Ah-Hyung Alissa Park

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???? ???? ?? ?? ??, ?? ? ???? Towards Sustainable
Energy Carbon Capture, Utilization and Storage
Ah-Hyung Alissa Park Departments of Earth and
Environmental Engineering Chemical
Engineering Lenfest Center for Sustainable
Energy Columbia University ULTRA August 9th, 2012
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Coal-fired Build Rate China and United States
Source http//www.netl.doe.gov/coal/refshelf/ncp.
pdf
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Energy, Economic Growth and Quality of Life
EIA Data 2009
Source http//www.netl.doe.gov/coal/refshelf/ncp.
pdf
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Towards Sustainable Energy and Environment
Use domestic energy sources to achieve energy
independence with environmental sustainability
Recycled CO2
Refining
Use carbon neutral energy sources
Fossil fuels are fungible
Integrate carbon capture, utilization and storage
(CCUS) technologies into the energy conversion
systems
Stored CO2
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Carbon Capture, Utilization and Storage
Technologies (CCUS)

• Required characteristics for CCS
• Capacity and economic feasibility
• Environmental benign fate
• Long term stability

Carbon Capture Technologies
(NETL, 2011)

• MEA Challenges
• Corrosion and solvent degradation
• High capital and operating costs
• High parasitic energy penalty

(NETL, 2010)
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Solid Sorbents Chemical Looping Technologies
Carbonation / Calcination cycle
Oxidation / Reduction cycle
Water-Gas Shift CO H2O ?? H2 CO2
KIERs 100kW CLC system (2006-2011)
MO CO2 ? MCO3 MCO3 ? MO CO2
MO CO ? M CO2 M H2O ? MO H2
Micro- vs. Mesopores
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))
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Novel CO2 Capture Solvents (2011 2012 NETL CO2
Capture Technology Meeting)

• Ionic liquids
• CO2BOLs
• Liquid-like Nanoparticle Organic Hybrid Materials

• Carbonic Anhydrase (Enzyme)
• Phase changing absorbents

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Nanoparticle Organic Hybrid Materials (NOHMs)

• Solvent-free liquid-like hybrid systems
• Solvent tethered to nanoparticle cores
• Zero-vapor pressure and improved thermal
  stability
• Tunable chemical and physical properties
• Liquid, solid, gel
• Solvation in NOHMs driven by both entropic and
  enthalpic interactions
• Straightforward synthesis
• Easy to scale up

Zero Vapor Pressure Tunable Properties
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Design and Synthesis of liquid-like NOHMs
NOHM-C-HPE-POSS POSS Polyhedral Oligomeric
Silsesquioxane
NOHM-I-HPE (or NOHM-I-PEG)
NOHM-C-HPE and NOHM-C-MPE
PEG

• PEG polyethylene glycol
• PE polyetheramine
• PEI polyethyleneimine
• H high, M moderate, and t tertiary

NOHM-I-PEI
NOHM-I-tPE
Temp Swing from 20 ºC to 120/140 ºC
Improved Thermal Stability
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Ordered and Frustrated Corona?
Pure Polymer
NOHMs
1H ROE signal marker
canopy
AFM Images
Less ROE signals
Significant entanglement
TEM Images
2D ROESY (Rotating-frame Overhauser Effect
SpectroscopY) NMR This technique enables
identification of through-space interactions
(presence of off-diagonal peaks)
Y. Park, J. Decatur, K.-Y A. Lin, A.-H. A. Park,
PCCP 2011
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CO2 Capture Mechanisms
ATR FT-IR spectra of NOHMs CO2

• A loss of double degeneration of the CO2 bending
  mode (n2) is observed upon exposure to CO2
• This feature is related to the presence of Lewis
  acid-base interactions between CO2 and the ether
  groups

Lewis acid-base interactions
Y. Park, J. Decatur, K.-Y A. Lin, A.-H. A. Park,
PCCP 2011 Y. Park, D. Shin, A.-H. A. Park, J.
Chem. Eng. Data 2011
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CO2 Packing Behaviors
CO2 bending modes (NOHM-I-HPE)
Linear chains
Branched chains
Area ratio n2in-plane to n2out-of-plane provides
insight into CO2 packing behaviors in NOHMs
C. Petit, Y. Park, K.-Y A. Lin, A.-H. A. Park,
JPC-C (2012) Y. Park, C. Petit, P. Han, A.-H. A.
Park, (in preparation)
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CO2-induced Swelling
NOHMs vs. polymer (NOHM-I-HPE)

• NOHMs swell less than the corresponding unbound
  polymer for the same CO2 loading
• This will impact the accessibility of CO2 to
  functional groups along the polymer chains

Y. Park, J. Decatur, K.-Y A. Lin, A.-H. A. Park,
PCCP 2011. Y. Park, D. Shin, A.-H. A. Park, J.
Chem. Eng. Data 2011. C. Petit, Y. Park, K.-Y A.
Lin, A.-H. A. Park, JPC-C 2012.
Effect of chain size (NOHM-I-PEG)
Swelling ratio at 60 oC PCO2 0.8-5.5 MPa
Delta swelling Rate of swelling at each CO2
loading level
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CO2 Capture Capacity Effect of Task-Specific
Functional Groups
Selectivity
Recyclability
Simulated flue gas (CO2, O2, N2)
K.-Y A. Lin, A.-H. A. Park, Environ. Sci.
Technol. 2011.
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Carbon Storage Schemes

• Ocean storage
• Biological fixation
• Geologic storage
• Mineral carbonation

• Mimics natural chemical transformation of CO2
• MgO CO2 ? MgCO3
• Thermodynamically stable product Exothermic
  reaction
• Appropriate for long-term environmentally benign
  and unmonitored storage

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Availability of Minerals
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Incongruent Dissolution of Silicate Minerals

• Challenges
• Slow dissolution kinetics of silicate minerals in
  nature
• Diffusion-limiting ash layer formation
• Highest reported conversion 9 (Gerdemann et
  al., 2007)

High Mg recovery (gt85 in lt1hr)
Mg-bearing mineral
Moderate Reaction Conditions 90C, pH 3.0 ,10-2
M Catalysts
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Chemical and Biological Catalytic Enhancement of
Weathering of Silicate Minerals as Novel Carbon
Capture and Storage Technology
Controlled Formation of Precipitated Magnesium
Carbonates

• No need for the solvent regeneration and CO2
  compression, straightforward MVA
• Alternative CO2 utilization option with improved
  economic feasibility

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Acknowledgements

• Current Former Group Members
• Seven Ph.D. students
• Three Post-Doctoral Researchers
• More than twenty Visiting Scholars Master
  students
• Sponsors (Current Past)
• National Science Foundation (CAREER, CBET,
  SEES-RCN)
• Department of Energy (CCS1, CCS2, MVA, ARPA-E)
• King Abdullah University of Science and
  Technology (KAUST-Cornell Center)
• ORICA Mining Services Ltd.
• POSCO (Fluidization, Biomass-to-H2)
• KIGAM
• CLIMAX GLOBAL ENERGY
• New York State Energy Research and Development
  Authority (NYSERDA)
• New York State Foundation for Science, Technology
  and Innovation (NYSTAR)
• Columbia University (Diversity Initiative, Earth
  and Engineering Center)
• U.S. Environmental Protection Agency STAR
  fellowship