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1 Carbon Dioxide Separations Using Polymer Membranes and Status of Carbon Capture Research in the United States Benny D. Freeman The University of Texas at Austin [email protected] http://membrane.ces.utexas.edu Symposium for Innovative CO 2 Membrane Separation Technology Molecular Gate Membrane Module Technology Research Association Tokyo, Japan November 4, 2011

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Page 1: Carbon Dioxide Separations Using Polymer Membranes … · Carbon Dioxide Separations Using Polymer Membranes and Status of Carbon Capture ... e coal-fired power plant. ... From D.W

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Carbon Dioxide Separations Using PolymerMembranes and Status of Carbon Capture

Research in the United StatesBenny D. Freeman

The University of Texas at [email protected]

http://membrane.ces.utexas.edu

Symposium for Innovative CO2 MembraneSeparation Technology

Molecular Gate Membrane Module TechnologyResearch Association

Tokyo, JapanNovember 4, 2011

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2

US Department of Energy Workshop

• Membrane section co-chaired byBenny Freeman and Sam Stupp.

• Complete report available at:

science.energy.gov/~/media/bes/pdf/reports/files/CCB2020_rpt.pdf

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Some Challenges Identified by DOE Workshop

• Enormous scale of carbon capture applications• 2x106 ft3 (56,633 m3) of flue gas at atmospheric pressure containing

< 15% CO2 released from 550 MWe coal-fired power plant.

• Current membranes are not permeable enough• 106 m2 of membranes required to capture 90% of CO2 from 550 MWe

coal-fired power plant.

• Current membranes limited by permeability/selectivity tradeoff relation,so one cannot prepare both high flux and high selectivity membranes.

• Current membranes may not have sufficient chemical/thermal stabilityfor some carbon capture applications.

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Priority Research Directions Identified by DOE Workshop

• Hierarchical Structures• Control 3D, asymmetric structure of matter using self-

assembly.• Use microelectronics lithographic technologies for preparing

ultra-high surface area, 3D (rather than 2D) membranes.

• Molecularly Tailored Membranes to Enhance SeparationPerformance

• Use either polymer or inorganic materials.• Design structures of controlled porosity with tailored

interactions with permeant (e.g., CO2) to provide both high fluxand high selectivity.

• Alternative Driving Forces and Stimuli-Responsive Materials• Is it possible to use driving forces other than pressure (e.g.,

light, electric or magnetic fields, etc.) to reduce energyrequirements for carbon capture?

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O

O

O8

O

O

OH7

polyethylene glycol diacrylate n=14 (PEGDA)

polyethylene glycol acrylate n=7 (PEGA7)

polyethylene glycol methyl ether acrylate: n=8 (PEGMEA8)Lin, H., Kai, T., et al. Macromolecules 38, 8381-93 (2005)Kalakkunnath, S., Kalika, D.S., et al. Macromolecules 38, 9679-87 (2005)

O

O

O14

O

Crosslinked Poly(ethylene oxide) (XLPEO)

10

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10-3

10-2

10-1

100

101

0 100 200 300 400

S[c

m3

(ST

P)/

cm3

atm

]

/ k [K]

He

H2

N2

O2

CH4

CO2

C2H

6

C3H

8

C4H

10

Block copolymer containing 57 wt% PEO and 43 wt% Nylon-6; 35oC, fromBondar et al., J. Polym. Sci., Part B: Polym. Phys., 37, 2463-75 (1999). 11

Ethylene Oxide-Based PolymersHave High CO2 Solubility

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Glass Transition of XLPEO

CH2 CH C

O

O CH2 CH2 OH[ ]7CH2 CH C

O

O CH2 CH2 OCH3[ ]8

PEGMEA: PEGA:

-70

-65

-60

-55

-50

-45

-40

-35

020406080100

Gla

ssT

ran

siti

on

Tem

per

atu

re[

oC

]

PEGDA Content [wt.%]

PEGDAPEGA7

PEGDAPEGMEA8

12

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CH2 CH C

O

O CH2 CH2 OH[ ]7

PEGA (monomer)

]13[ OCH2CH2O

O

CCHCH2 C

O

CH CH2

PEGDA (crosslinker)

CH2 CH C

O

O CH2 CH2 OCH3[ ]8

PEGMEA (monomer)

H. Lin, E. van Wagner, J.S. Swinnea, B.D. Freeman, S.J. Pas, A.J. Hill, S.Kalakkunnath, and D.S. Kalika, J. Membrane Sci., 276, 145-161 (2006).

Free Volume Characterized by PALS

3.1

3.15

3.2

3.25

3.3

3.35

020406080100

Rad

ius

of

Fre

eV

olu

me

Ele

men

ts[Å

]

PEGDA Content [vol.%]

PEGDA-co-PEGMEA

PEGDA-co-PEGA

13

I3 is approximately independent of composition.

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CO2/H2 Pure Gas Separation Properties

CH2 CH C

O

O CH2 CH2 OH[ ]7CH2 CH C

O

O CH2 CH2 OCH3[ ]8

5

10

15

020406080100In

fin

ite

Dilu

tio

nS

elec

tivi

ty

PEGDA Content [vol.%]

PEGDA/PEGA

PEGDAPEGMEA

PEGDA/H2O

CO2/H

2

Lin et al., Macromolecules, 38, 8381-8393 (2005) and 38, 8394-8407 (2005).

0

100

200

300

400

500

600

020406080100

Per

mea

bili

ty[b

arre

r]

PEGDA Content [wt.%]

PEGDA/PEGA7

PEGDA/PEGMEA8CO

2

14

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÷÷ø

öççè

æ-=

333

expI

BAP

t ÷øö

çèæ -=

FFVB

AP exp

Free Volume in PEGDA Copolymerswith PEGMEA and PEGA

4

5

6

7

8910

20

2 2.5 3 3.5 4

102

103

1000/

CO

2P

erm

eab

iltiy

[Bar

rer]

CO

2/H2

Sel

ecti

vity

[ns-3]

102

103

4

5

6

7

8910

20

7 8 9 10

1/FFVC

O2P

erm

eab

iltiy

[Bar

rer]

CO

2/H2

Sel

ecti

vity

15

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Mixed Gas Separation

10-1

100

101

102

10-2 10-1 100 101 102 103 104

CO

2/H2

CO2

Permeability [Barrer]

Upper Bound35oC

10oC

-20oC

PEGDA/PEGMEA-30H. Lin, E. van Wagner, B.D. Freeman, L.G. Toy, and R.P. Gupta, “Plasticization-Enhanced H2 Purification UsingPolymeric Membranes,” Science, 311, 639-642 (2006).

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Reduction to Practice

http://www.mtrinc.com/co2_removal_from_syngas.html

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1,000 gpu =100 Barrer (permeability)at 0.1 micron (thickness)

18

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Monomer to Enhance Permeability

V.A. Kusuma, B.D. Freeman, S.L. Smith, A.L. Heilman, & D.S. Kalika, “Influenceof Tris-based comonomer on structure and gas transport properties ofcrosslinked poly(ethylene oxide),” J. Membrane Sci., 359, 25-36 (2010).

TRIS-A

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V.A. Kusuma, B.D. Freeman, S.L. Smith, A.L. Heilman, & D.S. Kalika, “Influenceof Tris-based comonomer on structure and gas transport properties ofcrosslinked poly(ethylene oxide),” J. Membrane Sci., 359, 25-36 (2010).

CO2/N2 = 60 18

CO2 Permeability increasesabout 4.5x with TRIS-A content

Permeability/Selectivity Tradeoff

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TRIS-A Requires Toluene asCosolvent to Form Homogeneous

Solution – SiGMA Does Not

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CO2/N2 = 58 20

SiGMA Increases Permeability

Kusuma, V.A., G. Gunawan, Z.P. Smith, and B.D. Freeman, “Gas Permeability ofCross-Linked Poly(ethylene oxide) Based on Poly(ethylene glycol) Dimethacrylateand a Miscible Siloxane Comonomer,” Polymer, 51(24), 5734-5743 (2010).

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Summary

• Polar rubbery polymers exhibit interestingpermeation and selectivity characteristics for acidgas separations.

• End groups in the network are important. They cansignificantly influence chain motion and free volumeand, in turn, transport properties.

• Permeability is much higher in rubbery polymers thanin conventional glassy polymers.

• Polar rubbery polymers have been demonstrated forpost-combustion carbon capture.

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100

101

102

103

10-2 10-1 100 101 102 103 104

Glassy PolymersRubbery Polymers

H2 Permeability 1010 [cm3 (STP)cm/(cm 2 s cmHg)]

Upper Bound

H

2/N

2

The Upper BoundA/B=A/B/PA

A/B

33

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PA = SA x DA : Solution-Diffusion

DA = DoAexp(-EDA

/RT) : Activated Diffusion

lnDoA= a(EDA

/RT) - b : Linear Free Energy

EDA= cdA

2 - f : Strongly Size-Sieving

Results:

Theoretical Prediction of A/B and A/B

A/B=A/B/PAA/B

B.D. Freeman, Macromolecules, 32(2), 375 (1999).

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Comparison of Theory with Experimental Data

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Effect of Temperature on the Upper Bound

100

101

10-1 100 101 102

O2/N

2S

elec

tivi

ty

O2

Permeability (Barrer)

TBF PC-43-145 °C

-43°C

145 °C

UpperBound

TBF PC data from: Mollet al., US Patent5,352,272 (1994).

Rowe, B.W., L.M. Robeson, B.D. Freeman, and D.R. Paul, “Influence of Temperatureon the Upper Bound: Theoretical Considerations and Comparison with ExperimentalResults,” Journal of Membrane Science, 360, 58-69 (2010).

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Effect of Temperature on Solubility

From D.W. Van Krevelen, Properties ofPolymers, 3rd Edition (1997).

Results:

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100

101

102

103

104

10-1 100 101 102 103 104

CO

2/N2

Sel

ecti

vity

CO2

Permeability (Barrer)

200 K

250 K

300 K

350 K400 K

Predicted Effect of Temperature on the Upper Bound

Rowe, B.W., L.M. Robeson, B.D. Freeman, and D.R. Paul, “Influence of Temperatureon the Upper Bound: Theoretical Considerations and Comparison with ExperimentalResults,” Journal of Membrane Science, 360, 58-69 (2010).

• Diffusion selectivity decreaseswith increasing temperature.

• More soluble gas (CO2) is themore permeable gas.

• CO2 solubility decreases morewith increasing temperaturethan N2 solubility.

• Therefore, permeabilityselectivity decreases astemperature increases.

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10-2

10-1

100

101

102

10-2 10-1 100 101 102 103

H2/C

O2

Sel

ecti

vity

H2

Permeability (Barrer)

200 K250 K300 K350 K400 K

Predicted Effect of Temperature on the Upper Bound

• Diffusion selectivity decreaseswith increasing temperature.

• More soluble gas (CO2) is theless permeable gas.

• CO2 solubility decreases morewith increasing temperaturethan H2 solubility.

• Therefore, permeabilityselectivity increases astemperature increases,reflecting the competing effectsof solubility and diffusionselectivity.

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Comparison of Theory with Experimental Data

10-1

100

101

102

10-1 100 101 102

TBF PC230-418 K

O2

N2

Pre

dic

ted

per

mea

bili

ty(B

arre

r)

Experimental permeability (Barrer)

10-2

10-1

100

101

102

103

10-2 10-1 100 101 102 103

PBO A192-373 K

CO2

He

O2

N2

CH4

Pre

dic

ted

per

mea

bili

ty(B

arre

r)Experimental permeability (Barrer)

PBO A

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Summary

• Upper bound model can be extended to account foreffect of temperature.

• Reasonable agreement with experimental dataobtained with few additional parameters.

• Model provides a systematic mechanism to estimatedata at, for example, high temperature based on dataobtained at room temperature.

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THANK YOU!