Ah-Hyung Alissa ParkDepartments of Earth and Environmental Engineering & Chemical Engineering

Lenfest Center for Sustainable Energy

Columbia University

ULTRA

August 9th, 2012

지속가능 에너지를 위한 탄소 포집지속가능 에너지를 위한 탄소 포집 , , 이용 및 저장기술이용 및 저장기술

Towards Sustainable Energy :Towards Sustainable Energy :

CCarbon arbon CCapture, apture, UUtilization and tilization and SStoragetorage

Coal-fired Build Rate: China and United StatesC

apac

ity

(GW

)

90

Results are Stacked

273 GW of Undetermined Dates

of Chinese Plants

80

70

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

Source: http://www.netl.doe.gov/coal/refshelf/ncp.pdf

Energy, Economic Growth and Quality of Life

Source: http://www.netl.doe.gov/coal/refshelf/ncp.pdf

EIA Data 2009

Towards Sustainable Energy and Environment

Gas

Synthesis

Refining

Use domestic energy sources to achieve energy independence with environmental sustainability

Use carbon neutral energy

sources

Integrate carbon capture, utilization and storage (CCUS) technologies into the energy conversion systems

HeatElectricity

Carbon

HydrogenChemicalsEthanol

Methanol

DME

Gasoline

DieselJet Fuel

Wind ,Hydro

Geo

Nuclear

Solar

Fossil

Biomass

Municipal Solid

Wastes

Recycled CO2

Stored CO2

Fossil fuels are fungible…

Carbon Capture, Utilization and Storage Technologies (CCUS)

Carbon Capture Technologies

CaptureUtilization Storage

Required characteristics for CCS Capacity and economic feasibility

Environmental benign fate

Long term stability

MEA Challenges Corrosion and solvent degradation

High capital and operating costs

High parasitic energy penalty

(NETL, 2011)

(NETL, 2010)

Solid Sorbents & Chemical Looping Technologies

Water-Gas Shift: CO + H2O H2 + CO2

Carbonation / Calcination cycleCarbonation / Calcination cycle Oxidation / Reduction cycleOxidation / Reduction cycle

MO + CO2 MCO3

MCO3 MO + CO2

MO + CO M + CO2

M + H2O 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

Novel CO2 Capture Solvents (2011 & 2012 NETL CO2 Capture Technology Meeting)

Ionic liquids

CO2BOLs

Liquid-like Nanoparticle Organic Hybrid Materials Liquid-like Nanoparticle Organic Hybrid Materials

Carbonic Anhydrase (Enzyme)

Phase changing absorbents

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-I-PEI NOHM-I-tPE

NOHM-C-HPE-POSS* POSS = Polyhedral Oligomeric Silsesquioxane

Ionic Covalent

PEG

“PEG”: polyethylene glycol

“PE”: polyetheramine

“PEI”: polyethyleneimine

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

~80%

Unbound polymer

NOHMs120ºC

120ºC

140ºC

140ºC

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

Ordered and Frustrated Corona?

Y. Park, J. Decatur, K.-Y A. Lin, A.-H. A. Park, PCCP 2011

2D ROESY (Rotating-frame Overhauser Effect SpectroscopY) NMR

This technique enables identification of through-space interactions (presence of off-diagonal peaks)

Less ROE signals AFM Images

TEM Images

Pure Polymer NOHMs

Significant entanglement

: 1H ROE signal markercanopy

CO2 Capture Mechanisms

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

SiO2

O=C=O

O=C=O

O=C=O

Lewis acid-base interactions

CO2 bending mode (2)

CO2 in vapor

PCO2 = 3.5 MPa

PCO2 = 3.5 MPa0

− 55

bar

CO2

stretchingCO2

bending

Polymerband

Polymerband

A loss of double degeneration of the CO2 bending mode (2) is observed upon exposure to CO2

This feature is related to the presence of Lewis acid-base interactions between CO2 and the ether groups

ATR FT-IR spectra of NOHMs + CO2

CO2 “Packing” Behaviors

CO2 bending modes (NOHM-I-HPE)

in-planeout-of-plane

Ethomeen

3.3 chains/nm2

4.2 chains/nm2

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)

SO3-H+

SO3-H+

+H-O3S SO3-H+

SO3-H+

SO3-H+

+H-O3S

SO3-H+

SO3-H+

+H-O3S

+H-O3S

+H-O3S

SiO2

SiO2 SiO2

4 5

NH2 N

H3CO

ONH2

R6 35

N(CH2CH2O)yH

(CH2CH2O)xHR

R=H, or CH3 (ratio: 31:10)

2

x+y=15, R=C18H37

31

Linear chains Branched chains

Area ratio 2in-plane to 2

out-of-plane provides insight into CO2 “packing”

behaviors in NOHMs

CO2-induced Swelling

NOHMs vs. polymer (NOHM-I-HPE)

Less 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.

Swelling ratio at 60 oC & PCO2 = 0.8-5.5 MPa

Polymers

NOHMs

Effect of chain size (NOHM-I-PEG)

Delta swelling = Rate of

swelling at each CO2

loading level

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

CO2 Capture Capacity: Effect of Task-Specific Functional Groups

Amine

Amine

CO2

O2, N2

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

+ Simulated flue gas

(CO2, O2, N2)

Selectivity Recyclability

Carbon Storage Schemes

CaptureUtilization Storage

Mimics natural chemical transformation of CO2

MgO + CO2 MgCO3

Thermodynamically stable product & Exothermic reaction

Appropriate for long-term environmentally benign and unmonitored storage

Ocean storage

Biological fixation

Geologic storage

Mineral carbonationMineral carbonation

CO2 Injection Well

Gas Processing Platforms

1 million tons of CO2

injected every year since 2006

USD 100,000 saved daily on CO2 tax

Graphic courtesy of Statoil(Geotimes, 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(Geotimes, 2003)

Availability of Minerals

BasaltLabradorite

Magnesium-based Ultramafic Rocks (Serpentine, Olivine)

Mineral Carbonation of Peridotite

Photo by Dr. Jürg Matter at LDEO (2008)

Belvidere Mountain, Vermont

Serpentine Tailings

Incongruent Dissolution of Silicate Minerals

Catechol

Serpentine, Mg3Si2O5(OH)4

+ 2H+H+

H+

Moderate Reaction Conditions: 90°C, pH 3.0 ,10-2 M Catalysts

Challenges:

•Slow dissolution kinetics of silicate minerals in nature

•Diffusion-limiting ash layer formation

•Highest reported conversion: 9% (Gerdemann et al., 2007)

2H+

Oxalate

Mg2+

Mg-bearing mineral

High Mg recovery (>85% in <1hr)

Chemical and Biological Catalytic Enhancement of Weathering of Silicate Minerals as Novel Carbon Capture and Storage Technology

SerpentineDissolution reactorMg3Si2O5(OH)4 + 6H+ 3Mg2+ + 2Si(OH)4 + H2O

MgCO3

Mg2+(aq)

Flue gas

un-dissolved minerals

Carbonation reactorMg2+ + CO3

2- MgCO3

CO32-(aq)

Bubble column reactor with CA

CO2(g) + H2O H2CO3

H2CO3 H+ + HCO3-

HCO3- H+ + CO3

2-

L/S separator

L/S separator

Recycled process water

silica

Industrial CO2 sources

Mine

Value-added products (e.g., paper fillers, construction materials)

Disposal (mine reclamation)

Bio-catalystMake-up Carbonic

anhydrase (CA)

Chemical catalystMg and Si-targeting Chelating agents

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

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

Acknowledgements