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Polymeric Membranes for Gas

Separation
- A brief overview of material development
iCap workshop, Beijing
Professor May-Britt Hgg
Dr. Qiang Yu
Norwegian University of Science and Technology
Faculty of Science and Technology / Dep. of Chem. Eng.

Outline of presentation
Polymers the standard trade-off line
Modified polymers (PIMs, TR, block-copolymers)
Facilitated transport membranes
Mixed matrix membranes (microporous and nanoparticle fillers)
Carbon membranes
Other relevant for the membrane development

Polymers the upper bound

Polymeric membranes - Common polymers

More than 1000 glassy and rubbery polymers for

gas permeation properties
Note: The upper bound relationship will change
depending on operating temperature of
process and chemical stability of material
Robeson, L. M. J Membr Sci 2008, 320, (1-2), 390-400

Transport mechanism
Solution-diffusion
Free-volume

P SD
P Ap exp(

B
)
FFV

Modified polymers

Polymeric membranes - PIMs

Repeat unit of PIM-1

spirobisindane based plymer
Picture: Compliments of NRC Canada

Polymers of intrinsic microporosity (PIMs)

Relatively high gas permeability,
Large inner surface area
Large free volume
Great sorption capacity!
Budd, P. M., et.al, Adv Mater 2004, 16, (5), 456-459
Budd, P. M., et.al, J Membr Sci 2008, 325, (2), 851-860
Thomas, S., et. al, J Membr Sci 2009, 333, (1-2), 125-131
Ahn, J., et. al, J Membr Sci 2010, 346, (2), 280-287
Pinnau, I, et al.,ACS symposium series 876, ACS 2004 167-176

Polymeric membranes - TR polymers

TR polymers, an example*

Possible chain conformation of TR

polymers derived from PIOFG
(PolyImides with Orthopositioned Functional Groups)

Full conversion assumed at 450 C fully amorphous

*Park, H.B. et al J Membr Sci 2010, 359, (1-2), 11-24

Benzoaxole ring PBO

Polymeric membranes - TR polymers

Industrial
applicability

2008
1991

Thermally rearranged (TR) polymers

High chemical, thermal stability
High free volume:high permeability
Size-sieving: good selectivity
Park, H. B., et al. Science 2007, 318, (5848), 254-258
Robeson, L. M. J Membr Sci 2008, 320, (1-2), 390-400
Park, H. B., et. al. J Membr Sci 2010, 359, (1-2), 11-24

Polymeric membranes block-copolymers*

Block co-polymers contain a soft and a

hard segment in the given example,
also blended with a PDMS-PEG
additive

*Reijerkerk, S.R., Wessling, M.,

Nijmeijer K. , J Membr Sci, 2011
(378) 479-484

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Facilitated transport membranes

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Facilitated transport membranes; general

Several types are available:
Ion-exchange resins
Hydrophilic polymers with CO2-reactive
salts
Polyelectrolytes
Biomimetic membranes
Fixed-site carriers (FSC)
The category blue above, contains a
mobile carrier that can react with CO2 and
diffuse across the membrane typically a
supported liquid membrane (SLM)
In the fixed-site carrier the CO2-reactive
functionality is attached to the polymer
backbone, and the CO2 rather hops from
site-to-site

Ref.: M. Mulder, 1996

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1) Separation by solution-diffusion
partial pressure driven
2) Carrier added reaction driven

Ji

Di
D
ci ,0 ci ,l ic cic,0 cic,l

l
l

CO2/N2 selectivity

Fixed-site-carrier membrane an example, PVAm*

250
240
230
220
210
200
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
40

50

60

70

80

90

100

Relative humidity, %

Support structure: polysulfone

Crosslinked membrane: PVAm, l ~1m)
Facilitated transport in polyvinylamine (PVAm):
The amino group contributes to transport of CO2
through membrane as a bicarbonate ion (HCO3-)
in the wet membrane while N2 is being retained.
CO2-flux ~1.2 m3/m2.h.bar
at = 200
*PCT: Hgg, MB, Kim TJ, Li,B.: WO2005/089907

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Facilitated transport of CO2 using dendrimers*

Poly(amidoamine) PAMAM dendrimers

were shown to be successfully
immobilized in a PEG network by UVpolymerization of PEGDMA

*I. Taniguchi et al. J Membr Sci 2008 (322) 277-280

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Mixed matrix membranes

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Polymeric membranes - Mixed matrix membranes (MMMs)

MMMs with micro- or nanoporous fillers
(ex.: matrimid with CMS, chitosan)
High selectivity

Nanocomposites (ex.: PMP,

PTMSP with nanoparticles)
High permeability

High mechanical strength

Reduced costs compared to pure inorganic membranes
The separation mechanism will be different for the two types of MMM

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Crosslinked Nanocomposites (PMP + FS) for

CO2/CH4 Separation
PMP+HFBAA
+15wt%FS

8.0

PMP+HFBAA
+25%wtFS

6.0

PMP+HFBAA
+35%wtFS

1600

5.0
4.0

PMP

3.0
2.0
1.0
0.0
3000

PMP+35wt%FS(uncrosslinked)

1800

PMP+HFBAA
N2 Permeability (Barrer)

CO 2 /CH 4 Selectivity

7.0

PMP(uncrosslinked)

1400
1200

PMP+2wt%H FBAA(crosslinked)

1000
800

PMP+2wt%H FBAA+35%FS(crosslinked)

600
400
200
0

4000

5000

6000

7000

8000

9000

10000

11000

CO2 Permeability (Barrer)

The effect of fumed silica content on CO2 permeability and

CO2/N2 selectivity of uncrosslinked ( ) and crosslinked
PMP (
).
Crosslinked membranes contain 2 wt % HFBAA; T=35C.
HFBAA = 4,4 (hexafluoro-isopropylidene)diphenyl azide

*L. Shao, thesis NTNU 2008

50

100

150

200

Tim e (day)

Stability over time

the effect of crosslinking

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Adding nanoporous MOFs in MMMs some

interesting results

ZIF = zeolite imidazolate framework

W. J. Koros et al, J. Membr.Sci., 175, 181-196 (2000)

W. J. Koros et al, J. App. Polym. Sci., 86, 881-890 (2002)
Bae, T.-H., et. al, Angewandte Chemie International Edition 2010, 49, (51), 9863-9866

15 w% ZIF90 in 6FDA-DAM

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Carbon membranes

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Carbon membranes

Carbon selective
layer, 7 micron

Ceramic
support

Hollow fiber carbon membrane

Ceramic supported carbon membrane

Molecular sieving mechanism

High chemical stability
High stability at high temp. and
pressure environment

Molecular sieving or surface flow

High chemical and mechanical stability
High stability at high temp. and
pressure environment

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Carbon Molecular Sieve (CMS) membranes

1000

DCH4 = 3.8 ,
Tcrit = -82.6C

2008 Robeson upper bound

DCO2 = 3.3 ,
Tcrit = 34C

Selectivity (CO2/CH4 )

100

1991 Robeson upper bound

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Precursor

0.1
1

10

100

1000

CO2 permeability (Barrer)

Tailoring pore size

1. Precursor functionalization
add metal oxides, metal nitrates
2. Adjusting carbonization parameters
temperature, heating rate, purge gas..
3. Post treatment
post oxidation, CVD

He, X, et. al. Ind Eng Chem Res 2011, 50, (4), 2080-2087
Kiyono, M., et. al. J Membr Sci 2010, 359, (1-2), 2-10
Yoshimune, M., et.al. Carbon 2007, 45, (3), 553-560.
Lie, J. A., et.al. Carbon 2005, 43, (12), 2600-2607
Shao, L., et. al. J Membr Sci 2004, 244, (1-2), 77-87
Steel, K. M., et. al. Carbon 2003, 41, (2), 253-266
Vu, D.Q.; et. al. Ind Eng Chem Res 2002, 41,(3), 367-380

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Other relevant topics for

membrane development

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Challenges using polymer membranes for

CO2 containing gas streams
CHALLENGES TO BE
ADRESSED
1. Standard polymers may
swell
2. Driving force may be too low
for standard membranes
3. Durability towards H2S, H2O,
SO2, NOx, fly ash
4. Permeance or selectivity is
too low

ACTIONS
1. Materials can be crosslinked,
gas may have to be dried
2. Work on the process design
or redesign the membrane
3. Dryer, FGD must be installed
/ filters for fly ash
4. Still not good enough?
TRY TO OPTIMIZE THE
MATERIAL!

Creative design for materials with optimized separation properties for CO2
is ongoing all over the world also in the Memfo group at NTNU

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..not only the membrane itself, but also creative

process solutions are important*..

* Ref.: T.C. Merkel et al., J. Membr. Sci., 359 (1-2) 2010: Two step counter-flow/sweep membrane process

This membrane has a permeance of 1000 GPU (~2.7 m3(STP)/(m2.h.bar)), with

only a selectivity CO2/N2 = 50 ( high flux, low selectivity)
This design dramatically reduces the membrane area and energy demand while
also meeting the product spesification for CO2 purity (> 95%)

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Upscaling is challenging dont underestimate it!

Going from small lab tests to pilot tests

1st step: Lab,

diameter 5-7 cm

2nd step: Small

bench-pilot,
Flat sheets,0.5 2m2

3rd step: Demonstration

pilot with fibres, 5 -10m2

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.. further field tests are

needed.., an example:
..this time at EDP Sines coal
fired power plant in Portugal

Installed May 2011

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Thank you for your attention!

Special thanks to Dr. Xuezhong He who helped to put the presentation
together!

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