Molecular Simulation of Carbon Dioxide, Brine, and … Simulation of Carbon Dioxide, Brine, and Clay...
Transcript of Molecular Simulation of Carbon Dioxide, Brine, and … Simulation of Carbon Dioxide, Brine, and Clay...
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Molecular Simulation of Carbon Dioxide,
Brine, and Clay Mineral Interactions
Craig M. Tenney and Randall T. Cygan
Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation,
a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s
National Nuclear Security Administration under contract DE-AC04-94AL85000.
SAND 2013-6721P
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103 m 103 m
Carbon capture and geological storage
Big Picture
Time
104 years
1. Capture CO2
2. Inject it deep underground
3. Hope it stays there
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injection well abandoned well fault
caprock storage zone
caprock jointing
1 km Scale:
Slide from: CFSES EFRC Science Review;
Denver, CO; January 2012; Joe Bishop (SNL)
Field-scale modeling
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log Time (s)
-15 -12 -9 -6 -3 0 3 6 9 12 15
log D
ista
nce (m
)
-9
-6
-3
0
3
6
Finite
Element
Analysis
Continuum
Methods and
Mesoscale
Modeling
Molecular
Mechanics
Quantum
Mechanics Å
mm
m
mm
km
min year day Ma ms ms ns
ps fs
e
atoms
nm
blobs
s ka
bulk
Multiscale simulation
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Geological carbon storage
Up Close
reservoir rock cap rock
Source: Cooperative Research Centre
for Greenhouse Gas Technologies,
http://www.co2crc.com.au/
Source: Hongkyu Yoon (SNL)
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Sub-pore scale
• interfacial tension g12
– surface free energy
• contact angle θC – indication of wettability
C12S2S1 cosggg Source: Kuldeep Chaudhary (UT Austin)
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Pore- and field-scale
• capillary pressure pc
– overpressure required to
displace current fluid with
new fluid
• relative permeability
– fractional permeability of
a fluid in the presence of
other fluid(s)
rpc
C12 cos2 g
liquid CO2
Water (10% NaBr)
10-3 m
Source: Kuldeep Chaudhary (UT Austin)
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Molecular simulation of aqueous and
supercritical CO2 nanodroplets
H
Al
Si
O siloxane surface
(hydrophobic)
gibbsite surface (hydrophilic)
kaolinite
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Simulation details
• (20 x 20 x 17) nm
•3 kaolinite layers
(bottom two fixed)
•330K, 20MPa
•10-15 ns
•CO2 in H2O
– 600k atoms
•H2O in CO2
– 300k atoms
•brine systems
– 0.7 M NaCl
– 0.2 M CaCl2
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siloxane (hydrophobic) surface
0.7M NaCl in CO2 – initial configuration
front view oblique view
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siloxane (hydrophobic) surface
0.7M NaCl in CO2 – final configuration
front view oblique view
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siloxane (hydrophobic) surface
0.7M NaCl in CO2 – final configuration
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siloxane (hydrophobic) surface
0.7M NaCl in CO2 – final configuration
carbon dioxide water
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siloxane (hydrophobic) surface
0.7M NaCl in CO2 – final configuration
water Na+ Cl−
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gibbsite (hydrophilic) surface
CO2 in H2O – initial configuration
front view oblique view
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gibbsite (hydrophilic) surface
CO2 in H2O – final configuration
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gibbsite (hydrophilic) surface
CO2 in H2O – final configuration
carbon dioxide water
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gibbsite (hydrophilic) surface
CO2 in 0.7M NaCl – final configuration
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gibbsite (hydrophilic) surface
CO2 in 0.7M NaCl – final configuration
carbon dioxide water
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gibbsite (hydrophilic) surface
CO2 in 0.7M NaCl – final configuration
water Na+ Cl−
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gibbsite (hydrophilic) surface
CO2 in 0.2M CaCl2 – final configuration
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gibbsite (hydrophilic) surface
CO2 in 0.2M CaCl2 – final configuration
carbon dioxide water
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gibbsite (hydrophilic) surface
CO2 in 0.2M CaCl2 – final configuration
water Ca2+ Cl−
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Summary
• Simulation shows realistic behavior for CO2, H2O,
and ions on hydrophilic and hydrophobic basal
surfaces of kaolinite.
• Possible future application: rational design of
surfactants, coatings, enhanced oil or gas
recovery
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Acknowledgments
• Simulation development aided by discussions with
– Louise Criscenti (SNL)
– Ian Bourg (LBNL)
• This research is funded by the Center for Frontiers
of Subsurface Energy Security (CFSES), a U.S.
Department of Energy Office of Basic Energy
Sciences Energy Frontier Research Center, under
Contract No. DE-SC0001114.
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supplementary slides
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siloxane (hydrophobic) surface
CO2 in H2O
initial final
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siloxane (hydrophobic) surface
CO2 in H2O – final configuration
top view front view
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siloxane (hydrophobic) surface
CO2 in H2O – final configuration
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siloxane (hydrophobic) surface
CO2 in H2O – final configuration
carbon dioxide water
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siloxane surface – H2O in CO2
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siloxane surface – H2O in CO2
carbon dioxide water
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siloxane surface – 0.2M CaCl2 in CO2
water Ca2+ Cl−
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siloxane surface – 0.2M CaCl2 in CO2
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siloxane surface – 0.2M CaCl2 in CO2
carbon dioxide water
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siloxane surface – 0.2M CaCl2 in CO2
water Ca2+ Cl−
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CO2 and H2O in mica slit pores
initial configuration
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CO2 and H2O in mica slit pores
final configurations
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CO2 and H2O in mica slit pores
final configurations
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CO2 and H2O in mica slit pores
CO2 density
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CO2 and H2O in mica slit pores
H2O density
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CO2 and H2O in mica slit pores
K+ density
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Summary
• kaolinite hydrophilic surface
– layers of water (and ions) completely displace CO2
• kaolinite hydrophobic surface
– strong CO2 wetting in presence of water and brine
– weak water and brine wetting in presence of CO2
• mica slit pores
– unconfined CO2 is completely displaced by well-
developed water layers
– strongly confined CO2 displaces diffuse water
layers, slightly altering contact angle