Coupled HCTM Phenomena From Pore-scale Processes to Macroscale Implications
DE-FE0001826
J. Carlos Santamarina Georgia Institute of Technology
U.S. Department of Energy
National Energy Technology Laboratory
Carbon Storage R&D Project Review Meeting
Developing the Technologies and Building the
Infrastructure for CO2 Storage
August 21-23, 2012
Presentation Outline
Project Overview: The Proposal
Accomplishments: HTCM Coupled Processes
Appendices: Contact Information
Schedule
Bibliography
Presentation Outline
Project Overview: The Proposal
Accomplishments: HTCM Coupled Processes
Appendices: Contact Information
Schedule
Bibliography
Relevance
"Faustian bargain"?
long-term CO2 geo-storage needed (C-economy + climate change)
but, it must be reliable in the long time scales
High early probability of failure
new engineering solutions: high initial Pf (emergence phenomena)
Main concerns
complex geo-plumbing
unanticipated coupled hydro-chemo-thermo-mechanical processes
unrecognized emergent phenomena (including positive feedbacks)
Without paralyzing critically needed CCS, make all efforts to
anticipate potential challenges
develop proper engineering solutions
This has been the purpose of this research
Project Objectives / Goals
To reach this goal, we will:
better understanding of fundamental processes and couplings that may
either hinder or enhance the long-term C-geological storage
• explore the geomechanical consequences of HCTM on geo-storage of CO2
• identify emergent phenomena
• bound the parameter-domain for efficient injection and safe long-term storage
• fundamental pore and particle-scale experimental studies
• upscaling numerical simulations
• macroscale numerical modeling
Approach combines:
kick-off meeting 1/2010
Contact
grain-grain
dissolution
Droplet
surface tension
contact angle
solubility
2D Cell
2D observations
2D invasion
transients
1D 2D 3D - σ’
FEM: Code-bright Network Model DEM - PFC
m
g g g gS . ~ ft
q
Analytical
Short
Capillary
Interface
diffusion
Sediment
sediment
fracture
Long
Capillary
mixed fluid
Project Team
ES Bang (KIGAM)
Monitoring
M.S. Cha
Dissolution - DEM
H.S. Shin (Ulsan U)
Dissolution DEM
N Espinoza (ENPC)
Ts CO2-CH4 Clays
J.W. Jung (LSU)
CO2-CH4
SH Kim
HC coupling - NM
J. Jang (WSU)
Network Models
A. Sivaran
leaks - cements
Presentation Outline
Project Overview: The Proposal
Accomplishments: HTCM Coupled Processes
Appendices: Contact Information
Schedule
Bibliography
preliminary analyses
Reservoir - Zones
Caprock
Two phase flow: CO2 & brine
Single phase reactive flow CO2 dissolved brine
Q
CO2(aq) H+
CO2 Brine
buoyancy
capillarity
M
CO2
M
B
Reservoir - Zones
diffusion
Q
capillarity
pH dissolution contraction ko shear CO2 Brine
buoyancy
advection convection
capillarity
HR
tensile fracture
-fingering
HCO2
M
CO2
M
B
Caprock
0
5
10
15
10 100 1000
Permeability [md]
Th
ick
ne
ss
of
CO
2 p
lum
e [
m]
Mt.
Sim
on
Mo
nta
na
Weyb
urn
Citro
ne
lle
Fort
Nels
on
CO2 plume thickness (without a trap)
2COwpore
s2CO
R
T2H
-
for: Ts=50mN/m γw-γCO2=4kN/m3
HCO2
HCO2
2
poreperm
m
R2
md
kafter Bachu and Bennion (2008)
2COw2COw2CO Hpp -
pore
sw2CO
R
T2pp
water + CO2
CO2 Dissolution and H2O Acidification
10 mm
CO2 Solubility in Water
0
1
2
0 20 40 60 80 100
T=30(°C)
T=60(°C)
T=90(°C)
T=120(°C)
Pressure [MPa]
So
lub
ilit
y o
f C
O2 [
mo
le/ kg
wate
r]
Sleipner
Frio
Weyburn
Duan and Sun (2003)
T [ C]
30
60
90
120
(in 1M NaCl solution)
Surface Tension and Contact Angle
Hold Test in Liquid CO2: Water diffusion
0
20
40
60
80
100
0 5 10 15 20Pressure [MPa]
Inte
rfacia
l T
ensio
n
[m
N/m
] H2O - PTFE
H2O - PTFE
Brine - PTFE
Brine - PTFE
H2O - oil-wet quartz
H2O - oil-wet quartz
H2O - oil-wet quartz
Fitted data (a)
Exp. data points (b)
Exp. data points (c)
Exp. data points (d)
22
25
CO2 saturation pressure
at 298°Kat 295°K
Gaseous
CO2
Liquid CO2
a (Massoudi and King, 1974), b (Chun and Wilkinson, 1995), c (Kvamme et al., 2007), d (Sutjiadi-Sia et al., 2007)
Surface Tension
0
20
40
60
80
100
120
140
160
0 5 10 15 20
Pressure [MPa]
Co
nta
ct A
ng
le
[°]
4/18/2008 CO2-H2O-PTFE 5/12/2008 CO2-SalineH2O-PTFE7/7/2008 CO2-H2O-OilCtSiO2 7/10/2008 CO2-H2O-OilCtSiO2Series1 Series24/2/2008 CO2-H2O-PTFE 09/10/2008 CO2-H2O-PTFE09/16/2008 CO2-Saline H2O-PTFE 10/29/2008 CO2-oil.coat.SiO2-H2O09/11/2008 CO2-CaCO3-H2O 09/09/2008 CO2-SiO2-H2O5/7/2008 CO2-SalineH2O-CaCO3 09/15/2008 CO2-SiO2-SalineH2OSeries15 Series16
Calcite
Quartz
CO2 saturation pressure
at 298°Kat 295°K
Gaseous
CO2
Liquid CO2
CO2-wet
substrates
H2O-wet
substrates
PTFE
Oil-wet
quartzCO2
H2O
Oil-wet SiO2
CO2
H2O + NaCl
CaCO3
CO2
PTFE
H2O + NaCl
Contact Angle
Invasion = Viscosity + Capillarity
10+4 10-4 10+8 10-8
(Modified from Lenormand et al 1988)
viscous
fingering
capillary
fingering
stable
displacement
w
2COM
cosT
vC
s
2CO
10-4
10+4
10+8
10-8
Surfactant Surfonic POA-25R2
Q. Zhao
CO2
water+surfactant water
3.2 mm
CO2
0
20
40
60
80
100
0 2 4 6 8 10 12
Inte
rfacia
l te
nsio
n [m
N/m
]
Pressure [MPa]
CO2-water
CO2-brine
CO2-water-surfactant
at 295 KGaseous CO2
at 298 KLiquid CO2
CO2 L-V boundary
Engineered Injection
0
0.1
0.2
0.3
0.4
0.5
0 20 40 60 80
Sw
ee
p E
ffic
ien
cy
E [
%]
Interfacial tension [mN/m]
CO2(g) + water (w/ surfactant)
CO2(g) + water
CO2(l) + water
CO2(l) + water (w/ surfactant)
Interfacial tension Ts [mN/m]
Sw
eep
eff
icie
ncy
Q
CO2 Brine
(CO2 + H2O) + Mineral
acidification convection
1mm
1mm1mm
100 m
1 m
Droplet
zone
Calcite substrate
Water in CO2
acidification dissolution drying precipitation
Mass Balance Analyses
M
B (W+S+M)
CO2 VCO2<1>
VB<1>
VM<1>
Volume
VT<1>
1
11
21
T
BCO
V
VV
11
2
1
BCO
BB
VV
VS BCO SS 12
M
B (W+S+M+CO2)
CO2 (+W)
S
At equilibrium:
),,(2 TPCfCCO
W
),,(2 TPCfC B
CO
),,( TPCfC B
M
Concentration
),,(2
2 TPCfCO
),,(2 TPCfB
),,(2 TPCfM
Density Initial porosity:
Saturation:
Mass balance:
1
2
111
2 )1( COTBCO VSM
1111
BTBB VSM
11111111 1 BTBMMTM VSCVM
11111
BTBSS VSCM
B
CO
CO
CO
T
CO MMM 2
2
22
2CO
W
B
B
T
B MMM
B
M
M
M
T
M MMM
B
S
S
S
T
S MMM
2
2
2
22
2
CO
COCO
MV
2
22
B
BB
MV
2
22
M
MM
MV
CO2:
Brine:
Mineral:
Salt:
Final volume
Normalized change
in mineral volume
0.2%
Increase in
brine density
1.2%
-0.003
-0.002
-0.001
0
0 1 2 3 4 5 6
Salinity [mol/kg water]
∆V
M /
VM
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 1 2 3 4 5 6
Salinity [mol/kg water]
Bri
ne
de
ns
ity i
nc
rea
se
[%
]
Mineral Dissolution
k
Ht R
convConvection time
Case: k= 200 md HR=10 m tconv ≈ 9years
Convection
1 2 3
4 5 6
Bending Failure in Caprock
)2(6
)(6
4
13
323
2
32221
y
maxt
zc
Hc
Lfree
Ec
kr
Yield strength: σy
4
cc
r
IE4
k
y
cc1
z
c
free2
H
L
c3 H
Maximum tensile stress σtmax:
0
1
2
0 0.1 0.2 0.3 0.4 0.5
Frio project : π1=7.36, π3=2.55
π2 = Lfree/HC
π4 =
σtm
ax/σ
y
Caprock
where:
Mineral Dissolution - Implications
0.3
0.4
0.5
0.6
0.7
0 1000 2000
Time (sec)
Late
ral s
tre
ss c
oef
fici
en
t, k
0.00
0.02
0.04 Ve
rtic
al s
trai
n
90% glass bead + 10% NaCl
0.25
0.30
0.35
0.40
0.45
0.50
0.0 0.5 1.0 1.5
Vertical strain, εz (%)
Late
ral
str
ess c
oeff
icie
nt,
K a
b
c
DEM Simulation 2D - diameter gradually reduced - 20% of particles
Shear load
-0.04
-0.02
0
0.02
0.04
0.06
No
rm.
ve
rt.
dis
pla
ce
me
nt
0.5
0.6
0.7
0.8
0 0.1 0.2 0.3 0.4
Vo
id r
ati
o
Shear strain [radian]
0
10
20
30
40
50
Sh
ea
r s
tre
ss
[k
Pa
]
5
2
10
0(a)
(b)
(c)
5
2
10
0
5
2
10
0
SF% dissolved
SF% dissolved
SF% dissolved
1
2
3
Emergent: Shear Localization (b) Displacement vectors(a) Contact force chains
dR/dt = α·FN
& HR=80%
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
0.02
0.03
0.04
0.05
0.06
0.07
0.08
(c) Strain field
dR/dt = α·FN2
& HR=0%
dR/dt =α·FN
& HR=0%
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
0.02
0.03
0.04
0.05
0.06
0.07
0.08
PFC2D 3.10Step 29981100 16:37:55 Mon Jul 09 2012
View Size: X: -1.200e-002 <=> 1.100e-001 Y: -2.136e-002 <=> 1.194e-001
CForce ChainsCompressionTension
Maximum = 3.551e+002 Scale to Max = 5.000e+002
Wall
PFC2D 3.10Step 16219400 16:39:25 Mon Jul 09 2012
View Size: X: -1.200e-002 <=> 1.100e-001 Y: -2.136e-002 <=> 1.194e-001
CForce ChainsCompressionTension
Maximum = 2.935e+002 Scale to Max = 5.000e+002
Wall
PFC2D 3.10Step 31469200 16:39:57 Mon Jul 09 2012
View Size: X: -1.200e-002 <=> 1.100e-001 Y: -2.136e-002 <=> 1.194e-001
CForce ChainsCompressionTension
Maximum = 3.383e+002 Scale to Max = 5.000e+002
Wall 1km
250m
seabed
Contact Force Chains Displacement vectors Strain field
Cartwright (2005)
Dissolution Rate
-16
-12
-8
-4
0
2 3 4 5 6 7pH
pH controlled CO2(aq) controlled
pH controlled
Re
ac
tio
n r
ate
, lo
g (
kd /
[mo
l/m
2/s
])
Calcite
Anorthite
Kaolinite
pH
Calcite: Fredd and Fogler, 1998 & Renard et al., 2005 Anorthite & Kaolinite: Li et al., 2006
][][ )(221 aqd COkHkk
33.0
2
5.1 ][][ OHkkHkk OHOHHd
3.04.0 ][][ OHkHkk OHHd
Calcite:
Anorthite:
Kaolinite:
Single Rock Joint / Pore Scale (FEM)
Pe
Da
10-4
fast reaction
slow seepage
slow reaction
fast seepage
ndissolutio
advection
t
t
advection
diffusion
t
t
0.48
1.0[H+]
Min: 0.01
Max: 1.0 [mol/m3]
0.99
1.0
0.77
1.0
10-8
10-1
10-4 10-1
COV(R2)=0.49 COV(R
2)=1.26 COV(R
2)=1.95
Unco
rrel
ated
net
work
Isotr
opic
ally
corr
elat
ed
net
work
Network Simulation: Non-Reactive
Network Simulation: Storage Reservoir 0 10 20 30 40 50
0
10
20
30
40
50
Channel diameter distribution before dissolution
0 10 20 30 40 500
10
20
30
40
50
Channel diameter distribution after dissolution
0 10 20 30 40 500
10
20
30
40
50
Channel diameter differences
0 10 20 30 40 500
10
20
30
40
50
Channel diameter distribution before dissolution
0 10 20 30 40 500
10
20
30
40
50
Channel diameter distribution after dissolution
0 10 20 30 40 500
10
20
30
40
50
Channel diameter differences
0 10 20 30 40 500
10
20
30
40
50
Channel diameter distribution before dissolution
0 10 20 30 40 500
10
20
30
40
50
Channel diameter distribution after dissolution
0 10 20 30 40 500
10
20
30
40
50
Channel diameter differences
0 10 20 30 40 500
10
20
30
40
50
Normalized flow rate before dissolution
0 10 20 30 40 500
10
20
30
40
50
Normalized flow rate after dissolution
0 10 20 30 40 500
10
20
30
40
50
Flow rate differences
0 10 20 30 40 500
10
20
30
40
50
Normalized flow rate before dissolution
0 10 20 30 40 500
10
20
30
40
50
Normalized flow rate after dissolution
0 10 20 30 40 500
10
20
30
40
50
Flow rate differences
0 10 20 30 40 500
10
20
30
40
50
Normalized flow rate before dissolution
0 10 20 30 40 500
10
20
30
40
50
Normalized flow rate after dissolution
0 10 20 30 40 500
10
20
30
40
50
Flow rate differences
Normalized change in tube diameter ∆d/d0
Normalized change in flow rate ∆q/∆q0,max
(a) Da~10-3 (ih=10) (b) Da~10-4 (ih=100) (c) Da~10-5 (ih=1000)
Mean Pore Diameter and Flow Rate
1
1.1
1.2
1.3
1 1.01 1.02 1.03 1.04 1.05 1.06
No
rmali
zed
flo
w r
ate
, q
/q0
Normalized average diameter, d/d0
Da=10-3
Da=10-4
Da=10-5
Normalized mean tube diameter, d/d0
No
rma
lize
d f
low
ra
te, q
/q0
Qmax=1000 pore volumes
3
4
5
6
0 0.4 0.8 1.2 1.6
Ex
po
ne
nt fo
r d
iam
ete
r-fl
ow
ra
te
Coefficient of variation, COVCoefficient of variation, COV
E
xp
on
en
t
00 d
d
q
q
COV=0.4
Da≤10-4: several branches
of localized flow
Da>10-4: evolves towards
compact dissolution
Da=10-4
Reactive Fluid Transport
rateDiffusion
rateAdvection
D
dvPe
rate Advection
Reaction
v
lαDa
rate
diffusion
dominant
advection
dominant
low reaction rate
Fredd & Fogler 1988, 1998
Fredd & Miller’s 2000
Golfier et al. 2002
10-4 10-3 10-2 101 102 103 104 10-1
103
102
101
10-1
10-2
10-3
10-4
104
(water, CO2) + clay minerals
Fabric map
Kaolinite
pH
Edge IEP, pH 7.2
Face or Particle IEP
pH 4
log(co)co=0.1-0.15 mol/L
Edge IEP
Face or Particle IEP
pH < 4
co=0.25-0.3 mol/Lco=5 10-3 mol/L
? ? ? ?
pH
log(co)
Montmorillonite
Clay-CO2 interaction
1s 3s 6s 2s 4s 5s montmorillonite in liquid CO2
(N. Skipper - UCL)
Clay-CO2 interaction (a) Kaolinite (b) Montmorillonite
1
10
100
1000
water brine heptane liq CO2 sc CO2
Flo
c si
ze [
µm
]
0.1
1
10
100
1000
water brine heptane liq CO2 sc CO2
Flo
c si
ze [
µm
]
0.50
0.60
0.70
0.80
0.90
1.00
water brine heptane liq CO2 scCO2
Fin
al p
oro
sity
[ ]
0.50
0.60
0.70
0.80
0.90
1.00
water brine heptane liq CO2 scCO2
Fin
al p
oro
sity
[ ]
Fluid
permittivity 78.5 56 1.385 1.167 1.167 78.5 56 1.385 1.167 1.167
Ah [10-20
J] 1.57 1.24 0.84 4.20 4.20 0.98 0.73 0.42 3.14 3.14
Double
layer
large low c0
short high c0
none none none large low c0
short high c0
none none none
Aggregation disper-sed
face to face
edge to
edge
disper-sed
face to face
*
Montmorillonite
'
AH
Breakthrough – Healing (self-healing?)
’ = 1 MPa
PCO2
Δz
Pin
CO2 inlet
Sealing Solution
CO2 & water outlet
Caprock: Chattanooga Shale (b)
OD= 40mm
ID= 3.17mm
Height: 25mm<h<35mm
Initial breakthrough test
After sealing treatments
0
10
20
30
40
50
0 2 4 6 8
Pre
ss
ure
[k
Pa
]
Time [minute]
Pbt≈20kPa
0
1
2
3
4
5
6
0 100 200 300 400 500
Pre
ss
ure
[M
Pa
]
Time [hour]
Pd≈1.25MPa
Pd≈1.05MPa
1st treatment
2nd treatment
Caprock: Chattanooga Shale
Hydrates
Carbon geological storage
Temperature [°C]
Pre
ssu
re [
MPa
]
J Karl Johnson – NETL
Gas replacement in hydrates
CH4-hydrate
CH4 gas 1mm
(a) -2539min – Before repla-cement,
in CH4 atmosphere
(d) 18min – In liquid CO2 (e) 36min – In liquid CO2 (f) 186min – In liquid CO2
(g) 1176min – In liquid CO2 (h) 2178min – In liquid CO2 (i) 3768min – In liquid CO2
CH4 gas
(b) During liquid CO2 flooding (rising
from the bottom)
CH4-hydrate
Liquid CO2
(c) 0min – Immediately after liquid
CO2 flooding
CH4-hydrate
CH4 Hydrate flooded by liquid CO2 P=6MPa, T=275K
Gas replacement in hydrates
30
min
Hydrate-bearing sand in liquid CO2
CO2
injection
[4.2MPa,275.4K]
[4.3MPa,274.1K]
Hydrate-bearing sand in CH4
0 s 190 s
Initial Sw=0.045
0.0h
0.5h
1.0h
-0.5h
1.5h
Gas replacement in hydrates
Summary
Carbon geological storage
Capillarity
water
2COM
cos
k)(B w2COw
cos
vC 2CO
T. Hamida – U. Calgary
Viscosity
Buoyancy
Convection /Advection k
v
D
vPe
vDa
Péclet
Damköhler
Summary: HCTM phenomena
Complex HTCM material properties and couplings
Potential development of positive feedback mechanisms
Caution: poor understanding of some "common" processes
New emergent phenomena in CO2 geologic storage
Engineered injection
Sealing strategies (promote self-healing conditions)
CO2-CH4 replacement
Presentation Outline
Project Overview: The Proposal
Accomplishments: HTCM Coupled Processes
Appendices: Contact Information
Schedule
Bibliography
Contact Information
J. Carlos Santamarina
404-894-7605
http://pmrl.ce.gatech.edu/
Project Schedule
Graduate Students (funded by this project)
PhD 1: D. N. Espinoza (Numerical)
PhD 2: S. Kim (Experimental)
Carlos Santamarina
Calendar YearMar Jun Sept Dec Mar Jun Sept Dec Mar Jun Sept Dec
Team
Team
Team
Team
Team
Team
Team
Team
2.2 Dissolution
2.3 Breakthrough / Self-heal
2011 2012
Task #5 - Numerical Simulation: Coupled HCTM Processes
4.2 Particle-scale phenomena
2010
Task #1 - Project Management and Planning
Task #2 - Experimental studies 2.1 Pore scale
Task #3 - Analyses – Scales – Parameter Domain
Task #4 - Numerical Upscaling 4.1 Pore-scale phenomena
Bibliography Theses
• Seunghee Kim (2012). Carbon Geological Storage – CHM Coupling
• Nicolas Espinoza (2011). CO2 sequestration – Fundamental Studies.
• Minsu Cha (2012). Mineral Dissolution - Implications.
• Jaewon Jang (2011). Gas Production from Methane Hydrates
• Jong Won Jung (2010). Gas Production from Methane Hydrates.
• Hosung Shin (2009). Discontinuities.
Journal Papers (6 additional papers in preparation – Contact PI)
• Espinoza, D.N. and Santamarina J.C., Clay interaction with liquid and supercritical CO2: The relevance of electrical and
capillary forces, International Journal of Greenhouse Gas Control (submitted).
• Espinoza, D.N. and Santamarina J.C. (2010), Water-CO2-mineral systems: interfacial tension, contact angle and diffusion –
Implications to CO2 geological storage, Water Resources Research, vol. 46, DOI: 10.1029/2009WR008634.
• Espinoza, D.N., Kim, S.H., Santamarina, J.C. (2011), Carbon Geological Storage, KSCE Journal of Civil Engineering, vol. 15,
no. 4, pp. 707-719.
• Espinoza, D.N. and Santamarina, J.C. (2011), P-wave monitoring of hydrate-bearing sand during CH4-CO2 replacement, Int.
J. Greenhouse Gas Control, doi:10.1016/j.ijggc.2011.02.006.
• Jung, J.W., Espinoza, D.N. and Santamarina, J.C. (2010), Hydrate Bearing Sediments: CH4-CO2 Replacement, Journal of
Geophysical Research, vol. 115, B10102, doi:10.1029/2009JB000812
• Jung, J.W. and Santamarina, J.C. (2010), CH4-CO2 Replacement in Hydrate-Bearing Sediments: A Pore-Scale Study, G-
Cubed Geochemistry, Geophysics and Geosystems, Vol. 11, Q0AA13, doi:10.1029/2010GC003339.
• Shin, H., Santamarina, J.C. and Cartwright, J. (2010), Displacement Field In Contraction Driven Faults, J. Geophysical
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