Vol. 114, Issue B7
  • DOI: 10.1029/2008JB006237

A pressure core based characterization of hydrate-bearing sediments in the Ulleung Basin, Sea of Japan (East Sea)
journal, January 2011

  • Yun, Tae Sup; Lee, Changho; Lee, Jong-Sub
  • Journal of Geophysical Research, Vol. 116, Issue B2
  • DOI: 10.1029/2010JB007468

Electrical anisotropy of gas hydrate-bearing sand reservoirs in the Gulf of Mexico
journal, June 2012


The structure of methane gas hydrate bearing sediments from the Krishna–Godavari Basin as seen from Micro-CT scanning
journal, July 2011


Thermal conductivity of hydrate-bearing sediments: HYDRATED SEDIMENT THERMAL CONDUCTIVITY
journal, November 2009

  • Cortes, Douglas D.; Martin, Ana I.; Yun, Tae Sup
  • Journal of Geophysical Research: Solid Earth, Vol. 114, Issue B11
  • DOI: 10.1029/2008JB006235

Formation of natural gas hydrates in marine sediments: 2. Thermodynamic calculations of stability conditions in porous sediments
journal, October 1999

  • Henry, Pierre; Thomas, Michel; Clennell, M. Ben
  • Journal of Geophysical Research: Solid Earth, Vol. 104, Issue B10
  • DOI: 10.1029/1999JB900167

Electrical anisotropy of gas hydrate-bearing sand reservoirs in the Gulf of Mexico
text, January 2011

  • Cook, Ann E.; Anderson, Barbara I.; Rasmus, John
  • Columbia University
  • DOI: 10.7916/d8rf64h0

The difference between aspired and acquired hydrate volumes – A laboratory study of THF hydrate formation in dependence on initial THF:H2O ratios
journal, February 2018

  • Strauch, Bettina; Schicks, Judith M.; Luzi-Helbing, Manja
  • The Journal of Chemical Thermodynamics, Vol. 117
  • DOI: 10.1016/j.jct.2017.09.013

Long‐wavelength propagation in composite elastic media I. Spherical inclusions
journal, December 1980

  • Berryman, James G.
  • The Journal of the Acoustical Society of America, Vol. 68, Issue 6
  • DOI: 10.1121/1.385171

Electrical anisotropy due to gas hydrate-filled fractures
text, January 2010

  • Cook, Ann E.; Anderson, Barbara I.; Malinverno, Alberto
  • Columbia University
  • DOI: 10.7916/d8w66w8s

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