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Evaluation of amine-incorporated porous polymer networks (aPPNs) as sorbents for post combustion CO2 capture
DOE AWARD NUMBER: DE-FE0026472
08/14/2018 1
Project Overview
2
Research Team• Principle Investigator: Dr. Hong-Cai
“Joe” Zhou• Industrial partners: Koray “Ray”
Ozdemir (framergy)• Team leaders: Jeremy Willman,
Gregory Day• Team members: Elizabeth Joseph,
Hannah Drake, Xinyu Yang, Jialuo Li, Zachary Perry
• Past Members: Dr. Lanfang Zou, Dr. Mathieu Bosch, Dr. Xuan Wang, Dr. Yujia Sun, Dr. Ning Huang
Outline
• Introduction• Objectives• Porous Polymer Networks• PPN-151-DETA
• Sorbent Scale-up• Improving 250 g synthesis• Evaluation of Washing procedure• 1 kg reactor design and scale-up
• Remaining Tasks
3
Project Objectives
• A scalable highly-robust and highly-efficient sorbent that can be delivered and validated through lab-scale testing
• A sorbent that will be economically feasible to scale-up and use in commercial carbon capture processes
• An ideal sorbent for post-combustion CO2 capture that will approach the goal of 90% CO2 capture rate with 95% CO2 purity at a cost of electricity 30% less than baseline capture approaches
4
NH
NH2
NH
N NH2
NH2
NH
HN NH2
NH
HN N
HNH2
(PPN-6-CH2EDA)
(PPN-6-CH2DETA)
(PPN-6-CH2TETA)
(PPN-6-CH2TAEA)
R:CH2R
RH2C
PPN-6-R
Amine-decorated Porous Materials
• Porous Polymer Networks (PPNs)
A. M. Fracaroli, H. Furukawa, M. Suzuki, M. Dodd, S. Okajima, F. Gándara, J. A. Reimer, O. M. Yaghi, J. Am. Chem. Soc., 2014, 136, 8863-8866.McDonald, T. M.; Long, J. R., Nature 2015, 519 (7543), 303-308.Lu, W.; Sculley, J. P.; Yuan, D.; Krishna, R.; Wei, Z.; Zhou, H.-C., Angew. Chem. Int. Ed. 2012, 51, 7480. 5
Initial PPN Candidate Materials
6
Si
Si
Si
Si
Si
Si
HO OH
OH OHHO
OH
OH
HO OHOH
HO OH
OH
OHHO
Si
CHO
CHO
OHC
OHC
Dioxane/HCl(aq)
100 °C
PPN-60
Br
BrBr
BrBr
Br
alkylamine,
90°C, 48hr
PPN-200-EDAPPN-200-DETAPPN-200-TETAPPN-200-TAEA
Zou, L. et al. CrystEngComm. 2017
Yang, X. et al., Polymer. 2017
NH
N
N
N
NHHN
NH
N
N
N
HNHN
NH
N
N
N
NHN
hexanes
NH2
HN
NH2
NH2
NH
H2N
N
NH
N
HH
H
H
H
NH2N
N N
NH2
H2NNH
N
N
N
HNHN
NH
N
N
N
HNHN
NH
N
N
N
HNHN
DMSO
150°C, 72hr +
PPN-151-DETA
Cyanuric Acid (CA)
7
OHN
N N
OH
HOPPN-151
PPN-151-DETA
+
Tan, M. X., et al. ChemSusChem. 2013, 6, 1186
O
HH+
Diethylenetriamine (DETA)
CA CA
PPN-151 Porosity Measurements
8
0
200
400
600
800
0 0.2 0.4 0.6 0.8 1
Qua
ntity
Ads
orbe
d (c
m3 /
g ST
P)
Relative Pressure (P/P0)
N2 Isotherm PPN-151-DETA
0
0.005
0.01
0.015
0.02
0 50 100 150 200 250 300 350
DV/d
wPo
re V
olum
e (c
m3 /
g*Å)
Pore Width (Å)
PPN-151-DETA BJH Pore Size Desorption
BET SA (m2/g) Pore Volume (cm3/g) Average Pore Size (Å)
804 0.784 67.3
0
2
4
6
8
10
12
14
16
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33
CO2
Adso
rptio
n (w
t%)
Cycle Number
PPN-151-DETA CO2 wet gas cycling
PPN-151-DETA Fixed-bed Testing Long-term Wet Cycling
9
0.5
1
1.5
2
2.5
80 90 100 110 120
Rege
nera
tion
Ener
gy
Dem
and
(kJ •
g-1CO
2
Regeneration Temperature (°C)
Regeneration Energy Demand
Regenerative Energy Demand
• Heat of adsorption at 150 mbar CO2 and 40°C:
• PPN-151-DETA: 1.40 MJ/kg CO2
• Heat capacity increases exponentially with higher temperatures
• Regenerative energy demand at 85°C
• PPN-151-DETA: 1.8 MJ/kg CO2
(Typical MEA process: 3.8 MJ/kg CO2)
10
00.5
11.5
22.5
33.5
80 90 100 110 120Heat
Cap
acity
(J•g
-1•°
C-1)
Temperature (°C)
Sorbent Heat Capacity
250 g Scale-up
• The team utilized framergy’s 10 L jacketed solvothermal reactors to scale-up the sorbent synthesis to >250 g
• ~250 g of the sorbent was produced
11
Parameter ValueTemperature 150°CTime 5 dayHeadspace ~80%Melamine 201.62 gParaformaldehyde 108.00 gCyanuric acid 15.48 gDimethyl Sulfoxide (DMSO) 2080 mLBET surface area (m2/g) 500
The Importance of Formaldehyde Morphology
12
Granular form slows down dissolution, causing inhomogeneity in the polymer and reducing the overall surface area
The initial 250 g syntheses had low BET surface areas and showed a high degree of inhomogeneity
Initial 250 g batch utilizing granular paraformaldehyde
250 g batch utilizing powdered paraformaldehyde
Comparison of BET Surface Area Through Scale-Up
13
0100200300400500600700800900
1000
BET
Surf
ace
Area
(m2 /
g)
BET Surface Area of PPN-151
15 g(avg of 5 runs)
250 g
Granular CH2O
9-d
Top
5-d
7-d
9-d
bott
om
Powder CH2O
250 g Scale-up: Processing
• framergy’s Nutsche filter system utilized to wash sorbent (acetone, THF, DCM, methanol)
• For 250 g batch wash with 4 L of each solvent
• Solvent Exchange (heat to 60°C in sealed Nutsche filtration device for 12 hr while agitating) twice with methanol
• Additional 4 L
14
Reducing Solvent Washing: Improving Cost of Processing Steps
15
0
100
200
300
400
500
600
700
800
900
1000
*Full Wash Acetone THF DCM MeOH MeOH x1 MeOH x2
BET
Surf
ace
Area
(m2 /
g)BET Surface Area of Washed PPN-151
Solvent ExchangeWash
1 kg Scale-Up Reactor
16
1 kg Scale-up at Vapor Point
17
Reaction Set-up PPN Removal
Parameters and Performance of 1 kg Batch
18
0
100
200
300
400
500
0 0.2 0.4 0.6 0.8 1Qua
ntity
Ads
orbe
d (c
m3 /
g ST
P)
Relative Pressure (P/P0)
1 kg batch of PPN-151
02468
10121416
1 2 3
CO2
Upt
ake
(wt%
)
Cycle Number
1 kg PPN-151-DETA Wet Gas Breakthrough Runs
100 mL column cycling
19
• Previous Lab scale wet gas testing performed using a 5 mL column
• Long-term cycling tests will be done with 100 mL column
• Multiple thermocouples will inform us on temperature gradients
• Manual testing resulted in non-uniformity of runs.
• Tests will need to be repeated upon instrument repair
02468
10121416
1 2 3 4 5 6 7 8 9 10CO
2Ad
sorp
tion
(wt%
)Cycle Number
Remaining Tasks
• Final cycling tasks require the fabrication of 1.5 L adsorber:• 400 mm double walled column, adsorber stand, heat insulation, larger mass
flow controller and upgrade kit for software integration
• Instrument Manufacturer, Quantachrome Instruments, was recently bought out by Anton Paar USA Inc. delaying fabrication
• DynaSorb BT has also been shipped back for upgrades and repairs
20
Summary
• PPN-151-DETA can achieve > 0.1 g/g CO2 loading at large scale• Parameters that have been ignored during lab scale testing can have a large impact
on polymer porosity
• 1 kg synthesis performed in partnership with framergy and Vapor Point• 1 kg batch shows > 0.12 g/g CO2
• Final cycling tests will be performed• 1.5 L adsorber column has been ordered from Anton Paar
21
Acknowledgement and Disclaimer
• Acknowledgment: "This material is based upon work supported by the Department of Energy under
Award Number DE-FE0026472."
• Disclaimer: "This report was prepared as an account of work sponsored by an agency of the United States
Government. Neither the United States Government nor any agency thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy,
completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that
its use would not infringe privately owned rights. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constituteor imply its endorsement, recommendation, or favoring by the United States Government or any agency
thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the
United States Government or any agency thereof."
22
Acknowledgements
23
Publications• W. M. Verdegaal, K. Wang, J.
P. Sculley, M. Wriedt and H.-C. Zhou. ChemSusChem, 2016, 9, 636-643.
• Li, H.; Wang, K.; Feng, D.; Chen, Y.-P.; Verdegaal, W.; Zhou, H.-C., ChemSuschem, 2016, 9, 19, 2832-2840.
• Zou, L.; Yang, X.; Yuan, S.; Zhou, H.-C. CrystEngComm,2017.
• Huang, N.; Day, G.; Yang, X.; Drake, H.; Zhou, H.-C. Science China Chemistry, 2017.
• Yang, X.; Zou, L.; Zhou, H.-C. Polymer, 2017.
• Zou, L.; Sun, Y.; Che, S.; Yang, X.; Wang, X.; Bosch, M.; Wang, Q.; Li, H.; Smith, M.; Yuan, S.; Perry, Z.; Zhou, H.-C. Advanced Materials, 2017
• Framergy• Ray Ozdemir
• Vapor Point• Ken Mattheson
• DOE NETL • Project Manager - Andrew Jones