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Krista S. Walton
Yoshiaki Kawajiri, Matthew J. Realff, David S. Sholl, Ryan P. Lively
Stephen J. DeWitt, Rohan Awati, Jongwoo Park, Eli Carter, Hector Rubiera Landa
Georgia Institute of Technology
School of Chemical & Biomolecular Engineering
Atlanta, GA 30332
Enabling 10 mol/kg swing capacity in post-
combustion CO2 capture processes
BM Sanderson, BC O’Neill, C Tebaldi, Geophysical Research Letters 2017
RP Lively, MJ Realff. AIChE J. 2016
Adsorption (and membranes) are materials-enabled separations2
SH Pang, CW Jones et al., J. Am. Chem. Soc., 2017, 139, 3627-3630
Adsorption (and membranes) are materials-enabled separations3
Pressure (torr)
CO
2a
dso
rbe
d (
mm
ol/g
)
SH Pang, CW Jones et al., J. Am. Chem. Soc., 2017, 139, 3627-3630
Mmen-Co2(dobpdc)
Pressure (torr)
25°C
75°C
Adsorption (and membranes) are materials-enabled separations4
TM McDonald, JR Long et al., Nature, 2015, 519, 303-308
Pressure (torr)
CO
2a
dso
rbe
d (
mm
ol/g
)
SH Pang, CW Jones et al., J. Am. Chem. Soc., 2017, 139, 3627-3630
Connecting materials to engineering solutions—fibers lead the way5
WJ Koros, RP Lively. AIChE J. 2012, 58(9)
Connecting materials to engineering solutions—fibers lead the way6
2 µm
10,000 m2 / m3
module volume
Spinneret
Quench bath
Fiber collectionHollow fiber
sorbent spinning
Module
make-up
Sorbent dispersed in
polymer solution
WJ Koros, RP Lively. AIChE J. 2012, 58(9)
Connecting materials to engineering solutions—fibers lead the way7
10,000 m2 / m3
module volume
Spinneret
Quench bath
Fiber collectionHollow fiber
sorbent spinning
Module
make-up
Sorbent dispersed in
polymer solution
WJ Koros, RP Lively. AIChE J. 2012, 58(9)
Rapid thermal swing adsorption—amines/hollow fiber sorbents8
Mesoporous silica / PEI
Swing capacity and cycle time are
key for driving down capital costs of
adsorption-based CO2 capture
systems!
Key question: Can we increase swing
capacity by 10x and reduce cycle time by 5x
to dramatically drive down adsorbent costs?
Y Fan, CW Jones et al., Int. J. Greenhouse Gas Control 2014, 21, 61-71
Costs dominated by costs of adsorbent
Rapidly cycled pressure swing adsorption using MOFs9
Cycle times of ~20 seconds are common for industrial RCPSA (>5x faster than RTSA)
JM Simmons, T Yildirim et al., Energ. Env. Sci., 2011, 4(6), 2177-2185
Rapidly cycled pressure swing adsorption using MOFs10
Cycle times of ~20 seconds are common for industrial RCPSA (>5x faster than RTSA)
0.0 0.5 1.0 1.5 2.0 2.50
10
20
30
40
50
CO
2 U
pta
ke (
mol/kg)
Pressure (bar)
213 K
228 K
243 K
258 K
273 K
Pressure Swing Adsorption
ΔP = 1.9 bar
Sub-Ambient ΔNCO2
~ 40 mol/kg
210 220 230 240 250 260 270 2800
5
10
15
20
25
30
35
40
45
N
CO
2 (
mol/kg)
Temperature (K)
Pads = 2.0 bar
Pdes = 0.1 bar
Pdes = 0.2 bar
Pdes = 0.3 bar
Pdes = 0.5 bar
Pdes = 1.0 bar
J Park, RP Lively, DS Sholl, J. Mater. Chem. A. 2017, 5, 12258-12265
Rapidly cycled pressure swing adsorption using MOFs11
Cycle times of ~20 seconds are common for industrial RCPSA (>5x faster than RTSA)
𝑝𝐶𝑂2𝑎𝑑𝑠 = 2 𝑏𝑎𝑟
𝑝𝐶𝑂2𝑑𝑒𝑠 = 0.1 𝑏𝑎𝑟
J Park, RP Lively, DS Sholl, J. Mater. Chem. A. 2017, 5, 12258-12265
Enabling 10 mol/kg swing capacities via flue gas pretreatment12
Air Liquide Sub-Ambient Membrane System
Hollow fiber membrane
D Hasse, S Kulkarni et al., Energy Procedia, 2013, 37, 993-1003
Enabling 10 mol/kg swing capacities via flue gas pretreatment13
Air Liquide Sub-Ambient Membrane System
D Hasse, S Kulkarni et al., Energy Procedia, 2013, 37, 993-1003
Enabling 10 mol/kg swing capacities via flue gas pretreatment14
Air Liquide Sub-Ambient Membrane System
Key parameters: swing capacity & selectivity
Sub-Ambient Adsorption System
➢ DOE guideline: 90% CO2 removal from
flue gas
➢ Total heat integration with no external
cold (i.e., refrigerant) or hot (i.e., steam)
utility
➢ Costs between $35-$45/tonne CO2
➢ Parasitic loads of 18-30%D Hasse, S Kulkarni et al., Energy Procedia, 2013, 37, 993-1003
Enabling 10 mol/kg swing capacities: Potential MOF candidates15
0 1 2 3 4 50
2
4
6
8
10
12
14
16
18
Up
take
(m
mo
l/g
)
Pressure (bar)
223 K
233 K
243 K
253 K
263 K
273 K
HKUST-1 CO2 Isotherms
0 1 2 3 4 50
2
4
6
8
10
Up
take
(m
mo
l/g
)
Pressure (bar)
223 K
233 K
243 K
253K
263 K
273 K
UiO-66 CO2 Isotherm
0 1 2 3 4 50
5
10
15
20
25
30
Up
take
(m
mo
l CO
2/g
)
Pressure (Bar)
223 K
233 K
243 K
253 K
263 K
273 K
MIL-101(Cr) CO2 Isotherms
220 230 240 250 260 270 2800
5
10
15
20
CO2 single component
N
CO
2 (
mo
l/kg
)
Temperature (K)
Pads = 2.0 bar
Pdes = 0.1 bar
Pdes = 0.2 bar
Pdes = 0.3 bar
Pdes = 0.5 bar
Pdes = 1.0 bar
210 220 230 240 250 260 270 2800
1
2
3
4
5
6
7P
ads = 2.0 bar
Pdes
= 0.1 bar
UiO-66
UiO-66-NH2
UiO-66-(NH2)2
UiO-66-CH2NH
2
N
CO
2 (
mo
l/kg
)
Temperature (K)
210 220 230 240 250 260 270 2800
3
6
9
12
15
18
Cu-BTC
N
CO
2 (
mol/kg)
Temperature (K)
Pads = 2.0 bar
Pdes = 0.1 bar
Pdes = 0.2 bar
Pdes = 0.3 bar
[1] MJ Cliffe, AL Goodwin et al., Nature Comm, 2014, 5
[1] [3]
[3] L Hamon, GD Weireld et al., J. Am. Chem. Soc. 2009, 131, 8775-8777
[2]
[2] A Zukal, J Jagiello et al., Catal. Today 2015, 243, 69-75
UiO-66 HKUST-1 MIL-101(Cr)
Enabling 10 mol/kg swing capacities: Potential MOF candidates16
0 1 2 3 4 50
2
4
6
8
10
12
14
16
18
Up
take
(m
mo
l/g
)
Pressure (bar)
223 K
233 K
243 K
253 K
263 K
273 K
HKUST-1 CO2 Isotherms
0 1 2 3 4 50
2
4
6
8
10
Up
take
(m
mo
l/g
)
Pressure (bar)
223 K
233 K
243 K
253K
263 K
273 K
UiO-66 CO2 Isotherm
0 1 2 3 4 50
5
10
15
20
25
30
Up
take
(m
mo
l CO
2/g
)
Pressure (Bar)
223 K
233 K
243 K
253 K
263 K
273 K
MIL-101(Cr) CO2 Isotherms
220 230 240 250 260 270 2800
5
10
15
20
CO2 single component
N
CO
2 (
mo
l/kg
)
Temperature (K)
Pads = 2.0 bar
Pdes = 0.1 bar
Pdes = 0.2 bar
Pdes = 0.3 bar
Pdes = 0.5 bar
Pdes = 1.0 bar
210 220 230 240 250 260 270 2800
1
2
3
4
5
6
7P
ads = 2.0 bar
Pdes
= 0.1 bar
UiO-66
UiO-66-NH2
UiO-66-(NH2)2
UiO-66-CH2NH
2
N
CO
2 (
mo
l/kg
)
Temperature (K)
210 220 230 240 250 260 270 2800
3
6
9
12
15
18
Cu-BTC
N
CO
2 (
mol/kg)
Temperature (K)
Pads = 2.0 bar
Pdes = 0.1 bar
Pdes = 0.2 bar
Pdes = 0.3 bar
[1] MJ Cliffe, AL Goodwin et al., Nature Comm, 2014, 5
[1] [3]
[3] L Hamon, GD Weireld et al., J. Am. Chem. Soc. 2009, 131, 8775-8777
[2]
[2] A Zukal, J Jagiello et al., Catal. Today 2015, 243, 69-75
UiO-66 HKUST-1 MIL-101(Cr)
High stability
Low cost / high scalability
Low swing capacity
Low stability
Low cost / high scalability
High swing capacity
Good stability
Moderate cost
High swing capacity
Complexities of developing engineering solutions for post-
combustion CO2 capture (next 4 slides)
17
Scaling-up MOF contactors
• Synthesis
• Stability
• Etc.
Transport Limitations
• Heat effects
• Pressure drop
• Etc.
Contaminants
• Acid gases
• Water
• Etc.
Systems Engineering
• Optimized cycles
• Process Economics
• Etc.
Complexities: Scaling up MOF fiber sorbent contactors18
Spinneret
Quench bath
Fiber collectionHollow fiber
sorbent spinning
MOF
Module
make-up
UiO-66 or MIL-101(Cr)
dispersed in polymer
solution
Scale-up of MOFs—Inmondo Tech
Complexities: Scaling up MOF fiber sorbent contactors19
Spinneret
Quench bath
Fiber collectionHollow fiber
sorbent spinning
MOF
Module
make-up
UiO-66 or MIL-101(Cr)
dispersed in polymer
solution
3 μm
Unpublished data
Complexities: Scaling up MOF fiber sorbent contactors20
Spinneret
Quench bath
Fiber collectionHollow fiber
sorbent spinning
MOF
Module
make-up
UiO-66 or MIL-101(Cr)
dispersed in polymer
solution
3 μm
Unpublished data
Surface areas of fiber sorbents are
equivalent to (mass frac. MOF ) x
(MOF surface area)
Complexities: Scaling up MOF fiber sorbent contactors21
Peristaltic Pump
Swagelok®
Module
w/ fibers
Liquid Reservoir
Cu(NO3)2 BTC + Cu(NO3)2
ZnO (Zn, Cu)
HDSHKUST-1
Spinneret
Quench bath
Fiber collectionHollow fiber
sorbent spinning
ZnO
Module
make-up
ZnO dispersed in
polymer solution
BR Pimentel, RP Lively et al., Ind. Eng. Chem. Res. 2017, 56(17), 5070-5077
Complexities: Scaling up MOF fiber sorbent contactors22
Peristaltic Pump
Swagelok®
Module
w/ fibers
Liquid Reservoir
Spinneret
Quench bath
Fiber collectionHollow fiber
sorbent spinning
ZnO
Module
make-up
ZnO dispersed in
polymer solution
BR Pimentel, RP Lively et al., Ind. Eng. Chem. Res. 2017, 56(17), 5070-5077
∆𝑃 𝐿(𝑃𝑎/𝑐𝑚
)
Superficial velocity (cm/s)
Complexities: Transport Limitations23
Unpublished data
Te
mp
era
ture
Enthalpy
ADSORPTION
DESORPTION
Concept of Phase Change Material
for PSA Heat Management
∆𝑃 𝐿(𝑃𝑎/𝑐𝑚
)
Superficial velocity (cm/s)
Tem
pera
ture
[K
]
Complexities: Transport Limitations24
Sorbent-loaded
porous polymer
matrix
µPCM
Melt/
Freeze
Sorption/
desorption
enthalpy
Fiber Module
Phase Change
Material
Impermeable
microcapsule
Unpublished data
μPCM
UiO-6610 μm
Complexities: Transport Limitations25
Sorbent-loaded
porous polymer
matrix
µPCM
Melt/
Freeze
Sorption/
desorption
enthalpy
Fiber Module
Phase Change
Material
Impermeable
microcapsule
Unpublished data
μPCM
UiO-6610 μm
Complexities: Transport Limitations26
Unmodulated
0 100 200 300 400 500 600 700 800 900
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
Modulated Fibers
Unmodulated FibersF
ibe
r C
ap
acity (
mm
ol/g
)
Flow Rate (sccm)
Breakthrough Capacity at 5% leakage(238K, 16 bar)
Bre
akth
rough c
apacity
at 5%
le
akage (
mm
ol/g)
Unpublished data
9x
Unpublished data
Complexities: Contaminants and Stability27
Unpublished data
Complexities: Contaminants and Stability28
0 2 4 6
-2
0
2
4
6
8
10
12
14
16
18
Bed P
ressure
(bar)
Time (Hours)
Bed Pressure
Fiber sorbents were cycled in
CO2/N2 for 4 weeks (~4000
cycles)
Complexities: Cycle optimization and systems engineering29
Unpublished data
Complexities: Cycle optimization and systems engineering30
Unpublished data
Conclusions and perspectives31
Key question: Can we increase swing capacity by 10x and reduce cycle time by 5x to dramatically
drive down adsorbent costs?
• Combining RCPSA cycles with appropriate metal-organic frameworks in sub-ambient conditions
results in highly productive adsorption systems (i.e., tonne CO2/tonne adsorbent-day)
220 230 240 250 260 270 2800
5
10
15
20
CO2 single component
N
CO
2 (
mo
l/kg
)
Temperature (K)
Pads = 2.0 bar
Pdes = 0.1 bar
Pdes = 0.2 bar
Pdes = 0.3 bar
Pdes = 0.5 bar
Pdes = 1.0 bar
• Significant “real world” complexities exist, but hollow fiber sorbent platform provides solutions to
many of these (scalability, transport limitations, etc.)
• Costs in the range of $35-$45/tonne CO2 may be achievable using these materials in this
process concept, but significant work remains
Process Scope—Key Topics, BP3 (Jan 18-Dec 18)
Eight major activity areas for BP2: Task 15.0: Process flowsheet refinement —Ongoing, 80% complete
Task 16.0: Generate >250 g/quarter of UiO-66 and spin fibers —Ongoing, 80% complete
Task 17.0: Construct/test RCPSA system for dirty gas testing—Ongoing, 50% complete
Task 18.0: Model Validation for fiber module —Complete
Task 19.0: Monolithic Fiber sorbent stability in dirty gases —Ongoing, 25% complete
Task 20.0: Composite (PCM containing) fiber testing in sub-ambient PSA—Complete
Task 21.0: Sub-ambient Technical Feasibility Study —Ongoing, 50% complete
Task 22.0: Large module testing in sub-ambient PSA —Task Initiated this quarter
32
Collaborators and funding 33
Collaborators
• Yoshiaki Kawajiri (GT)
• Ryan Lively (GT)
• Matthew Realff (GT)
• David Sholl (GT)
• Eli Carter
Walton Lab 2018
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