geophysics, geomechanics and geochemistry of co...
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Geophysics, Geomechanics and
Geochemistry of CO2 Geological Store
Marcelo Ketzer
CEPAC – Centre of Excellence in Research and Innovation in Petroleum,
Mineral Resources, and Carbon Storage (www.pucrs.br/cepac)
21st -23rd March 2012
Mexico
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Agenda1. Introduction.
2. Types of reservoirs for CO2 storage.
3. The fate of stored CO2: trapping mechanisms.
4. Applied geophysics: site selection and monitoring.
5. Applied geomechanics: site selection (and monitoring).
6. Applied geochemistry: site selection and monitoring.
5.1 Changes in the geochemical system,
5.2 Forms of investigations (experiments and modelling),
5.3 Rock integrity (mineral dissolution and precipitation):
A case study in Brazil.
7. Final remarks.
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Creation of CEPAC / October 2007(Joint initiative PUCRS-PETROBRAS)
Center of Excellence in Research and Innovation in Petroleum,
Mineral Resources, and Carbon Storage.
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AREAS OF RESEARCH AND DEVELOPMENT
CO2
Geological Storage
Exploration and Production of
Gas Hydrates in the continental margin
Geochemistry of giant pre-salt
reservoirs (CCS)
Reservoir characterization
(E&P)
Other projects (cooperation):
Palaeogeography and Palaeoclimatology applied to petroleum exploration.
Genomic Stratigraphy.
Non-destructive imaging of sedimentological experiments.
CO2 capture with ionic liquids.
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Building with 1100 m2 (3800 m2 in 2013)
in the Technological Park of PUCRS: TECNOPUC
Infrastructure
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Loboratories• High-pressure CO2 lab
• Coal characterization lab
• Reservoir characterization lab
• Well bore integrity lab
• Numerical modelling lab
• X-ray difractometry lab
• Isotopic geochemistry lab
• Water analyses lab
• Gas analyses lab
• Gas hydrate lab
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Human Resources
• 10 Professors at PUCRS
• 14 researchers
• 18 graduate students
• 14 undergraduate students
7
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Porto Batista CCS Pilot Site (coal)
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Porto Batista CCS Pilot Site (coal)
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CONEGAS Project (gas hydrate exploration)
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Types of geological reservoirs for CO2 storage:
petroleum fields, saline aquifers, and coal seam..
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The fate of stored CO2 storage: Trapping mechanisms.
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Applied geophysics: Site selection and monitoring.
http://www.pesa.com.au/publications/pesa_news/feb_06/images/tech_focus/bremer/Bremer_Fig7.jpg
- Seismic (depth and type of trap, volume, type and migration of fluids).
- Others: Well logs, electromagnetic survey, gravimetric survey, etc.
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http://noc.ac.uk/f/content/science-technology/marine-resources/carbon-capture-img3.png
www.rite.or.jp/English/lab/.../ccsws2007/6_xue.pdf
Cross-well seismic tomography
(Nagaoka Project, Japan)
4D seismic monitoring
(Sleipner Project,
Norway)
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Applied geomechanics: Site selection (and monitoring).
- Hydraulic fracturing threshold for reservoir and caprock (site selection).
- Pressure threshold for fault activity (site selection).
- Use of tiltmeters, microseismographs, etc (monitoring).
http://www.geology.wisc.edu/courses/g112/Images/salv_faults.jpg
http://bellona.org/ccs/typo3temp/pics/b5712e213f.jpg
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Applied geomechanics: Site selection (and monitoring).
http://www.netl.doe.gov/technologies/carbon_seq/corerd/images/simulation_1.jpg
http://geophysics.ou.edu/geol1114/notes/structure/confining%20pressure%20lab.jpg
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Uniaxial/Triaxial rock experiments
CEPAC/PUCRS
Mohr-diagram showing failure
envelopes for a pre-existing
fracture, and for wet and dry
sand.
Windhoffer et al. (2005)
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Morris et al. (2011)
Surface displacement observed by InSAR
(Interferometric Synthetic Aperture Radar)
In Salah Project
(Algeria)
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Applied Geochemistry:
changes in the geochemical system.
http://www.netl.doe.gov/technologies/carbon_seq/FAQs/images/capture_6.jpg
http://netsains.com/wp-content/uploads/2011/02/purba-co23.jpg
CO2 as a supercritical fluid…
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Bachu & Adams (2003)
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Reactions of CO2 in water:
CO2 (g) ↔ CO2 (aq)
CO2 (aq) + H2O ↔ H2CO3 (aq)
H2CO3 ↔ H+ (aq) + HCO3-
(aq)
HCO3-(aq) ↔ H+
(aq) + CO3-2
(aq)
Acidification of the formation water…
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Experiments to simulate
CO2-water-rock interactions
Bateman et al. (2005)
“Batch experiments”
“Flow experiments”
High pressure
(autoclaves)
Atmospheric pressure
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Experiments to simulate
CO2-water-cement (materials) interactions
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“Batch experiment workflow”
System is locked from
hours to months…
Rock sample (powder or cut/chunk)
Reactants (solution)
Carbon dioxide
Experiment preparation
(assembly, P+T set)
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“Flow experiment”
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Characterization before and after experiments:
WATER
pH, resistivity, alkalinity
Major and trace elements
(ICP-EOS)
ROCK
Optical petrography
Scanning Electron Microscopy
X-ray diffractometry
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CO2 (g)
A+
B-
[AB]
Numerical modelling to simulate
CO2-water-rock interactions
“Batch” geochemical models
Equilibrium among phases,
dissolution, precipitation,
solubility of CO2
Kinetics, evolution of quantities of
minerals and species in water
Reactive transport models
Multiphase flow and reactive transport
in porous/fractured media
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PHREEQC v2 (USGS)
• Chemical species,
equilibrium, 1D transport.Ketzer et al. 2009, App. Geochem. 24, 760
Gaus et al. 2005, Chem. Geol. 217, 319
Wigand et al. 2009, App. Geochem.
23, 2735
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The Geochemist’s Workbench 7.0
(GWB) (Rockware, Inc.)
• Chemical species, equilibrium, kinetics
of dissolution and precipitation, 2D
single phase transport reactions.
20
10082490 Wed Oct 08 2008
Kaolinite (moles/cm3)
.000665 .00069.0006775500 m
500 m
Co
lor
ma
p K
ao
linite
fro
m .0
00
66
5 m
ole
s/cm
3 (
Wh
ite)
to .0
00
69
mo
les/
cm3 (
Re
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mid
.00
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77
5 m
ole
s/cm
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Ye
llow
)
Co
nto
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2(g
) fr
om
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to 8
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ga
city
by
inte
rva
l of 1
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t = 100 years
CEPAC
CEPAC
Zerai et al. 2006, App. Geochem 21, 223
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TOUGH2 (LBNL)
• 3D Multiphase and
multicomponente flow in
porous/fractured media.
TOUGHREACT (LBNL)
• Inclusion of reactive models
inTOUGH2.
Xu et al. 2005, Chem. Geol. 217, 295 (TOUGHREACT)
Gherardi et al. 2007, Chem. Geol. 244, 103 (TOUGH2)
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Rock integrity (mineral dissolution and precipitation):
A case study in Brazil for reservoir rock
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Numerical modeling and experiments to “test” sandstones
of the Rio Bonito Formation (saline aquifer in the Paraná Basin)
Sandstone composition:
Batch experiments:
Rock mass ca. 5 g
Temperature 200 °C
Pressure 10-15 Mpa
Time: 100 h
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(a) Dissolution of detrital grains (K-feldspar)
(b) Precipitation of ordered kaolinite/disordered dickite
(c) Precipitation of opal (botrioidal texture)
(d) Precipitation of gypsite
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Different forms of carbonates (calcite) precipitated in the reactor:
(a) framboidal aggregates
(b) blocky crystals
(c) acicular
(d) microcrystalline
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Numerical models using PHREEQC v2 Mineral phases
Dissolved species
Example of dissolution/precipitation reaction
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Rock integrity (mineral dissolution and precipitation):
A case study in Brazil for caprock
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4 Author name / Energy Procedia 00 (2012) 000–000
of the CO2 effect, while RB1 analysis after 6 months showed probable attack on interstrafied illite/
smectite with initial development of illite in CO2 reaction (Figure 1 (a) and (b)).
PAL XRD analysis in air dry mode after 3 months shows the same behavior of RB2 sample,
change in I/S peak for reactions without CO2 and with CO2. Air dry PAL analysis after 6 months of
reaction in presence of CO2 demonstrated significant alteration of I/S phase with changes in peaks
at 10 and 5,02 Å, probably due to the development of illite phase from interstratified phase (Figure
1 (c) and (d)).
(a)
(b)
Author name / Energy Procedia 00 (2012) 000–000 5
Figure1: XRD spectrums: (a) RB1 sample after 3 months, (b) RB1 sample after 6 months, (c), PAL sample after 3
months, (d) PAL sample after 6 months
(c)
(d)
Initial - without CO2 - with CO2
Author name / Energy Procedia 00 (2012) 000–000 5
Figure1: XRD spectrums: (a) RB1 sample after 3 months, (b) RB1 sample after 6 months, (c), PAL sample after 3
months, (d) PAL sample after 6 months
(c)
(d)
Initial - without CO2 - with CO2
Results of low pressure experiments
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6 Author name / Energy Procedia 00 (2012) 000–000
- SEM analysis
SEM analysis on reservoir (RB1) and caprock (PAL) samples after 3 and 6 months of reaction
demonstrated mainly attack (dissolution) on quartz and feldspar grains and the new phases
precipitation was not observed.
- TEM analysis
Were performed TEM analyses for initial PAL sample and for PAL sample after 6 months of
reaction at atmospheric pressure. This sample was selected due the results obtained by XRD, where
it was observed important reactivity of illite/smectite clay phase. Figure 2 (a) and (b) corresponding
to I/S interstratified phase in initial sample and others images corresponding to precipitated phases
after 6 months in CO2 presence: (c) typical crystal of neoformed illite, (d) and (f) I/S altered crystals
with neoformed ilitic phases and (e) pure illite neoformed.
(b)
(c)
(a)
(d)
Altered
initial I/S
Neoformed
illite
Author name / Energy Procedia 00 (2012) 000–000 7
Figure 2: TEM analyses of PAL sample: (a) and (b) illite crystals and/or interstratified I/S in initial sample; c)
neoformed illite, (d) altered I/S and neoformed illite, (e) pure illite neoformed, (f) illite crystals (detail) and I/S after 6
months of reaction in CO2 presence.
3.2 High pressure reactions
Initially we chosen PAL and IR1 caprock samples for reactions a high pressure. Here we present
XRD analysis for PAL sample during reaction of 3 and 6 months (Figure 3 (a) and (b)). Analysis
for PAL sample after 3 months do not presents significant changes, while in 6 months it was
verified probable I/S alteration.
(e)
initial - after reaction with CO2
Pure illite
neoformed
(f)
(a)
Author name / Energy Procedia 00 (2012) 000–000 7
Figure 2: TEM analyses of PAL sample: (a) and (b) illite crystals and/or interstratified I/S in initial sample; c)
neoformed illite, (d) altered I/S and neoformed illite, (e) pure illite neoformed, (f) illite crystals (detail) and I/S after 6
months of reaction in CO2 presence.
3.2 High pressure reactions
Initially we chosen PAL and IR1 caprock samples for reactions a high pressure. Here we present
XRD analysis for PAL sample during reaction of 3 and 6 months (Figure 3 (a) and (b)). Analysis
for PAL sample after 3 months do not presents significant changes, while in 6 months it was
verified probable I/S alteration.
(e)
initial - after reaction with CO2
Pure illite
neoformed
(f)
(a)
8 Author name / Energy Procedia 00 (2012) 000–000
Figure 3: XRD spectrums of PAL sample submitted to high pressure: (a) after 3 months, (b) after 6 months.
SEM analysis of PAL sample demonstrated attack on quartz and feldspar grains. It was observed
the same behaviour that for samples submitted to atmospheric pressure reactions.
4. Discussion
Samples submitted to reactions at high pressure did not show significant alterations, only PAL sample after 6 months of reaction evidenced probable I/S alteration. Reactions with dissolved CO2
demonstrated dissolution on quartz and feldspar in the reservoir samples; and dissolution/re-
precipitation of the argillaceous phase (Illite-Smectite and Illite) in the Palermo caprock.
These results demonstrated bigger reactivity of dissolved CO2 in relation to supercritical fluid. It
is well established [18] that in the aqueous phase the CO2 is able to react with the minerals in the
geological formations to promote dissolution and precipitation processes.
These preliminary results demonstrated a mineralogical transformation from illite-smectite to
illite in Palermo caprock. It’s known that smectite can be slowly transformed to illite upon heating.
This process leads to destruction of smectite and a release of Si wich may precipitate as SiO2
cement (Equation 1) [19].
Na-smectite + K
+ + Al
3+ ! illite + Si
4+ Equation (1)
Smectites formed from high temperature silicates in low temperature environments as marine
sediments (as Palermo case) or in hydrothermal systems, when submitted to higher temperatures
can be transformed to more stable silicate phases such as illite/smectite mixed layers, illite, chlorite,
etc [20]. Diagenetic or sedimentary series has been studied using illitisation from smectite approach
[21]. Smectite to illite transition is defined by XRD as transformation of mixed-layer illite-smectite
(smectite rich) to highly ordered minerals (illite rich).
Mineral dissolution and/or precipitation in geological means are important parameter to safety of
the CO2 geological storage process. Mineral transformations can be affect the surface area, number
of sorption sites, can change the porosity and concentration of dissolved species. These changes
(b)
Example of dissolution/precipitation reaction:
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Author name / Energy Procedia 00 (2012) 000–000 7
Figure 2: TEM analyses of PAL sample: (a) and (b) illite crystals and/or interstratified I/S in initial sample; c)
neoformed illite, (d) altered I/S and neoformed illite, (e) pure illite neoformed, (f) illite crystals (detail) and I/S after 6
months of reaction in CO2 presence.
3.2 High pressure reactions
Initially we chosen PAL and IR1 caprock samples for reactions a high pressure. Here we present
XRD analysis for PAL sample during reaction of 3 and 6 months (Figure 3 (a) and (b)). Analysis
for PAL sample after 3 months do not presents significant changes, while in 6 months it was
verified probable I/S alteration.
(e)
initial - after reaction with CO2
Pure illite
neoformed
(f)
(a)
8 Author name / Energy Procedia 00 (2012) 000–000
Figure 3: XRD spectrums of PAL sample submitted to high pressure: (a) after 3 months, (b) after 6 months.
SEM analysis of PAL sample demonstrated attack on quartz and feldspar grains. It was observed
the same behaviour that for samples submitted to atmospheric pressure reactions.
4. Discussion
Samples submitted to reactions at high pressure did not show significant alterations, only PAL sample after 6 months of reaction evidenced probable I/S alteration. Reactions with dissolved CO2
demonstrated dissolution on quartz and feldspar in the reservoir samples; and dissolution/re-
precipitation of the argillaceous phase (Illite-Smectite and Illite) in the Palermo caprock.
These results demonstrated bigger reactivity of dissolved CO2 in relation to supercritical fluid. It
is well established [18] that in the aqueous phase the CO2 is able to react with the minerals in the
geological formations to promote dissolution and precipitation processes.
These preliminary results demonstrated a mineralogical transformation from illite-smectite to
illite in Palermo caprock. It’s known that smectite can be slowly transformed to illite upon heating.
This process leads to destruction of smectite and a release of Si wich may precipitate as SiO2
cement (Equation 1) [19].
Na-smectite + K+ + Al
3+ ! illite + Si
4+ Equation (1)
Smectites formed from high temperature silicates in low temperature environments as marine
sediments (as Palermo case) or in hydrothermal systems, when submitted to higher temperatures
can be transformed to more stable silicate phases such as illite/smectite mixed layers, illite, chlorite,
etc [20]. Diagenetic or sedimentary series has been studied using illitisation from smectite approach
[21]. Smectite to illite transition is defined by XRD as transformation of mixed-layer illite-smectite
(smectite rich) to highly ordered minerals (illite rich).
Mineral dissolution and/or precipitation in geological means are important parameter to safety of
the CO2 geological storage process. Mineral transformations can be affect the surface area, number
of sorption sites, can change the porosity and concentration of dissolved species. These changes
(b)
8 Author name / Energy Procedia 00 (2012) 000–000
Figure 3: XRD spectrums of PAL sample submitted to high pressure: (a) after 3 months, (b) after 6 months.
SEM analysis of PAL sample demonstrated attack on quartz and feldspar grains. It was observed
the same behaviour that for samples submitted to atmospheric pressure reactions.
4. Discussion
Samples submitted to reactions at high pressure did not show significant alterations, only PAL sample after 6 months of reaction evidenced probable I/S alteration. Reactions with dissolved CO2
demonstrated dissolution on quartz and feldspar in the reservoir samples; and dissolution/re-
precipitation of the argillaceous phase (Illite-Smectite and Illite) in the Palermo caprock.
These results demonstrated bigger reactivity of dissolved CO2 in relation to supercritical fluid. It
is well established [18] that in the aqueous phase the CO2 is able to react with the minerals in the
geological formations to promote dissolution and precipitation processes.
These preliminary results demonstrated a mineralogical transformation from illite-smectite to
illite in Palermo caprock. It’s known that smectite can be slowly transformed to illite upon heating.
This process leads to destruction of smectite and a release of Si wich may precipitate as SiO2
cement (Equation 1) [19].
Na-smectite + K+ + Al
3+ ! illite + Si
4+ Equation (1)
Smectites formed from high temperature silicates in low temperature environments as marine
sediments (as Palermo case) or in hydrothermal systems, when submitted to higher temperatures
can be transformed to more stable silicate phases such as illite/smectite mixed layers, illite, chlorite,
etc [20]. Diagenetic or sedimentary series has been studied using illitisation from smectite approach
[21]. Smectite to illite transition is defined by XRD as transformation of mixed-layer illite-smectite
(smectite rich) to highly ordered minerals (illite rich).
Mineral dissolution and/or precipitation in geological means are important parameter to safety of
the CO2 geological storage process. Mineral transformations can be affect the surface area, number
of sorption sites, can change the porosity and concentration of dissolved species. These changes
(b)
Results of high pressure experiments
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Final remarks
Geophysics is very important for site selection of CCS projects and monitoring
stored CO2, particularly seismics.
Geomechanical properties are key for site selection, notably those related to
fracturing of reservoirs and caprocks, and reactivation of existing faults.
Changes in geochemical properties related to massive injection of CO2 in reservoirs
can be constrained by numerical modelling and experiments.
Minerals in the reservoir and caprock interact with stored CO2 and formation water,
changing trapping mechanisms with time.
Reactivity of minerals is an important factor to consider during site selection of CCS
projects as they affect reservoir and caprock integrity .
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