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1
New Amine-Containing Membranes for CO2 Capture
Kai Chen, Yang Han, Witopo Salim, Zi Tong,
Dongzhu Wu and W.S. Winston Ho
William G. Lowrie Department of Chemical & Biomolecular Engineering
Department of Materials Science and Engineering
The Ohio State University, Columbus, Ohio, USA
The Carbon Management Technology Conference 2017 Houston, TX, July 17 – 20, 2017
2
Outline
• CO2 Capture from Flue Gas in Coal-
and/or Natural Gas-fired Power Plants
• CO2 Capture from <1% CO2
Concentration Sources, e.g.,
– Residual flue gas after the primary CO2 capture system
– Coal-mine gas streams
3
● Coal-fired power plants
40% of global CO2 emission
Remain as major energy supply
● Membranes for CO2 capture from flue gas
System compactness
Energy efficiency
Operational simplicity
Kinetic ability to overcome thermodynamic
solubility limitation
Introduction
4
Challenges and Goals
● High CO2 Permeance
Reduce Membrane Area
Thin Membrane Thickness Needed
● High CO2/N2 Selectivity
Provide High CO2 Purity
High Selective Membrane Material Needed
>700 GPU CO2 permeance and >140 CO2/N2
selectivity at 57oC To meet the DOE target < $40/tonne CO2 (2007 $)
𝑷𝑪𝑶𝟐=
𝑱𝑪𝑶𝟐
𝒑𝑪𝑶𝟐,𝒇 − 𝒑𝑪𝑶𝟐,𝒑
𝜶𝑪𝑶𝟐 𝑵𝟐 =𝑷𝑪𝑶𝟐
𝑷𝑵𝟐
5
Amine Polymer Layer Contains Mobile and Fixed Carriers: Facilitated Transport
CO2 CO2
Membrane
CO2+
CO2
CO2 CO2
Mobile
Carrier
Facilitated Transport
Feed Side Permeate Side
Non-Reacting
Gas: N2 N2
Physical Solution-Diffusion
Mobile
Carrier
CO2 Mobile
Carrier
CO2 Mobile
Carrier
6
Amine-Containing Polymer Membrane Structure
Non-woven fabric
Porous PES or PSf
Amine layer
Simplicity of Membrane for Low Cost
7
Amine Layer Composition
Fixed-site carrier:
Polyvinylamine (PVAm)
Mobile carrier:
Piperazine glycinate (PG)
O
NH2 O-
NHNH2+
NH2 NH2 NH2 NH2 NH2
Surfactant:
Sodium dodecyl sulfate (SDS)
Na+
CH3 O S
O
O
O-
8
High-Molecular-Weight PVAm
Synthesis
Polymer
Monomer
Conc.
(wt.%)
Initiator/Monomer
Weight Ratio
3 wt.%
Polymer
Solution
viscosity (cp)
Weight
Average MW
PVAm (a) 30 0.5/100 486 719,000
PVAm (b) 40 0.14/100 1,400 1,200,000
Lupamin® N/A N/A 50 340,000
• MW measured by Dynamic Light Scattering (DLS)
• Lupamin® contains ~66% sodium formate
9
a) High viscosity - Decrease coating solution concentration
- Allow for preparation of thinner membrane
- Improve adhesion to support – less defects
b) Low salt amount - Improve membrane stability
High-Molecular-Weight PVAm Synthesized
Viscosity:
3 wt.% commercial PVAm: 50 cp
3 wt.% high MW PVAm: 450 – 1950 cp
10
Composite Membrane Synthesized Selective Amine Polymer Layer on PES Support
Selective layer
Selective layer = 165 nm
PES support
11
Membrane Scale-up: Continuous Roll-to-Roll Fabrication Machine at OSU
Oven
Unwind
Roll
Coating
Knife
Rewind
Roll
12
𝒍 × 𝝆𝒅𝒓𝒚 = 𝟎. 𝟓 × 𝒄 × 𝝆𝒔𝒐𝒍 × 𝒍𝒈𝒂𝒑
Tuning Membrane Thickness
𝒍: dry membrane thickness (µm)
𝝆𝒅𝒓𝒚: density of dry membrane (g/cm3)
𝝆𝒔𝒐𝒍: density of coating solution (g/cm3)
c: total solid concentration of coating
solution (by weight)
𝒍𝒈𝒂𝒑: gap setting of coating knife (µm)
13
• A thinner thickness with a higher web speed for a
given coating solution supply rate
Coating Technique Modification: Insert
After Modification Before Modification
Substrate
Motion
Unwind
Roll
Coating Knife Coating Knife
Insert
Substrate
Motion
Unwind
Roll
14
Coating knife
assembly
configuration
Polymer
concentration
(wt.%)
Viscosity of
Coating
Solution
(cp)
Web
speed
(ft/min)
Selective
amine layer
thickness
(nm)
Insert with
1-inch flow
channel height a
1.8 870
3 175
4 135
5 115
2.4 940 3.25 210
3.5 195
3 1180 3.5 185
Insert with
2-inch flow
channel height a
1.5 690
1 230
2 165
4 135
1.8 870 2 220
3 155
3.4 1430 1.6 210
2 178
Thin 14”-Wide Amine Coatings on Substrates
a 2.5 mil of flow channel opening
15
Membrane Element Fabrication
Spiral-Wound Membrane Element Element Rolling Machine
Membrane Module
Sweep
Inlet
Sweep
Outlet
Feed Inlet
Feed Outlet
16
Good Membrane Module Stability Obtained
Wu et al., JMS in press (2017)
0
100
200
300
400
500
600
700
0
200
400
600
800
1000
1200
1400
1600
0 50 100 150 200
CO
2/N
2 s
ele
cti
vit
y
CO
2 p
erm
ea
nc
e (
GP
U)
Time (hour)
Simulated Flue Gas
16% CO2 + 64% N2 + 17%H2O +
3% O2 and 3 ppm SO2
Change
CO2 con.
17
Process Proposed for CO2 Capture from Flue Gas in Coal-Fired Power Plants
Air
2200 psia
CompressorCoal
Combustor
Membrane
Module 1
Membrane
Module 2
Vacuum
Pump
Treated
Flue Gas
Coal Feed
Air Stream
With CO2
Flue Gas
6% CO2
0.2 atm
20% CO2
*
• Proposed membrane process does not require cryogenic distillation (compared to competition)
* Air Sweep first used by MTR
1.4% CO2
>95% CO2
Ramasubramanian et al., JMS, 421-422, 299 (2012)
Amine
PEO
18
SO2 Polishing & Membrane Process
• Absorption into 20 wt% NaOH Solution – Polishing step based on NETL baseline document
• Estimated to be ~ $4.3/tonne CO2 (in 2007 $, 6.5% COE increase)
– Non-plugging, low-differential-pressure, spray baffle scrubber
– High efficiencies (>95%)
Baghouse
Air
2200 psi
Compressor
Membrane Module 1
Membrane Module 2
Vacuum
pump
Treated flue gasFGD
Primary Air Fans
Induced Fan Draft
Forced Fan Draft
Steam to Turbine
Feed Water
Coal Feed Bottoms Ash
PulverizedCoal
Boiler
SO2 Polishing
19
Techno-Economic Analysis
• Basis: In 2007 dollar • DOE target: $40/tonne CO2 set for 2025
• Include membrane module installation cost
• Also include 20% process contingency
• Membrane Results at 57oC • Amine-containing membrane with >140 selectivity
key for stand-alone membrane process
• Membrane process does not require cryogenic
distillation
• PEO-containing membrane with 2000 GPU CO2
permeance and 20 selectivity
20
0
50
100
150
200
250
300
350
400
200 400 600 800 1000 1200 1400
CO
2/N
2 S
ele
cti
vit
y
CO2 Permeance (GPU)
Scale-up amine/PES
Spiral-wound Module: Scale-up Amine/PES
Sprial-wound Module: Scale-up Amine/ZY/PES
Plate-and-frame Module: Scale-up Amine/PES
Lab Amine/PES
Lab Amine/Lab PES
Lab Amine/ZY/PES
Scale-up Amine/ZY/PES
Scale-up membrane
(14-inch wide)
Prototype module
(2.25” dia. by 14” long)
Composite Membranes Containing Amine Cover Layer: Simulated Flue Gas at 57oC
$40/ tonne CO2
$42/ tonne CO2
21
Process Proposed for CO2 Capture from <1% CO2 Sources
•Proposed membrane process does not require cryogenic distillation (compared to competition)
Membrane
Module 1
Membrane
Module 2
Vacuum
Pump 1
Vacuum Pump 2
<1% CO2
Feed Gas Treated Gas
Compressor
152 bar
>95% CO2
<0.1% CO2
0.2 atm
0.2 atm
Location of Proposed Technology in
Coal-fired Power Plant
22
Pulverized
Coal
Boiler
Coal
Feed Bottom Ash
Feed Water
Steam to
Turbine
Primary
Air Fans
Secondary
Air Fans
Primary
CO2
Capture
System
Baghouse
Induced
Draft Fans
FGD
Vacuum
Pump 2
Membrane
Module 1
Membrane
Module 2
Vacuum
Pump 1 Compressor
152 bar
<1% CO2
Feed Gas <0.1% CO2
Treated Gas
>95% CO2
Performance Improves as CO2 Conc. Reduces
100
300
500
700
900
500
750
1000
1250
1500
0 5 10 15 20 25
CO
2/N
2 s
ele
cti
vit
y
CO
2 p
erm
ea
nc
e (
GP
U)
Feed CO2 Concentration (%) 23
24
High-Level Techno-Economic Calculations
• Calculated Cost Results • 32.1 tonne/h of CO2 captured from 1% CO2 source
• $107.8 million bare equipment cost Membrane 34%, blowers and vacuum pumps 62%, others 4%
• 1.76 ¢/kWh (1.24 ¢/kWh capital cost, 0.22 ¢/kWh fixed cost,
0.26 ¢/kWh variable cost, and 0.04 ¢/kWh T&S cost) COE = 8.09 ¢/kWh for 550 MW supercritical pulverized coal power plant
• $302/tonne capture cost ($17.6/MWh × 550 MW/(32.1 tonne/h))
• 21.8% Increase in COE (1.76/8.09 = 21.8%)
• Basis: Membrane Results at 57oC • 982 GPU & 211 Selectivity for 1% CO2 concentration feed gas
• 806 GPU & 173 Selectivity for 20% CO2 concentration feed gas
• Include Membrane Module Installation Cost and 20% Process
Contingency
• In 2011 dollar: NETL Case 12 of Updated Costs (June 2011
Basis) for Selected Bituminous Baseline Cases
25
Effect of CO2 Permeance on Techno-economic Analysis Results
18
20
22
24
26
28
250
270
290
310
330
350
700 900 1100 1300 1500
CO
E i
nc
reas
e (
%)
Cap
ture
co
st
($/t
on
ne)
CO2 permeance (GPU)
CO2/N2 selectivity = 200
982 GPU
26
Summary • CO2 Capture from Flue Gas – High-Molecular-Weight PVAm Membrane Synthesized
– Composite Membranes Synthesized in Lab
+ ~800 GPU with >200 Selectivity at 57°C
– Membrane Scaled up Successfully
– Scale-up Membrane Promising for Meeting DOE Cost
Target of $40/tonne CO2 (in 2007 dollar) for 2025
• CO2 Capture from <1% CO2 Conc. Sources – Membrane showed 982 GPU with 211 CO2/N2 selectivity
obtained at 57oC using 1% CO2 concentration feed gas
+ 806 GPU with 173 selectivity obtained using 20% CO2
conc. feed gas due to carrier saturation phenomenon
– Performance improves as CO2 conc. reduces
– High-level techno-economic analysis conducted + Capture cost of ~$302/tonne CO2 (in 2011 $)
+ 21.8% increase in COE
27
Acknowledgments
Norman N. Li Richard Song – Nanoporous Membrane Support
José Figueroa – Strong Efforts & Helpful Inputs for CO2-Sel. Membranes
Yuanxin Chen Kartik Ramasubramanian Varun Vakharia Lin Zhao – CO2-Selective Membranes
BASF in Wyandotte, MI – Free PES Samples
Purolite Corporation, Bala Cynwyd, PA – Free Ion-Exchange Resin Samples
28
• U.S. Department of Energy - DE-FE0007632 and DE-FE0026919
• Ohio Development Services Agency - OER-CDO-D-15-09 for Continuous Membrane
Fabrication Machine
Acknowledgments for Financial Support