mineralization: co2 conversion to carbonates for co2 utilization and storage
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Mineralization: CO2 Conversion to Carbonates for
CO2 Utilization and Storage
Greeshma Gadikota Dept. of Chemical Engineering & Dept. of Earth and Environmental Engineering
Lenfest Center for Sustainable Energy Columbia University in the City of New York
New York, NY
RECS June 10, 2015
CO2 Capture Materials
2
q MEA Challenges § Corrosion and solvent degradation
§ High capital and operating costs
§ High parasitic energy penalty
(NETL, 2011)
Song at Penn State
Giannelis at Cornell and Park at Columbia
Novel Materials
Solid Sorbents & Chemical Looping Technologies
Water-‐Gas Shi-: CO + H2O !" H2 + CO2
Carbonation / Calcination cycle Oxidation / Reduction cycle
MO + CO2 à MCO3
MCO3 à MO + CO2
MO + CO à M + CO2
M + H2O à MO + H2
e.g., ZECA process (Los Alamos National Lab)
e.g., Chemical Looping process for H2 production (Ohio State Univ.: U.S. Patent No. 11/010,648 (2004))
KIER’s 100kW CLC system (2006-2011)
Micro- vs. Mesopores
CO2 Utilization
4 (NETL, 2011)
Challenges and Opportunities • Carbonate formation is thermodynamically
favored
• Using CO2 as an alternative processing fluid for unconventional hydrocarbon extraction reduces the need for water
Carbon Storage Schemes
Capture U8liza8on Storage
§ Mimics natural chemical transformation of CO2
MgO + CO2 → MgCO3
§ Thermodynamically stable product & Exothermic reaction
§ Appropriate for long-term environmentally benign and unmonitored storage
q Ocean storage
q Biological fixation
q Geologic storage
q Mineral carbonation
CO2 Injec8on Well
Gas Processing PlaBorms 1 million tons of CO2 injected every year since 2006
USD 100,000 saved daily on CO2 tax
Graphic courtesy of Statoil (Geo3mes, 2003)
Statoil’s Sleipner West Gas reservoir in the North Sea
600,000 tons of CO2 injected every year since
2004
In Salah Gas Project in Algeria
Graphic courtesy of BP (Geo3mes, 2003)
Research Objectives
6
Comprehensive understanding of CO2 interactions with natural and engineered materials
§ Closing the carbon cycle within energy conversion processes via engineered carbonation using both its own wastes and natural sources
§ Enable efficient extraction of unconventional energy sources (e.g., shale) with combined CO2 storage
§ Understanding of long-term fate of injected CO2 in the earth system
Develop transformative approaches towards sustainable energy with integrated carbon capture, utilization, and storage
Various Materials for Carbon Fixation
7
Source: Kurt Houz
Availability silicate minerals >> industrial wastes Crystallinity industrial wastes < minerals Reactivity industrial wastes > minerals Pre-processing requirements (e.g., mining, crushing etc.,) industrial wastes < minerals
Carbonation of industrial wastes results in reclassification of these materials as non-hazardous hence safe for landfilling and for long-term carbon storage
Carbon Mineralization
8
CO2 Conversion to Carbonates
9
Source: Gadikota and Park, 2014, Carbon Dioxide Utilization, 1st Edition, Elsevier
q Develop technologies to integrate carbonation of industrial wastes at the site of CO2 generation
q Determine the fate of hazardous components such as Cr, Ni during carbonation
q Use CO2 to treat hazardous Asbestos Containing Materials (ACM)
Source: Gadikota et al., 2014, Journal of Hazardous Materials
Worldwide Availability of Ca and Mg-bearing Alkaline Materials for CCUS
10
Belvidere Mountain, Vermont Serpentine Tailings
Mineral Carbonation of Peridotite
Photo by Dr. Jürg Matter at LDEO (2008)
Effect of Chemical Composition on CCS Storage Potential
11
Magnetite Anorthite B as a lt T a lc Augite L iza rdite Antigorite F aya lite F ors terite Wollas tonite
0
20
40
60
80
100
Extent of Carbonation (%)
Experiments performed at 185oC, PCO2 of 150 atm in 1.0M NaCl+0.64M NaHCO3. 15 wt. % solid Reaction time:
Abundance of less reactive minerals vs. limited availability of highly reactive minerals
1 hr 0.5 hr 4 hr
4 hr dry attrition grinding All others – 1 hour dry attrition grinding
Carbonation efficiency defines whether mineral is utilized for ex-situ or in-situ storage
Ex-situ CO2 Storage
In-Situ CO2 Storage
Shorter time scales (~hours)
Longer time scales (~years)
Limited spatial scale Larger spatial scale with utilization of earth as a reactor (~hundreds of miles)
Relatively homogenous 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 CO2 trapping mechanisms Relatively economical at this time
O’Connor et al., AAPG Annual Meeting, 2003
Silicates Alumino-silicates
Direct vs. Two-Step Carbonation
12 Gadikota and Park, 2014, Carbon Dioxide Utilization, 1st Edition, Elsevier
Synthesis of High Purity Products and By-Products
13 Gadikota and Park, 2014, Carbon Dioxide Utilization, Elsevier
(Mg,Fe)2SiO4 and (Mg,Fe)3(OH)4(Si3O5)Mg-bearing Silicates
(CaSiO3) Ca-bearing Silicates
Mg-CarbonatePhases
30 µm
Nesquehonite (MgCO3.3H2O)
30 µm
Hydromagnesite(Mg5(CO3)4(OH)2·4H2O)
30 µm
Magnesite(MgCO3)
1 µm
Geothite(a-FeO(OH))
Silica(SiO2)
500 nm
Ca-CarbonatePhases
1 µm
1 µm
1 µm
Vaterite
Aragonite
Calcite
• Products of the pH swing process where silica isobtained at pH ~2, geothite is precipitated at pH~8.6, and magnesium or calcium carbonate at pH ~10.
• Increasing temperature and PCO2 favor theformation of anhydrous magnesium carbonatephases such as magnesite (MgCO3).
• Optimal conditions for forming calcite are pH > 12,aragonite at pH 11, and vaterite at a pH between9.0 and 9.5.
Achieving high degree of control over desired chemical and morphological composition for CO2 utilization remains a challenge
Gadikota et al., 2014, Green Building Materials (Book Chapter) – Submitted
Fundamental Challenges in Carbon Mineralization
14
Need for novel reactor systems and comprehensive material characterization
• Inadequate and inaccurate kinetic data
• Variability in rates – fast, initial kinetics vs. long-term, slow kinetics
• Formation of mass transfer limiting passivation layers
• Competing reactions – challenging to produce pure components
• Formation of meta-stable carbonates
• Considerable heterogeneity in the starting materials and product phases
• pH control with additives needed
• Modeling and prediction uncertainties
Fundamental Challenges in Carbon Mineralization
15
• Inadequate and inaccurate kinetic data
• Variability in rates – fast, initial kinetics vs. long-term, slow kinetics
• Formation of mass transfer limiting passivation layers
• Competing reactions – challenging to produce pure components
• Formation of meta-stable carbonates
• Considerable heterogeneity in the starting materials and product phases
• pH control with additives needed
• Modeling and prediction uncertainties
Need for novel reactor systems and comprehensive material characterization
Better Design of Kinetic Studies for Complex Reactions
16 Gadikota et al., I&ECR 2014
Dissolution Kinetics & Rate Laws for Magnesium Silicate
17
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 Ω−
++=
−−
−
))(
20425.2(5.0
))(
20421.0(2
1, 10003.0)(10)./( KTKTdisMg Hscmmolr
−−+
−
×+×=
Fundamental Challenges in Carbon Mineralization
18
• Inadequate and inaccurate kinetic data
• Variability in rates – fast, initial kinetics vs. long-term, slow kinetics
• Formation of mass transfer limiting passivation layers
• Competing reactions – challenging to produce pure components
• Formation of meta-stable carbonates
• Considerable heterogeneity in the starting materials and product phases
• pH control with additives needed
• Modeling and prediction uncertainties
Need for novel reactor systems and comprehensive material characterization
Metastability in MgO-CO2-H2O System
§ 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
Swanson et al., PCCP 2014 19
Significant Complexity in Mg-CO2-H2O Systems
- Maximum saturation index (Ω) achievable under the experimental conditions reported in 23+ publications
- Significant variety in carbonate formation over similar reaction conditions !
Ω = log IAPKSP
"
#$
%
&'
20 Swanson et al., PCCP 2014
Effect of Temperature on Mg(OH)2 Slurry Carbonation
à Biggest factor influencing phase is Temperature
à Easily distinguishable by TGA and XRD analyses
Magnesite: MgCO3 Hydromagnesite: Mg5(CO3)4(OH)2·4H2O Nesquehonite: MgCO3·3H2O
Fricker et al., I&ECR 2014 21
Effect of Temperature on Mg(OH)2 Slurry Carbonation
At 150 ºC Make Hydromagnesite
At 30 ºC Make Nesquehonite
At 200 ºC Make Magnesite
22 Fricker et al., I&ECR 2014
Effect of Seeds on Mg(OH)2 Slurry Carbonation
Starting materials
Mg(OH)2
Al2O3
MgCO3
Carbonation at 150 ⁰C for 120 min
23 Swanson et al., PCCP 2014
Fundamental Challenges in Carbon Mineralization
24
• Inadequate and inaccurate kinetic data
• Variability in rates – fast, initial kinetics vs. long-term, slow kinetics
• Formation of mass transfer limiting passivation layers
• Competing reactions – challenging to produce pure components
• Formation of meta-stable carbonates
• Considerable heterogeneity in the starting materials and product phases
• pH control with additives needed
• Modeling and prediction uncertainties
Need for novel reactor systems and comprehensive material characterization
Better Design of Kinetic Studies for Complex Systems
25 Gadikota et al., I&ECR 2014
Effect of Temperature on Magnesium Silicate Carbonation
26
1 10 100 10000
2
4
6
8
10
Volum
e (%
)
P a rtic le D iameter (µm)
1 10 100
10-‐4
10 -‐3
10 -‐2
Cum
ulative Pore Volum
e (m
l/g)
P ore D iameter (nm)
Unreac ted O liv ine 90 oC 125 oC 150 oC 185 oC
80 100 120 140 160 180 2000
20
40
60
80
100
Exten
t of C
arbo
natio
n (%
)
T emp era ture ( oC )
T G A T C A AR C [1 hr]
Experimental Conditions: PCO2 = 139 atm, 3 hrs, 1.0 M NaCl + 0.64 M NaHCO3, 15 wt% solid, 800 rpm
Coupled effects of (i) CO2 hydration (ii) mineral dissolution, and (iii) formation of carbonates are evident. Increasing temperature aids mineral dissolution kinetics and reduces the solubility of magnesite
1 10 100
10-‐4
10 -‐3
10 -‐2
Cum
ulative Pore Volum
e (m
l/g)
P ore D iameter (nm)
Unreac ted O liv ine 90 oC 125 oC 150 oC 185 oC
Gadikota et al., PCCP (2014)
Formation of anhydrous MgCO3 at lower temperature
27
(a)
20 30 40 50 60 70 80
2θ
Unrea cte d
90oC
125oC
185oC
150 oC
Relative Intensity
MagnesiteOlivine
0.1 1 10
Relativ
e Intensity
ke V
(a)
(II)
(I)
C
O
Mg
OMg
Si
(b)
Magnesite
Si-rich Phase
0.1 1 10
Relativ
e Intensity
ke V
(a)
(II)
(I)
C
O
Mg
OMg
Si
(b)
Magnesite
Si-rich Phase10 µm
0.1 1 10
Relative Intens
ityke V
(a)
(II)
(I)
C
O
Mg
OMg
Si
(b)
Magnesite
Si-rich Phase
0.1 1 10
Relative Intens
ity
ke V
(a)
(II)
(I)
C
O
Mg
OMg
Si
(b)
Magnesite
Si-rich Phase10 µm
• 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
Gadikota et al., PCCP (2014)
Effect of NaHCO3 on Magnesium Silicate Carbonation
28
0.0 0.5 1.0 1.5 2.0 2.50
20
40
60
80
100
Exten
t of C
arbo
natio
n (%
)
[N aHC O3] (M)
T G A T C A A S U [1 hr]
1 10 100 10000
2
4
6
8
10
Volum
e (%
)
P a rtic le D iameter (µm)
Unreac ted D .I.W ater 0.32 M 0.48 M 0.64 M 1.00 M 2.00 M
1 10 100
10-‐4
10 -‐3
10 -‐2
Unreac ted D .I.W ater 0.32 M 0.48 M 0.64 M 1.00 M 2.00 MC
umulativ
e P
ore V
olume (ml/g
)
P ore D iameter (nm)
0 .0 0.5 1 .0 1.5 2 .0 2.50
20
40
60
80
1 00
Exten
t of C
arbona
tion (%
)
[N a H C O3] (M)
TG A T C A A S U [1 hr]
0 .0 0 .5 1.0 1 .5 2.01 0 -‐6
1 0-‐5
1 0-‐4
1 0 -‐3
1 0-‐2
1 0-‐1
Con
centratio
n (mol/kg)
[N a H C O 3] (M)
Mg -‐equ ilibrium C arbona te -‐ equ ilib rium
1 1 0 1 0 0
1 0 -‐4
1 0-‐3
1 0 -‐2
Unreac ted D .I .Wa ter 0.32 M 0.48 M 0.64 M 1.00 M 2.00 MC
umulativ
e P
ore V
olume (m
l/g)
P ore D iam e te r (nm)
(c)
1 10 10 0 1 0 000
2
4
6
8
10
Volume (%)
P a rtic le D ia me ter (µm)
Unreac ted D .I .Wa ter 0.32 M 0.48 M 0.64 M 1.00 M 2.00 M
(a)
(d)
(b)
Speciation calculations show that NaHCO3 buffers pH (6.4-7.0) and serves as a carbon carrier Buffering the pH in the range of 6-7 facilitates dissolution and carbonation
Experimental Conditions: 185 oC, PCO2 = 139 atm, 3 hours, 15 wt% solid, 800 rpm
Gadikota et al., PCCP (2014)
Can we predict the long-term fate of CO2 based on our laboratory data?
29
Need dissolution and carbonation rate data in addition to choice of reaction conditions
Selected Magnesium Silicate-CO2-Fluid System
30
0.1 1 10
Relative Intens
ity
keV
(a)
(2)
(1)
(b)
C
OMg
Magnesite
Si-rich Phase
O
Mg
Si
10 µm
2
1
0.1 1 10
Relative Intens
ity
keV
(a)
(2)
(1)
(b)
C
OMg
Magnesite
Si-rich Phase
O
Mg
Si
0.1 1 10keV
Rela
tive I
nten
sity
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)
(a)
(b)
90 oC (Low)
125 oC (Medium)
150 oC (High)
n
time
time
time
time
VV
RateRate
⎥⎦
⎤⎢⎣
⎡=
== 00
Gadikota et al., to be submitted (2014)
Sensitivity Analyses (temperature, degree of fracture formations, rate constant)
31
(a) (b)
(d)(c)
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.,
Hanchen et al., Geochim. Cosmochim. Ac. (2006)
Gadikota et al., to be submitted (2014)
Temperature
Pressure
Salinity of fluid pH of fluid
Mineral reactivity
Reactive surface area
Mineral dissolution
Mineral carbonation
Porosity
Permeability
Formation of micro-fractures
+ +
+ +
+ + +
+
+ +
+
+ + + -‐
-‐
+
+
+ pH>7
pH<5
+
Coupling Kinetic and Transport Phenomena in Complex Systems
32
Research Objectives
33
Comprehensive understanding of CO2 interactions with natural and engineered materials
§ Closing the carbon cycle within energy conversion processes via engineered carbonation using both its own wastes and natural sources
§ Enable efficient extraction of unconventional energy sources (e.g., shale) with combined CO2 storage
§ Understanding of long-term fate of injected CO2 in the earth system
Develop transformative approaches towards sustainable energy with integrated carbon capture, utilization, and storage
Global shale gas reserves
34
Deeper formations Lack of water
Unconventional Energy Sources (e.g., shale)
35
Technological advancements q Horizontal drilling q Hydraulic fracturing But significant water consumption and contamination
q Chemically functionalized proppants to immobilize heavy metals
q “waterless fracking” with gases such as CO2 Potential carbon storage
But what are the coupled reactive-transport phenomena that would impact CO2-shale interactions?
Possible solutions
Proposed Interaction of CO2 and Clays (for shale)
Berrezueta et al., 2013, International Journal of Greenhouse Gas Control 36
q Initial arrangement of clay matrix
q Before CO2 injection
q Gas drag force breaks inter-clay particle physical bonds q Clay particles pulled through pore spaces
q CO2 diffuses into clay-layered structures q Changes in interlayer electrical forces => inter-clay break-up
q CO2 occupies space created from clay matrix disruption
Characterization of Various Types of Shales Shale
Non-calcite Calcite-bearing Oil-rich Components Carbonaceous
(wt%) Argillaceous
(wt%) Bituminous
(wt%) SiO2 58.6 55.7 40.3 Al2O3 21.4 17.5 9.5 Fe2O3 5.1 6.6 4.1 MgO 1.6 2.3 1.7 CaO 0.2 3.6 19.4 Na2O 0.3 0.2 0.8 K2O 4.1 4.2 2.1 TiO2 1.1 0.8 0.5 P2O5 0.1 0.1 0.2 MnO 0.03 0.04 0.05 Cr2O3 0.05 0.04 0.03 V2O5 0.03 0.04 0.02 LOI 7.2 8.0 19.4 Total Carbon (%) 1.26 1.62 6.49 Organic Carbon (%) 0.74 0.67 2.48 Inorganic Carbon (%) 0.52 0.95 4.01
37
Supercritical CO2 Interaction with Shale
Loring et al., Langmuir, 2012
CO2 intercalation with clays => expansion CO2 is rotationally constrained and does not appear to react with trapped water
38
Research Questions
• What is the effect of dry vs. wet scCO2?
• What are the effects of variable chemical compositions of shale?
• Can CO2 be used as an alternative for acid-induced fracking?
Effect of CO2 and Water on Pore Volume Changes
Combination of water and CO2 => significant morphological changes
Are these changes chemically induced ?
Experimental conditions: PCO2 = 150 atm, 80 oC, 3 hr
39
Effect of CO2 and Water on Chemical Changes
40
Insufficient acidity to induce significant chemical changes in Al and oil-rich shales Phase changes evident in C & Al-rich shales
Effect of CO2 and Water on Clay CO2 interactions with montmorillonite
Espinoza et al., 2012, International Journal of Greenhouse Gas Control
41
Effect of Temperature on Pore Volume Changes
Higher temperatures result in greater pore volume changes Utilize the geothermal gradient for greater energy extraction – but deeper drilling is more expensive
42
Effect of Temperature on Chemical Changes
43
Some changes in carbonaceous shales No significant changes in argillaceous and bituminous shales
How can we accelerate increase in pore spaces?
Acid fracking
44
Courtesy: The Chronicle
Typical shale deposit Monterey Shale, California
• Uneven geological formations make horizontal drilling harder • Injecting strong acids (e.g., HCl) rapidly disorders or dissolves clays, carbonates etc., • Environmentally hazardous
Are there are any alternative benign chemicals that can be used to induce chemical changes?
Effect of Na-citrate and CO2
45
0.1 M Na-citrate, pH = 3.0
Unreacted Reacted Calcite-rich
Oil-rich
Unreacted Reacted
Non-calcite
Calcite-rich
Non-calcite
Oil-rich
Experiments performed at 80 oC for 3 hours
0.1 M Na-citrate, PCO2 = 150 atm
Research Objectives
46
Comprehensive understanding of CO2 interactions with natural and engineered materials
§ Closing the carbon cycle within energy conversion processes via engineered carbonation using both its own wastes and natural sources
§ Enable efficient extraction of unconventional energy sources (e.g., shale) with combined CO2 storage
§ Understanding of long-term fate of injected CO2 in the earth system
Develop transformative approaches towards sustainable energy with integrated carbon capture, utilization, and storage
Summary
47
• Combination of multi-scale experimental and modeling studies are needed to develop CCUS technologies
• Investigation of coupled physical and chemical phenomena is essential for predicting the fate of CO2 above and below the ground
• Accurate kinetic and mechanistic data are needed to predict multi-scale and multi-temporal interactions of CO2 with different materials
• Identification of all processes that emit CO2 and determination of methods to limit these emissions are needed to close the carbon balance
Acknowledgements
48
Advisors and Collaborators Prof. Alissa Park (Columbia)
Prof. Peter Kelemen (Columbia)
Prof. Juerg Matter (Southampton)
Dr. Pat Brady (Sandia)
Prof. Venkat Venkatasubramanian (Columbia)
Dr. Babji Srinivasan (IIT)
Dr. Claudio Natali (IGR, Italy)
Dr. Chiara Boschi (IGR, Italy) Park Group Members
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