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Electrochemically-Mediated Sorbent Regeneration
in CO2 Scrubbing Processes (FE0026489)
T. Alan Hatton
Ralph Landau Professor of Chemical Engineering
Director, David H. Koch School of Chemical Engineering Practice
Co-Director, MITEI Low Carbon Energy Center for CCUS
Massachusetts Institute of Technology, Cambridge MA 02139
Project Overview
Award Name: Electrochemically-Mediated Sorbent Regeneration in CO2 Scrubbing Processes
(FE0026489)
Funding:
DOE $1,202,052
Cost Share $ 310,601
Total $1,512,653
Project Period:August 1, 2017 – July 31, 2020
Project PIs: T. Alan Hatton, Howard Herzog
DOE Project Manager: Ted McMahon
Overall Project Objectives: Develop, characterize and implement electrochemically mediated
sorbent regeneration and CO2 release in amine scrubbing processes
2
Feed Gas
Lean Gas
CO2
Cooling Water
ProcessSteam
Amine
Amine + CO2
AbsorberT<60 °C
DesorberT>110 °C
Benchmark CO2 Capture Technology: Thermal Amine
3
HeatCool
CO2 Amine Amine/CO2 Complex
CO2
Amine
Electrochemically Mediated Amine Regeneration (EMAR)
4Plug and Play Efficient High Pressure Release✓ ✓ ✓
CO2 Amine Amine/CO2 Complex
Add M++
M2+
CO2
Amine/Meta
l
Complex
Remove M++
+-
Metal
Anode
Metal
Cathode
M2+
Feed Gas
Lean Gas
CO2
Amine
Amine+ CO2
AbsorberT<60 °C
DesorberT<60 °C
P = 5–10 bar
Feed Gas
Lean Gas
CO2
Cooling Water
ProcessSteam
Amine
Amine + CO2
AbsorberT<60 °C
DesorberT>110 °C
Electrochemically Mediated Amine Regeneration (EMAR)
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+-
Feed Gas
Lean Gas
CO2
Amine
Amine+ CO2
AbsorberT<60 °C
DesorberT<60 °C
EMAR Anatomy
6
• Cost
• Electrochemical transition happens within the aqueous stability window
• Metal ion has sufficiently strong binding to displace CO2 (amine specific!)
• Solubility
• Electrochemical kinetics
Se
lec
tio
n
Cri
teri
a
Effect of Copper on CO2 Loading
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EDATETAAEEA
2mols CO
mols N
2mols Cu4
mols N
T = 50oC , [Am] = 2N , 1M KNO3 , yCO2 = 0.15
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0 0.2 0.4 0.6 0.8 1
CO
2 L
oadin
g,
Copper Loading,
EDA
TETA
AEEA
0.0
0.50
1.0
1.5
2.0
2.5
EDA AEEA TETA
Moles of CO2 Released per Moles of Copper Added
2.04 1.95 1.84
M.C. Stern, F. Simeon, H. Herzog, T.A. Hatton, Energy and Environmental Science. 2013
Thermodynamic Cycle
Carnot Cycle EMAR Cycle
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Volume, V
Pre
ssu
re, P
State of Charge, Q (xCu)
Op
en C
ircu
it P
ote
nti
al, E
Thermodynamic Cycle
9Feed Gas
Lean Gas
CO2
Amine
Amine+ CO2
Thermodynamic Cycle
10Feed Gas
Lean Gas
CO2
Amine
Amine+ CO2 1
2
3
1
2
3
Thermodynamic Cycle
11Feed Gas
Lean Gas
CO2
Amine
Amine+ CO2 1
2
3
1
2
3
Total Work for EMAR Cell
12
0 0.2 0.4 0.6 0.8 1
Copper Loading Shift, xCu
0
10
20
30
40
50
Wo
rk (
kJ/m
ol)
EMAR Cell
Pump
Compressor
Total
Thermodynamic Results
Feed Gas
Lean GasCO2
13Thermodynamic minimum work of CO2 capture and compression to 150 bar of a 15% CO2 stream
Thermodynamic Results
Feed Gas
Lean GasCO2
14Thermodynamic minimum work of CO2 capture and compression to 150 bar of a 15% CO2 stream
Lowest
Capital
Expensive
Absorber
Expensive
Compressor
Anatomy of EMAR Cell
15
Scaling Up Electrochemical Systems
16
Experimental Demonstration of CO2 Release
17Liquid flow rate = 10mL/min
Process Automation
18
CO2 Release in Response to Applied Current
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0.0
2.0
4.0
6.0
8.0
10.0
0 0.1 0.2 0.3 0.4 0.5 0.6
CO
2 A
bsorb
ed (
mL/m
in)
Current (A)
Theoretical Max
Experiment
Cyclic Stability of EMAR Operations
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Series Geometry
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Series geometry
high voltage
low current
Anode
Ca
thode
V
stack= nV
cell
I
stack= I
cell
P = nV
cellI
cell
Copper Loading Effect on Current Density
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Anode (+)
Inlet
Cathode (-)
Inlet
[(CuIIAm2)2+]
(mol/L)]
Copper Loading Effect on Current Density
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Anode (+)
Inlet
Cathode (-)
Inlet
[(CuIIAm2)2+]
(mol/L)]
Series Experiments – Current Density
Theoretical Current Density (A/m2) Experimental Current Density (A/m2)
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• Change in the anodic reaction as CO2 loading drops or increased advection (diminishing
boundary layer resistance) caused by CO2 production in the anode.
• Parasitic side reactions (especially in the cathode) (e.g.,. formation of CuO).
EMAR Advantages
Electrochemical Thermal
Energy Consumption 15 – 40 kJ/mole 50-70 kJ/mole
Low temperature
OperationYes No
Ease of Deployment Plug-and-Play Expensive Retrofit
High Pressure
DesorptionYes No
Overpotentials for Electrochemical Reactions
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0 exp exp2 2
)(1F F
RT Ri i
T
In absence of CO2, formation of EDA complex does not significantly
hinder Cu deposition and dissolution. EDA Stabilizes Cu2+ in solution
Overpotentials for Electrochemical Reactions
27
In presence of CO2, kinetics are significantly hindered. However, chlorides were
observed to improve performance significantly.
EMAR Cathode
ideally operates in
absence of CO2
Effects of Supporting Electrolyte on Copper Reduction
28
NaCl NaNO3
Project Risks and Mitigation Strategies
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Technical Risks Probability Impact Risk Mitigation
CO2 sorbents and metal ion
systems unsuccessful
Medium Low Wide range of candidate sorbents
available. Initial results are
promising
Electrochemical cell models low in
fidelity and do not permit
optimization
Moderate Low Complexity of underlying
mechanisms in electrochemical
cell presents risk for modeling.
Parametric experiments will
generate sufficient data for
empirical optimization.
Process found to be too sensitive
for long-term operations and
disturbances
Moderate Moderate Preliminary testing is encouraging.
Degradation of electrodes or
sorbents possible, but can be
mitigated through design of
electrode configurations
Resource and Management Risks
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Resource Risks Probability Impact Risk Mitigation
Cost of bench-scale system after
optimization more expensive than
planned
Low Low Most of the components of the
system have been procured and
operated in previous work, but the
optimized system might involve
more expensive equipment,
especially for automation.
Management Risks Probability Impact Risk Mitigation
Process performance reaches a
plateau that does not satisfy DOE
research goals
Moderate High The progress reports will allow the
project team to evaluate the
performance of the process and
determine whether it is possible to
explore new dimensions for
performance improvements.
Experimental Design and Work Plan
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Task SubTask
Evaluate and Test CO2 Sorbents and Metal Ions for
Electrochemical Regeneration
• Identify and Shortlist Candidate Molecules
• Thermodynamic and Kinetic Experiments on Candidate
Molecules
• Cycling Stability Experiments on Candidate Molecules
Process Modeling and Cost Estimation • Develop process model and evaluate pressure effects
• Develop cost estimates
Electrochemical Cell Model Development • Establish kinetics and mass transfer model
• Model validation
Flow Channel Design and Optimization • Model-aided design of candidate flow channels
• Construction and testing of candidate flow channel
configurations
Optimization of Electrode Configuration and Cell
Architecture
• Evaluation of different electrode materials
• Evaluation of cell architectures
Evaluation of Optimized Chemistries and Cell
Designs
• Design and build instrumented lab-scale apparatus
• Testing of candidate systems under wide operating
conditions
• Stability testing
Budget
Period
1
2
3
Acknowledgements
3232
Mike Stern Aly Eltayeb Miao WangRyan Shaw
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