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November 28, 2017
National Academy of Science Workshop on Geologic Capture and Sequestration of Carbon
Stanford University, Palo Alto, CA
Accelerated reaction-driven carbon storage:Insights from laboratory-scale studies for field-scale geologic carbon storage
Department of Civil and Environmental Engineering Environmental Chemistry & Technology Program
Geological Engineering Program Wisconsin Energy Institute
University of Wisconsin, Madison
Greeshma Gadikota
Gadikota and Park, 2014, inCarbon Dioxide Utilization: Closing the Carbon Cycle
Contributions from Peter Kelemen, Columbia University & Greg Dipple, University of British Columbia
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Carbon Mineralization at the Field Scale
http://gwsgroup.princeton.edu/SchererGroup/Salt_Crystallization.html
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CO2 Trapping Mechanisms
Contribution to CO2Storage Security
Solubility Trapping Positive – CO2 stored as fluid
Mineral Trapping Positive – CO2 stored as solid
Mineral Trapping with Reactive Cracking
Facilitates CO2dispersion - reduces pressure build-up but increases CO2 leakage potential
CO2 Storage in Geologic Reservoirs
Uncertainties in the time scales of carbon mineralization exist
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Worldwide Availability of Ca- and Mg-bearing Minerals and Rocks
Belvidere Mountain, VermontSerpentine Tailings
Mineral Carbonation of Peridotite
Photo by Dr. Jürg Matter at LDEO (2008)
The most permanent method of carbon storage
Exothermic transformation Thermodynamically stable product Long-term environmentally benign
and unmonitored storage
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Direct versus Two-Step Conversion to Carbonates
Gadikota and Park, 2014, Carbon Dioxide Utilization, 1st Edition, Elsevier
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Reactivity of Ca- and Mg-bearing Minerals and Rocks and Implications for Carbon Storage
Magnetite Anorthite Basalt Talc Augite Lizardite Antigorite Fayalite Forsterite Wollastonite 0
20
40
60
80
100
Exte
nt o
f Car
bona
tion
(%)
Experiments performed at 185oC, PCO2 of 150 atm in 1.0M NaCl+0.64M NaHCO3. 15 wt. % solidReaction time:
Abundance of less reactiveminerals vs. limited availabilityof highly reactive minerals
1 hr0.5 hr 4 hr
4 hr dry attrition grindingAll others – 1 hour dry attrition grinding
Carbonation efficiency defineswhether mineral is utilized forex-situ or in-situ storage
Ex-situ CO2Storage
In-Situ CO2Storage
Shorter time scales (~hours)
Longer time scales (~years)
Limited spatial scale Larger spatial scale with utilization of earth as a reactor (~hundreds of miles)
Relativelyhomogenous mineralogy
Heterogeneous mineralogy
More flexible tuning in reaction conditions
Possible production of value-added products
No monitoring required
Not limited by reactor size; Use of geothermal gradient
Multiple CO2trappingmechanisms
Relatively economical at this time
O’Connor et al., AAPG Annual Meeting, 2003
Silicates Alumino-silicates
Fe3O
4
CaA
l 2Si 2O
8
rock
mix
ture
Mg 3
Si 4O
10(O
H) 2
Ca(
Mg,
Fe)S
i 2O6
Mg3Si2O5(OH)4
Fe2S
iO4
Mg2SiO4
CaSiO3
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Role of Carbon Mineralization in Enabling Geologic Carbon Storage
To develop a comprehensive understanding of CO2 mineralization behavior and its implications for CO2 storage potential
Comparison of dissolution rates and direct mineralization rates
Determination of the feedback mechanisms due to chemo -morphological - mechanical changes
Evaluation of the impacts on CO2 storage potential and net CO2
emission reductions & costs
• Develop thermodynamically downhill routes for permanent CO2storage with reduced monitoring needs
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Better Design of Kinetic Studies
Gadikota et al., I&ECR, 2014
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Laboratory Scale Dissolution Rates: Novel Reactor Designs to Probe Surface and Bulk Dissolution
Variations in surface dissolution vs. bulk dissolution rates observed in serpentine ((Mg,Fe)3Si2O5(OH)4)
Custom-built Differential Bed Reactor to Determine Surface and Bulk Dissolution Rates
Gadikota et al., I&ECR, 2014
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Better Design of Kinetic Studies
Gadikota et al., I&ECR, 2014
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Minerals and Rocks of Interest
Analyte Olivine(wt%)
((Mg,Fe)2SiO4)
Labradorite(wt%)
((Ca,Na)(Al, Si)4O8)
Anorthosite(wt%)
Basalt(wt%)
CaO 0.16 10.20 14.10 8.15MgO 47.30 0.24 8.74 4.82Fe2O3 13.90 0.97 10.60 14.60SiO2 39.70 54.30 41.80 51.90Al2O3 0.20 28.00 24.20 13.40Na2O 0.01 5.05 0.59 2.91Carbonation Potential, (assuming that Fe does not react to form FeCO3)
0.343 0.171 0.105 0.076
Carbonation Potential, (assuming that Fe reacts to form FeCO3)
0.374 0.206 0.157 0.081
Mg#1 87 - 66 48An#2 - 53 98 60
Anorthosite comprised 63% anorthite (CaAl2Si2O8), 14% forsterite (Mg2SiO4), 10% fayalite (Fe2SiO4), and 3% albite (NaAlSi3O8), and diopside (MgCaSi2O6)Basalt comprised 20% anorthite, 25% albite, 8% diopside, 8% enstatite (MgSiO3)
I (single mineral)
II (minerals and mixture rocks)
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Chemo-Morphological Coupling during Carbon Mineralization:Effect of Reaction Temperature on Olivine Carbonation
1 10 100 10000
2
4
6
8
10
Volu
me
(%)
Particle Diameter (m)
1 10 100
10-4
10-3
10-2
Cum
ulat
ive
Pore
Vol
ume
(ml/g
)
Pore Diameter (nm)
Unreacted Olivine 90 oC 125 oC 150 oC 185 oC
80 100 120 140 160 180 2000
20
40
60
80
100
Ext
ent o
f Car
bona
tion
(%)
Temperature (oC)
TGA TCA ARC [1 hr]
Experimental Conditions: PCO2 = 139 atm, 3 hrs, 1.0 M NaCl + 0.64 M NaHCO3, 15 wt% solid, 800 rpm
Gadikota et al., 2014, Physical Chemistry Chemical Physics
Temperatures > 150oC are needed to achieve high conversions via direct carbonation
Carbonate formation increases the particle size and reduces porosityC
umul
ativ
e In
tern
al V
oid
Vol
ume
(ml/g
)
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Chemo-Morphological Coupling during Carbon Mineralization:Effect of Solution Composition on Olivine Carbonation
0.0 0.5 1.0 1.5 2.0 2.50
20
40
60
80
100
Ext
ent o
f Car
bona
tion
(%)
[NaHCO3] (M)
TGA TCA ASU [1 hr]
1 10 100 10000
2
4
6
8
10
Volu
me
(%)
Particle Diameter (m)
Unreacted D.I.Water 0.32 M 0.48 M 0.64 M 1.00 M 2.00 M
1 10 100
10-4
10-3
10-2
Unreacted D.I.Water 0.32 M 0.48 M 0.64 M 1.00 M 2.00 MC
umul
ativ
e P
ore
Volu
me
(ml/g
)
Pore Diameter (nm)
0.0 0.5 1.0 1.5 2.010-6
10-5
10-4
10-3
10-2
10-1
Con
cent
ratio
n (m
ol/k
g)[NaHCO3] (M)
Mg-equilibrium Carbonate - equilibrium
(b)
Experimental Conditions: 185 oC, PCO2 = 139 atm, 3 hours, 15 wt% solid, 800 rpm
Speciation calculations show that NaHCO3 buffers pH (6.4 – 7.0).
Buffering the pH in the range of 6 – 7 facilitates dissolution and carbonation.
Progressive growth of carbonates reduces overall porosity and increases particle size.
Cum
ulat
ive
Inte
rnal
Voi
d V
olum
e (m
l/g)
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Formation of Anhydrous MgCO3 at Lower Temperatures
20 30 40 50 60 70 80
2
Unreacted
90oC
125oC
185oC
150oC
Rel
ativ
e In
tens
ity
MagnesiteOlivine
Dominant formation of magnesite (MgCO3)
Hydrous phases such as nesquehonite (MgCO3.3H2O) and hydromagnesite (Mg5(CO3)4(OH)2·4H2O) were not formed in the range of 90-185 oC
I
II
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Direct Carbon Mineralization: Compositional Effects
0.5 h
1.0 h 6.0 h
5.0 h
Reaction time
* this study
alumino-silicate bearing mineralsor rocks
silicate bearing minerals
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Gadikota et al., in progress
Experimental Conditions: 185 oC, PCO2 = 139 atm in 1.0 M NaCl + 0.64 M NaHCO3, 15 wt% solid, 800 rpm
Rapid passivation in labradorite, anorthositeand basalt limit extent of carbonation …
but not for olivine!
Direct Carbon Mineralization: Effect of Passivation on Carbon Mineralization
16
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Direct Carbon Mineralization: Effect of Reaction Time on Olivine Carbonation
Olivine carbonation is well-
modeled as exhaustion of the
remaining reactant at a
constant rate.
Experimental Conditions: 185 oC, PCO2 = 139 bars
1.0 M NaCl + 0.64 M NaHCO3, 15 wt% solid, 800 rpm
Ext
ent o
f Car
bona
tion
(%)
time (hours)17
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Comparison of Direct Mineralization Rates with Dissolution Rates:Olivine ((Mg, Fe)2SiO4)
Experimental conditions for carbonation experiments :Minerals and rocks1-3 hours, 1.0 M NaCl + 0.64 M NaHCO3
Direct olivine carbon mineralization rates at higher CO2 partial pressures
are an order of magnitude greater compared to measured dissolution rates.
vertical and horizontal ranges
are constanton next several
plots of temperatureversus rate
0 to 250°C
10-13 to 10-2 mol/(m2 s)
Rea
ctio
n R
ate
(mol
/(m2 .s
)
Temperature (oC)
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Direct Carbon Mineralization Rates:Comparison of Ca- and Mg-bearing Mineral and Rocks with Mine Tailings
Experimental conditions for carbonation experiments :Minerals and rocks 3 hours, 1.0 M NaCl + 0.64 M NaHCO3
Olivine carbon mineralization rates at higher CO2 partial pressures
are two orders of magnitude greater than carbon mineralization rates for other
common rocks and minerals.
Rea
ctio
n R
ate
(mol
/(m2 .s
)
Temperature (oC)
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Comparison of Direct Mineralization Rates with Dissolution Rates:Brucite (Mg(OH)2) and Serpentine ((Mg, Fe)3Si2O5(OH)4)
Rea
ctio
n R
ate
(mol
/(m2 .s
)
Temperature (oC)
Among peridotite alteration minerals, brucite dissolution is faster than olivine at lowtemperature, while serpentine minerals (chrysotile, lizardite) are much slower
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Comparison of Dissolution Rates:Anorthite, Labradorite, Basalt, and Basaltic Glass vs Olivine
Rea
ctio
n R
ate
(mol
/(m2 .s
)
Temperature (oC)
With the exception of amorphous basalticglass, olivine dissolution rates attemperature > 50°C are much faster thanfor basalt and alumino-silicate mineralssuch as plagioclase (anorthite, bytownite,labradorite, andesine)
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Comparison of Dissolution and Carbonation Ratesat Low Temperature with Elevated CO2
Brucite dissolves and carbonates faster than olivine
High PCO2 increases dissolution and carbonation rates
Rea
ctio
n R
ate
(mol
/(m2 .s
)
CO2 Partial Pressure (bars)
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Olivine Carbonation Kinetics over Similar Temperature Ranges
Experimental conditions for carbonation experiments :Minerals and rocks1-3 hours, 1.0 M NaCl + 0.64 M NaHCO3
Rea
ctio
n R
ate
(mol
/(m2 .s
)
1/T (K-1)
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Olivine Dissolution Kinetics and Rate Laws
Our rate law:
Hanchen’s rate law: )(76.6362
46.022, )(0854.0)./( KT
disMg eHscmmolr
))(
20425.2(5.0
))(
20421.0(2
1, 10003.0)(10)./( KTKTdisMg Hscmmolr
Mg (
aq):S
i (aq)
time (minutes)
Ea = 52.9 kJ/mol
Ea = 31 kJ/mol
log
(r)
1/T (K-1)
pH: 3.0
Magnesite Precipitation Rate:(Saldi et al., 2012)
)1()()./(33
23
32,
MMg
M
OHCOOHCOCOOH
OHCOMgprecipMg aKKKaK
KKkscmmolr
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Incorporating the Morphological Changes in the Kinetic Model
Temperature conditions chosen based on the single step carbonation rate data (Gadikota, PCCP 2014)
Assume changing volume of rock due to surface passivation: n <0, increasing surfaces available (e.g., through fractures): n> 0 no changes: n = 0
Simulations set up in PhreeqC (geochemistry software)
90 oC(Low)
125 oC(Medium)
150 oC(High)
n
time
time
time
time
VV
RateRate
00
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Carbonate Conversion Predictions Based on the Rate Data
T (oC) rMg,dis1, t = 0(mol/m2.s)
90 2.1 x 10-12
125 6.5 x 10-12
150 1.3 x 10-11
T (oC) rMg,dis2, t = 0(mol/m2.s)
90 1.4 x 10-11
125 6.7 x 10-11
150 1.7 x 10-10
Our work
Hanchen et al., 2006
(a)
(b)
Carbonation rates are highly sensitive to the temperature, rates of dissolution, and assumptions of changes in the morphology of the rocks
Rates that are greater by an order of magnitude predict complete carbonation by a time difference of a decade
=> There is a critical need to constrain rates of mineral dissolution, carbonate precipitation, and coupled dissolution and precipitation behaviors
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Role of Carbon Mineralization in Enabling Geologic Carbon Storage
To develop a comprehensive understanding of CO2 mineralization behavior and its implications for CO2 storage potential and costs
Comparison of dissolution rates and direct mineralization rates
Determination of the feedback mechanisms due to chemo -morphological - mechanical changes
Evaluation of the impacts on CO2 storage potential and net CO2
emission reductions & costs
• Develop thermodynamically downhill routes for permanent CO2storage with reduced monitoring needs
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What is the Impact on Net CO2 Emissions if Olivine is Reacted at 25 oC vs. 155 oC?
25 oC 155 oC
Kirchofer et al., Energy & Envr. Sci., 2012
Experimental evidence of higher olivine carbonation kinetics at elevated temperatures
translates into overall gains in reduced CO2 emissions.
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What is the Carbon Storage Potential via Ex-situ Mineralization Approaches?
Kirchofer et al., Energy & Envr. Sci., 2012
Natural alkalinity sources ‘‘a’’ assumes a production rate of 18 Mt per year, equivalent to U.S. lime production, and ‘‘b’’ of 760 Mt per year, equivalent to U.S. sand and gravel production
Carbon mineralization contributes to the portfolio of options
available for reliable carbon storage.
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Opportunities and Challenges in Accelerated Carbonate Formationfor Industrial Decarbonization
Gadikota et al., 2015, Advances in CO2 Capture, Sequestration, and Conversion
Gadikota et al., 2014, Journal of Hazardous Materials
Control20% SiO210% cSSS
Gadikota et al., 2015, Advances in CO2 Capture, Sequestration, and Conversion
Variable compositions of industrial wastescan complicate the development of consistentprocesses
May need high temperatures and pressuresto achieve reasonable conversions
Incorporate these materials into constructionmaterials
Safe for landfilling due to reduced alkalinity
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Opportunities in Accelerated Carbonate Formationfor Industrial Decarbonization: Synthesis of High-Value Products
Gadikota and Park, 2014, Carbon Dioxide Utilization, Elsevier
Achieving high degree of control over desired chemical and morphological composition for CO2 utilization remains a challenge
Gadikota et al., 2015, Advances in CO2 Capture, Sequestration, and Conversion
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Preliminary Estimated Costs
Storage approach US$/ton CO2
Geologic carbon storage* 0.5 - 8
Geologic carbon storage: monitoring and storage*
0.1 - 0.3
Mineral carbonation* 50 – 100*
Mine tailings carbonation with co-production of value-added commodities (Ni)
10 - 60
Grinding and milling ~ $10/ton of rockChemical processing cost ~ varies from $ 10 - $ 50/ton of rock (path dependent)Cost estimates for mineral carbonation ~ $ 20 - $ 60
Offsets for costs include the production of value-added materials ~ $ 5 - $15/tonFeasible range for mineral carbonation: $ 5 - $ 45/ton
*IPCC special report on carbon capture and storage, 2005
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Conclusions and Summary
Development of consistent experimental methodologies has led to an improved understanding of carbon mineralization rates.
Significant variations in predicted mineralization rates translate into field scale uncertainties in monitoring costs.
Mineralization rates are accelerated at higher temperatures and high pCO2in situ carbon mineralization achieves high T and P at low cost ex situ potential for utilizing industrial waste heat may offset energy costsco-production of energy and useful commodities may offset overall costs
Advanced mineralization approaches have the potential to be used in industrial decarbonization in addition to enabling clean fossil energy production.
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34
Acknowledgments
Geo-Chemo-Mechanical Studies for Permanent CO2 Storage in Geologic Reservoirs
NSF Research Coordination NetworkCarbon Capture, Utilization & Storage
Accelerated CO2 conversion to carbonates
Peter Kelemen and Alissa Park, Columbia University
Greg Dipple, University of British Columbia
Funding Sources
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Questions?
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Laboratory Scale Dissolution Rates: Novel Reactor Designs to Probe Surface and Bulk Dissolution
Variations in surface dissolution vs. bulk dissolution rates observed in serpentine ((Mg,Fe)3Si2O5(OH)4)
Gadikota et al., 2014, Industrial and Engineering Chemistry Research
Custom-built Differential Bed Reactor to Determine Surface and Bulk Dissolution Rates
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Chemo-Morphological Coupling during Carbon Mineralization:Effect of Reaction Temperature on Olivine Carbonation
1 10 100 10000
2
4
6
8
10
Volu
me
(%)
Particle Diameter (m)
1 10 100
10-4
10-3
10-2
Pore Diameter (nm)
Unreacted Olivine 90 oC 125 oC 150 oC 185 oC
80 100 120 140 160 180 2000
20
40
60
80
100
Ext
ent o
f Car
bona
tion
(%)
Temperature (oC)
TGA TCA ARC [1 hr]
Experimental Conditions: PCO2 = 139 atm, 3 hrs, 1.0 M NaCl + 0.64 M NaHCO3, 15 wt% solid, 800 rpm
Gadikota et al., 2014, Physical Chemistry Chemical Physics
Temperatures > 150oC are needed to achieve high conversions via direct carbonation
Carbonate formation increases the particle size and reduces porosity
Cum
ulat
ive
Inte
rnal
Voi
d V
olum
e (m
l/g)
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Chemo-Morphological Coupling during Carbon Mineralization:Effect of Solution Composition on Olivine Carbonation
0.0 0.5 1.0 1.5 2.0 2.50
20
40
60
80
100
Ext
ent o
f Car
bona
tion
(%)
[NaHCO3] (M)
TGA TCA ASU [1 hr]
1 10 100 10000
2
4
6
8
10
Volu
me
(%)
Particle Diameter (m)
Unreacted D.I.Water 0.32 M 0.48 M 0.64 M 1.00 M 2.00 M
1 10 100
10-4
10-3
10-2
Unreacted D.I.Water 0.32 M 0.48 M 0.64 M 1.00 M 2.00 M
Pore Diameter (nm)
0.0 0.5 1.0 1.5 2.010-6
10-5
10-4
10-3
10-2
10-1
Con
cent
ratio
n (m
ol/k
g)[NaHCO3] (M)
Mg-equilibrium Carbonate - equilibrium
(b)
Experimental Conditions: 185 oC, PCO2 = 139 atm, 3 hours, 15 wt% solid, 800 rpm
Speciation calculations show that NaHCO3 buffers pH (6.4 – 7.0)
Buffering the pH in the range of 6 – 7 facilitates dissolution and carbonation
Progressive growth of carbonates reduces overall porosity and increases particle size
Cum
ulat
ive
Inte
rnal
Voi
d V
olum
e (m
l/g)
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Formation of anhydrous MgCO3 at lower temperatures
20 30 40 50 60 70 80
2
Unreacted
90oC
125oC
185oC
150oC
Rel
ativ
e In
tens
ity
MagnesiteOlivine
Dominant formation of magnesite (MgCO3)
Hydrous phases such as nesquehonite (MgCO3.3H2O) and hydromagnesite (Mg5(CO3)4(OH)2·4H2O) were not formed in the range of 90-185 oC
I
II
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Direct Carbon Mineralization Rates:Comparison of Ca- and Mg-bearing Mineral and Rocks with Mine Tailings
100% 50%
10%
0.04%
Brucite mine tailings(vol % CO2 at 1 atm)
Experimental conditions :Minerals and rocks: 185 oC, PCO2 = 139 atm, 3 hours, 1.0 M NaCl + 0.64 M NaHCO3Brucite (Mg(OH)2) mine tailings: ambient temperature, reaction time > 70 hours (Harrison et al., ES&T, 2013)
*Rate data normalized to BET surface area
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41
Comparison of Direct Mineralization Rates with Dissolution Rates:Olivine ((Mg, Fe)2SiO4)
Rea
ctio
n R
ate
(mol
/(m2 .s
)
Temperature (oC)
*Rate data normalized to geometric surface area
Direct olivine carbon mineralization rates at higher CO2 partial pressures
are an order of magnitude greater compared to measured dissolution rates.
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Comparison of Direct Mineralization Rates with Dissolution Rates:Brucite (Mg(OH)2) and Serpentine ((Mg, Fe)3Si2O5(OH)4)
Rea
ctio
n R
ate
(mol
/(m2 .s
)
Temperature (oC)
(100 vol% CO2)( 50 vol% CO2)( 10 vol% CO2)
( 4 vol%)
direct mineralization rates of brucite bearing mine tailings
*Rate data normalized to geometric surface area
At low CO2 concentrations (~4 vol. %), direct mineralization rates of brucite mine tailingsare comparable with dissolution rates. Reaction rates increases with CO2 concentrations.
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Comparison of Direct Mineralization Rates with Dissolution Rates:Anorthite, Labradorite, and Basalt
*Rate data normalized to geometric surface area
Rea
ctio
n R
ate
(mol
/(m2 .s
)
Temperature (oC)
Shaded region represents direct mineralization rates of labradorite, anorthite, and basalt
Direct mineralization rates are 1-2 orders of magnitude higher compared to dissolution rates of anorthite, labradorite, and basalt
Hypothesis: Continuous removal of carbonate ions in solution to form solid precipitates drives the forward dissolution reaction rate => higher direct mineralization rates
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Magnesite Formation in Fractured Porous Media: Evidence of Chemo-Morphological-Mechanical Coupling
During Carbon Mineralization
(a) (b)
Evidence of magnesite formation along olivine fractures
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45
Rate Data for Predicting the Time Scale of Carbonate Formation
Ea = 52.9 kJ/mol
Ea = 31 kJ/mol
Our rate law:
Hanchen’s rate law:
Magnesite Precipitation Rate:(Saldi et al., 2012)
)(76.6362
46.022, )(0854.0)./( KT
disMg eHscmmolr
)1()()./(33
23
32,
MMg
M
OHCOOHCOCOOH
OHCOMgprecipMg aKKKaK
KKkscmmolr
))(
20425.2(5.0
))(
20421.0(2
1, 10003.0)(10)./( KTKTdisMg Hscmmolr
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Incorporating the Morphological Changes in the Kinetic Model
Temperature conditions chosen based on the single step carbonation rate data (Gadikota, PCCP 2014)
Assume changing volume of rock due to surface passivation: n <0, increasing surfaces available (e.g., through fractures): n> 0 no changes: n = 0
Simulations set up in PhreeqC (chemistry software)
90 oC(Low)
125 oC(Medium)
150 oC(High)
n
time
time
time
time
VV
RateRate
00
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Carbonate Conversion Predictions Based on the Rate Data
T (oC) rMg,dis1, t = 0(mol/m2.s)
90 2.1 x 10-12
125 6.5 x 10-12
150 1.3 x 10-11
T (oC) rMg,dis2, t = 0(mol/m2.s)
90 1.4 x 10-11
125 6.7 x 10-11
150 1.7 x 10-10
Our work
Hanchen et al., 2006
(a)
(b)
Carbonation rates are highly sensitive to the temperature, rates of dissolution, and assumptions of changes in the morphology of the rocks
Rates that are greater by an order of magnitude predict complete carbonation by a time difference of a decade
=> There is a critical need to constrain rates of mineral dissolution, carbonate precipitation, and coupled dissolution and precipitation behaviors
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Role of Carbon Mineralization in Enabling Geologic Carbon Storage
To develop a comprehensive understanding of CO2 mineralization behavior and its implications for CO2 storage potential and costs
Comparison of dissolution rates and direct mineralization rates
Determination of the feedback mechanisms due to chemo -morphological - mechanical changes
Evaluation of the impacts on CO2 storage potential and net CO2
emission reductions & costs
• Develop thermodynamically downhill routes for permanent CO2storage with reduced monitoring needs
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What is the impact on net CO2 emissions if olivine is reacted at 25 oC vs. 155 oC?
25 oC 155 oC
Kirchofer et al., Energy & Envr. Sci., 2012
Experimental evidence of higher olivine carbonation kinetics at elevated temperatures
translates into overall gains in CO2 emissions reduced.
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What is the carbon storage potential via ex-situ mineralization approaches?
Kirchofer et al., Energy & Envr. Sci., 2012
Natural alkalinity sources ‘‘a’’ assumes a production rate of 18 Mt per year, equivalent to U.S. lime production, and ‘‘b’’ of 760 Mt per year, equivalent to U.S. sand and gravel production
Carbon mineralization contributes to the portfolio of options
available for reliable carbon storage
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Direct Carbon Mineralization: Compositional Effects
0.5 h1.0 h 6.0 h
5.0 hReaction time
* this study
alumino-silicate bearing minerals or rocks
silicate bearing minerals
In-situ storage potential
Ex-situ storagepotential
Storage approach US$/ton CO2
Geologic carbon storage
0.5 - 8
Geologic carbon storage: monitoring and storage
0.1 - 0.3
Mineral carbonation 50 – 100*
Estimates from IPCC Special Report on Carbon Capture and Storage, 2005
Significant uncertainties exist in reporting costs for carbon mineralization
Potential of using waste heat at a power plant as heating source
Availability of pre-ground mine tailings as low-cost substrates
Potential reuse of industrial acidic and alkaline waste water streams
Tailored use of passive vs. active carbonation approaches
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Opportunities in Accelerated Carbonate Formationfor Industrial Decarbonization: Synthesis of High-Value Products
Gadikota and Park, 2014, Carbon Dioxide Utilization, Elsevier
Achieving high degree of control over desired chemical and morphological composition for CO2 utilization remains a challenge
Gadikota et al., 2015, Advances in CO2 Capture, Sequestration, and Conversion
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Conclusions and Summary
Development of consistent experimental methodologies has led to an advanced understanding of carbon mineralization rates.
Significant variations in predicted mineralization rates translates into field scale uncertainties in monitoring costs.
Mineralization rates are accelerated at higher temperatures and in water-rich environments => potential for utilizing industrial waste heat or waste water may result in significant offset of overall energy costs.
Advanced mineralization approaches have the potential to be used in industrial decarbonization in addition to enabling clean fossil energy production.
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Metastability in MgO-CO2-H2O Systems
Magnesite is the most stable and least soluble carbonate under most conditions (including PCO2)
Despite this, magnesite is seldom the main product reported in literature:- Brucite: Mg(OH)2
- Lansfordite: MgCO3·5H2O
- Nesquehonite: MgCO3·3H2O
- Hydromagnesite: Mg5(CO3)4(OH)2·4H2O
- Magnesite: MgCO3
Driven by reaction kinetics, given enough time, magnesite should form
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Effect of Temperature on Mg(OH)2 Slurry Carbonation
At 150 ºCMake Hydromagnesite
At 30 ºCMake Nesquehonite
At 200 ºC Make Magnesite
Fricker et al., I&ECR, 2014.