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Ryan P. Lively Yoshiaki Kawajiri, Matthew J. Realff, David S. Sholl, Krista S. Walton
Stephen J. DeWitt, Rohan Awati, Jongwoo Park, Eli Carter, Hector Rubiera Landa
Georgia Institute of TechnologySchool of Chemical & Biomolecular Engineering
Atlanta, GA 30332
Novel Process That Achieves 10 mol/kg Sorbent Swing Capacity in a Rapidly Cycled Pressure Swing Adsorption Process
Spinneret
Quench bath
Fiber collection50 m/minHollow fiber
sorbent spinning
Module make-up
Sorbent dispersed in polymer solution
AR Sujan, RP Lively et al., Ind. Eng. Chem. Res. 2018, 57(1)SJA DeWitt, RP Lively et al., Ann. Rev. Chem. Bio. Eng. 2018
Ryan P. Lively Yoshiaki Kawajiri, Matthew J. Realff, David S. Sholl, Krista S. Walton
Stephen J. DeWitt, Rohan Awati, Jongwoo Park, Eli Carter, Hector Rubiera Landa
Georgia Institute of TechnologySchool of Chemical & Biomolecular Engineering
Atlanta, GA 30332
Novel Process That Achieves 10 mol/kg Sorbent Swing Capacity in a Rapidly Cycled Pressure Swing Adsorption Process
Spinneret
Quench bath
Fiber collection50 m/minHollow fiber
sorbent spinning
Module make-up
Sorbent dispersed in polymer solution
AR Sujan, RP Lively et al., Ind. Eng. Chem. Res. 2018, 57(1)SJA DeWitt, RP Lively et al., Ann. Rev. Chem. Bio. Eng. 2018
Rapid thermal swing adsorption 3
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
Capital cost of RTSA system for NETL 550 MWe baseline: ~$1B
RP Lively, WJ Koros et al., Int. J. Greenhouse Gas Control 2012, 10(1)RP Lively et al., U.S. Patent 8,409,332 WJ Koros, U.S. Patent 8,658,041
Rapidly cycled pressure swing adsorption using MOFs 4
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 MOFs 5
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 Upt
ake
(mol
/kg)
Pressure (bar)
213 K
228 K
243 K
258 K
273 K
Pressure Swing AdsorptionΔP = 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
∆NC
O2 (
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
𝑝𝑝𝐶𝐶𝐶𝐶𝐶𝑎𝑎𝑎𝑎𝑎𝑎 = 2 𝑏𝑏𝑏𝑏𝑏𝑏𝑝𝑝𝐶𝐶𝐶𝐶𝐶𝑎𝑎𝑑𝑑𝑎𝑎 = 0.1 𝑏𝑏𝑏𝑏𝑏𝑏
Rapidly cycled pressure swing adsorption using MOFs 6
Cycle times of ~20 seconds are common for industrial RCPSA (>5x faster than RTSA)
J Park, RP Lively, DS Sholl, J. Mater. Chem. A. 2017, 5, 12258-12265
How to economically achieve these pressurized, sub-ambient conditions?
Enabling 10 mol/kg swing capacities via flue gas pretreatment 7
Air Liquide Sub-Ambient Membrane System
Key parameters: swing capacity & selectivity
Sub-Ambient Adsorption System
D Hasse, S Kulkarni et al., Energy Procedia, 2013, 37, 993-1003
MIL-101(Cr) emerged as a promising candidate 8
220 230 240 250 260 270 280
CO2/N2 0.14/0.86 mixture
Temperature (K)
PCO2,ads = 2.0 bar PCO2,des = 0.1 bar PCO2,des = 0.2 bar PCO2,des = 0.3 bar PCO2,des = 0.5 bar PCO2,des = 1.0 bar
220 230 240 250 260 270 2800
5
10
15
20CO2 single component
∆NC
O2 (
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
Low cost ligands (benzene dicarboxylate)Relatively low cost metal centers (chromium nitrate)Scale-up is straight forward (70% yield on large batches)Water stable
J Park, RP Lively, DS Sholl, J. Mater. Chem. A. 2017, 5, 12258-12265L Hamon, GD Weireled et al., J. Am. Chem. Soc. 2009, 131, 8775-8777
9
Manufacturing MIL-101(Cr) fiber sorbents
2 µm
~50 wt% MOF73-80 vol% MOF200 µm
10 µm
10
PressurizationFeed Blow-
downEvacuation
PSA separation of simulated flue gas mixtures
11
0 500 1000 1500
0.0
0.2
0.4
0.6
0.8
1.0
C/C
0
Time (Seconds)
He-273 CO2-273 CO2-263 CO2-253 CO2-243
-50 0 50 100 150 200 250 3000
20
40
60
80
100
Frac
tion
of G
as in
out
let (
%)
Time (Seconds)
N2 CO2
Simulated Evacuation (5 second Blowdown, then He sweep)
0 2 4 6-2
0
2
4
6
8
10
12
14
16
18
Bed
Pres
sure
(bar
)
Time (Hours)
PressurizationFeed Blow-
downEvacuation
PSA separation of simulated flue gas mixtures
Fiber sorbents were cycled in CO2/N2 for 4 weeks
(~4000 cycles)
12
0 200 400 600 800 1000
0
5
10
15
20
25
30
35
Pristine 99.5% Dry SO2
1000ppm Dry So2
Qua
ntity
Ads
orbe
d (m
mol
/g)
Absolute Pressure (mbar)
CO2 Isotherms on SO2 Exposed MIL-101(Cr)
Stability to acid gases
Fiber sorbents stable to aggressive acid gas
exposures
13
Tem
pera
ture
[K]
Issues with heat effects
50K increase in temperatureduring adsorption
Sorbent-loaded porous polymer
matrix
µPCM
Melt/Freeze
Sorption/desorptionenthalpy
Fiber Module
Phase Change Material
Impermeable microcapsule
SJA DeWitt, RP Lively et al., Ind. Eng. Chem. Res. 2018, 58(15)SJA DeWitt, RP Lively et al., PCT US18/48110; WO 2019/09908
14
Tem
pera
ture
[K]
Issues with heat effects
Sorbent-loaded porous polymer
matrix
µPCM
Melt/Freeze
Sorption/desorptionenthalpy
Fiber Module
Phase Change Material
Impermeable microcapsule
Tem
pera
ture
Enthalpy
ADSORPTION
DESORPTION
Concept of Phase Change Material for PSA Heat Management
SJA DeWitt, RP Lively et al., Ind. Eng. Chem. Res. 2018, 58(15)SJA DeWitt, RP Lively et al., PCT US18/48110; WO 2019/09908
15
“Passive” thermal management via microPCM capsules
SJA DeWitt, RP Lively et al., Ind. Eng. Chem. Res. 2018, 58(15)
16
0 200 400 600 800 1000
Time , [ s ]
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
Mol
ar fr
actio
n , [
- ]
CO2 breakthrough profiles , 100 sccm
“Passive” thermal management via microPCM capsules
17
“Passive” thermal management via microPCM capsulesMIL-101(Cr) at 243 K, cyclic steady state simulations
Inclusion of thermal modulation pushes Pareto front into the “attractive” zone for post-combustion CO2 capture
Process economics – from molecular models to PSA simulation to flowsheet analysis
10 -1 10 0 10 1 10 2 10 3 10 4
Concentration , [ mol / m 3 ]
10 -4
10 -3
10 -2
10 -1
10 0
10 1
10 2
Am
ount
ads
orbe
d , [
mol
/ kg
ads.
]
Nitrogen / SENWOZ , "in silico"
213 K
228 K
243 K
258 K
273 K
dual-site Langmuir fit
qsat1 = 1.705b1 = 2.451e-08B1 = 2140
qsat2 = 20.13b2 = 1.293e-05B2 = 862.7
10 -2 10 0 10 2 10 4
Concentration , [ mol / m 3 ]
10 -5
10 -4
10 -3
10 -2
10 -1
10 0
10 1
10 2
Am
ount
ads
orbe
d , [
mol
/ kg
ads.
]
Carbon dioxide / SENWOZ , "in silico"
213 K
228 K
243 K
258 K
273 K
tripleSiteLF fit
10 -1 10 0 10 1 10 2 10 3 10 4
Concentration , [ mol / m 3 ]
10 -4
10 -3
10 -2
10 -1
10 0
10 1
10 2
Am
ount
ads
orbe
d , [
mol
/ kg
ads.
]
Nitrogen / SENWIT , "in silico"
213 K
228 K
243 K
258 K
273 K
dual-site Langmuir fit
qsat1 = 2.041b1 = 3.538e-08B1 = 2044
qsat2 = 17.79b2 = 1.28e-05B2 = 912.8
10 -2 10 0 10 2 10 4
Concentration , [ mol / m 3 ]
10 -4
10 -2
10 0
10 2
Am
ount
ads
orbe
d , [
mol
/ kg
ads.
]
Carbon dioxide / SENWIT , "in silico"
213 K
228 K
243 K
258 K
273 K
tripleSiteLF fit
qsat1 = 13.75
b1 = 4.343e-06
B1 = 0.0006933
1 = 0.09992
qsat2 = 4.597
b2 = 6.154e-06
B2 = 1906
2 = 0.5396
qsat3 = 9.802
b3 = 6.759e-08
B3 = 3025
3 = 0.7413
…Prediction of binary
isotherms from CoreMOF database
0 0.2 0.4 0.6 0.8 1
Purity
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Rec
over
y UTEWOG_tripleSiteLF
0 0.2 0.4 0.6 0.8 1
Purity
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Rec
over
y SENWITPareto fronts from PSA optimizer
0 0.2 0.4 0.6 0.8 1
Purity
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Rec
over
y SERKEG_quadPlusL
0 0.2 0.4 0.6 0.8 1
Purity
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Rec
over
y WONZOP
18
…
Flowsheet optimization
for each material
19
A B C D E F G H I0
102030405060708090
100
82.6
Process economics – from molecular models to PSA simulation to flowsheet analysis
52.254.449.3
41.8
52.5
41.1
335.7
MIL-101(Cr)UiO-66
Cos
t of C
aptu
re ($
/tonn
e C
O2)
13X
122.3
75.94%
9.63%
14.44%
MOF Sorbent µPCM Fiber Manufacture
Fiber sorbent cost:
Total capex: $216M (25% of RTSA)
20
Accomplishments and outcomes
• Developed a “template” flowsheet for any sub-ambient pressure-driven CO2 capture process
• Created multi-scale workflow for process-driven material screening and selection for adsorption processes
• Scaled-up two different MOFs (MIL-101(Cr) and UiO-66) to >1 kg scale• Fabricated MOF fiber sorbents with integrated, passive thermal management• Constructed two PSA minipilot systems (~500 grams of CO2/day productivity)• Humid acid gas stability of MOFs, PSA, and fiber sorbents demonstrated• Capital and operating cost estimation for sub-ambient PSA CO2 capture
1. J Park, RP Lively, DS Sholl, ″Establishing upper bounds on CO2 swing capacity in sub-ambient pressure swing adsorption via molecularsimulation of metal-organic frameworks″, J. Mater. Chem. A 2017, 5, 12258-12265.2. J Park, JD Howe, DS Sholl, ″How Reproducible Are Isotherm Measurements in Metal-Organic Frameworks?″, Chem. Mater. 2017, 29, 10487-104953. SJA DeWitt, HO Rubiera Landa, Y Kawajiri, MJ Realff, RP Lively. “Development of Phase-Change-Based Thermally Modulated FiberSorbents”, Ind. Eng. Chem. Res. 2019, 58, 155, 768-57764. SJA DeWitt, A Sinha, J Kalyanaraman, F Zhang, MJ Realff, RP Lively. “Critical Comparison of Structured Contactors for Adsorption-BasedGas Separations” Annu Rev Chem Biomol Eng. 2018 Jun 7;9:129-152.5. SJA DeWitt, Y Kawajiri, HOR Landa, MJ Realff, RP Lively. “Incorporation of microencapsulated phase change materials into wet-spin dry jetpolymer fibers”. PCT US18/48110; WO 2019/099086. BR Pimentel, AW Fultz, KV Presnell, RP Lively, “Synthesis of water-sensitive metal-organic frameworks within fiber sorbent modules”, Ind.Eng. Chem. Res. 2017, 56, 17, 5070-5077
Papers and Patents
1 submitted, 5 to be submitted Fall 2019
Conclusions and perspectives 21
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., ~30 tonne CO2/tonne adsorbent-day)
220 230 240 250 260 270 2800
5
10
15
20CO2 single component
∆NC
O2 (
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
• 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 $40-$50/tonne CO2 at sequestration pressures may be achievable using these materials in this process concept, but significant work remains. Advantages of small size, material stability to flue gas conditions, and modularity are important.
22
https://lively.chbe.gatech.edu