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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
 Coal-fired Build Rate: China and United States
Source: http://www.netl.doe.gov/coal/refshelf/ncp.pdf 273 GW of
Undetermined Dates
90 of Chinese Plants
Results are Stacked

80
70
Capacity (GW)

60
50
40
30
20
10
0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016

Online Year
Planned no date
(evenly distributed
over 4 years)
16

Source: USA data - Ventyx – Velocity Suite (1/13/2012)

China data – Platts - UDI WEPPDB December 2011
Energy, Economic Growth and Quality of Life

EIA Data 2009

Source: http://www.netl.doe.gov/coal/refshelf/ncp.pdf
 Towards Sustainable Energy and Environment
Use domestic energy
sources to achieve energy Carbon
Wind ,
independence with
Hydro Hydrogen
environmental sustainability Geo Ethanol Chemicals

Recycled CO2
Nuclear Refining Methanol
DME
Synthesis Gasoline
Solar
Gas
Diesel
Fossil Jet Fuel

Biomass
Use carbon Municipal Electricity
neutral energy Solid Heat
Wastes
sources

Fossil fuels are fungible…

Integrate carbon capture, utilization
and storage (CCUS) technologies into
the energy conversion systems Stored CO2
Carbon Capture, Utilization and Storage Technologies (CCUS)

 Required characteristics for CCS

Utilization Capture Storage  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
(NETL, 2010)  High parasitic energy penalty
Solid Sorbents & Chemical Looping Technologies

Carbonation / Calcination cycle Oxidation / Reduction cycle

Water-Gas Shift: KIER’s 100kW CLC

CO + H2O  H2 + CO2 system (2006-2011)

MO + CO2  MCO3 MO + CO  M + CO2

Micro- vs. Mesopores MCO3  MO + CO2 M + H2O  MO + H2

e.g., ZECA process e.g., Chemical Looping process for H2 production

(Los Alamos National Lab) (Ohio State Univ.: U.S. Patent No. 11/010,648 (2004))
 Novel CO2 Capture Solvents (2011 & 2012 NETL CO Capture Technology Meeting)
2

 Ionic liquids  Carbonic Anhydrase (Enzyme)

 CO2BOLs
 Phase changing absorbents

 Liquid-like Nanoparticle Organic Hybrid Materials

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
 Design and Synthesis of liquid-like NOHMs
NOHM-I-HPE (or NOHM-I-PEG) NOHM-C-HPE and NOHM-C-MPE NOHM-C-HPE-POSS PEG
* POSS = Polyhedral Oligomeric Silsesquioxane

Ionic Covalent
NOHM-I-PEI NOHM-I-tPE “PEG”: polyethylene glycol

“PE”: polyetheramine

“PEI”: polyethyleneimine

“H”: high, “M”: moderate, and “t”: tertiary

Improved Thermal Stability Temp Swing from 20 ºC to 120/140 ºC

140ºC
NOHMs
120ºC

140ºC ~80%

Unbound polymer

120ºC
 Ordered and Frustrated Corona?
Pure Polymer NOHMs

: 1H ROE signal marker

canopy

Significant entanglement Less ROE signals AFM Images

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
 CO2 Capture Mechanisms
ATR FT-IR spectra of NOHMs + CO2 CO2 bending mode (2)
Polymer
CO2 in vapor
CO2 band
stretching
CO2
PCO2 = 3.5 MPa
Polymer bending
band

PCO2 = 3.5 MPa

 A loss of double degeneration of the CO2

bending mode (2) is observed upon
exposure to CO2
Lewis acid-base interactions
 This feature is related to the presence of
Lewis acid-base interactions between CO2
and the ether groups Si
O2

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
 CO2 “Packing” Behaviors

CO2 bending modes (NOHM-I-HPE)

Linear chains Branched chains

in-plane
out-of-plane

Ethomeen
3.3 chains/nm2
4.2 chains/nm2

Area ratio 2in-plane to 2out-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)
 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
Less groups along the polymer chains
swelling
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

NOHMs
Polymers

Delta swelling = Rate of

swelling at each CO2
loading level
CO2 Capture Capacity: Effect of Task-Specific Functional Groups

Amine

Amine

Selectivity Recyclability
CO2

+
Simulated flue gas
(CO2, O2, N2)
O2, N2

K.-Y A. Lin, A.-H. A. Park, Environ. Sci. Technol. 2011.

 Carbon Storage Schemes

Gas Processing Platforms

1 million tons of CO2
Utilization Capture Storage injected every year
since 2006

 Ocean storage CO2 Injection Well

 Biological fixation
Statoil’s Sleipner

 Geologic storage West Gas reservoir USD 100,000 saved

in the North Sea daily on CO2 tax

Graphic courtesy of Statoil

 Mineral carbonation (Geotimes, 2003)

In Salah Gas Project in Algeria

600,000 tons of CO2

injected every year
since 2004

 Mimics natural chemical transformation of CO2

MgO + CO2  MgCO3
Graphic courtesy of BP
(Geotimes, 2003)

 Thermodynamically stable product & Exothermic reaction

 Appropriate for long-term environmentally benign and unmonitored storage
 Availability of Minerals

Belvidere Mountain, Vermont

Serpentine Tailings
Mineral Carbonation of Peridotite

Basalt
Labradorite
Magnesium-based Ultramafic Rocks
(Serpentine, Olivine) Photo by Dr. Jürg Matter at LDEO (2008)
 Incongruent Dissolution of Silicate Minerals
Serpentine, Mg3Si2O5(OH)4 H+ 3 x10-7

Mg Reaction Rate
mol m-2 s-1
10-7 Catechol
+ 2H+ H+ & Oxalate
Oxalate
Catechol
Challenges: No Catalyst
10 -8
•Slow dissolution kinetics of silicate minerals
0.1 1 10 60
in nature Time (min) High Mg recovery
•Diffusion-limiting ash layer formation (>85% in <1hr)
100
Catechol
•Highest reported conversion: 9% (Gerdemann et

Mg Recovery (%)
80 & Oxalate
al., 2007)
Mg2+
60
2H+
Oxalate 40 Oxalate

20 Catecho
Mg-bearing
No Catalys
mineral
0
0 20 40 60
Time (min)

Catechol Moderate Reaction Conditions:

90°C, pH 3.0 ,10-2 M Catalysts
 Chemical and Biological Catalytic Enhancement of Weathering of
Silicate Minerals as Novel Carbon Capture and Storage Technology

Bio-catalyst
Industrial Make-up
CO2 sources Carbonic
Flue gas anhydrase (CA)
Bubble column
Chemical catalyst reactor with CA
Mg and Si-targeting CO2(g) + H2O  H2CO3
Chelating agents H2CO3  H+ + HCO3-
HCO3-  H+ + CO32-
Dissolution reactor
Serpentine CO32-(aq)
Mg3Si2O5(OH)4 + 6H+ 
3Mg2+ + 2Si(OH)4 + H2O Recycled
Carbonation reactor process
Mine water
Mg2+(aq) Mg2+ + CO32-  MgCO3
L/S separator

un-dissolved L/S separator Controlled Formation of

minerals silica Precipitated Magnesium Carbonates
MgCO3
Disposal (mine reclamation) Value-added products
(e.g., paper fillers, construction materials)

 No need for the solvent regeneration and

CO2 compression, straightforward MVA
 Alternative CO2 utilization option with
improved economic feasibility
 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