Mixed Matrix Membrane For Gas Separation:

PDMS Filled with Ionic liquid Coated Zeolite (ZSM-5)

By

Muhammad Hussain Axel König

Lehrstuhl für Thermische Verfahrenstechnik Friedrich-Alexander-Universität Erlangen-Nürnberg

Introduction • Gas Separation with Membranes • Diffusivity vs Solubility-Based Gas Separation

Hybrid Membrane Materials • Design Concept • Implementation and Synthesis

Results • Single Gas Permeability • Modified Maxwell Model

Conclusion

Contents

2

Membrane-Based Gas Separation

3

Advantages of Membrane-Based Gas Separations • Low capital and operational cost • Low energy cost • Ease of Operation

Disadvantages of Membrane-Based Gas Separations • Fouling • Difficult to get both high selectivity(separation) and high through put

Membrane-Based Gas Separation

4

Gas Separation Membranes

Polymeric Dense Membranes e.g.

PDMS;

Poros Inorganic Membranes e.g.

Zeolite ,Pyrolyzed carbon

Hybrid Membranes Materials

1-Solubility selective 2-Separation mechanism (Solution Diffusion)

1-Size Exclusion 2-Solubility – selectivity through surface effects e.g. Cappillary condensation

Hybrid Membran Materials

Combine the best characteristics of Porous and polymeric materials

Different types of orgaine-inorganic hybrids

– Incorporation of inorganic materials into the polymer matrix Chandak et al. (1997), Merkel et al. (2002)

– Organic-Inorganic sol-gel materials Smaihi et al. (1996)

– Chemical attachment of organic groups to the inorganic surface Miller & koros (1990), Paterson et al (1996), Javaid et al (2001), Macarley & way (2001)

– Present work is focused on incorporation of Zeolite materials into the polymer matrix Kiran (2005),Oksoyuglu (2008), Hussain (2009)

5

B

A

B

A

B

ABA

S

S

D

D

P

P*/

dt

dp

RT

V

ppAP

FAAutoclave

pAFAM

MA

,

,,

**)(

MA

A

ppP

pAFA

MA

n*

)( ,,

Theory

6

Permeability =Flux *Thickness/Driving Force

Permeability= Solubility (S) * Diffusivity(D)

Diffusivity-Based Solubility-Based

MA

B

ppP

pBFB

MB

n*

)( ,,

Autoclave

1,4 Litre

Screw Valve

Vent

Needle Valve

Retantate

Permeate

Flow Diagram

CO2

N2

CH4

0,00515

m2

1

PSV

1

PI

2

PR

2

PSV

4

DPIR

1

FR

Fe

ed

2

FR

1

CIR

1

TR

2

TR

Room Temperature

3

PIR

Experimental Setup

7

Mixed-Matrix Membrane

Continuous polymer phase

Pc

Zeolite particles as dispersed phase Pd ;

Volume fraction of the dispersed phase

Pc/d Permeability of continuous/ dispersed phase

8

3000

5000

7000

9000

11000

13000

15000

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1

Pe

rme

ab

ilit

y /

[b

arr

er]

Zeolite mass fraction / [-]

Maximum (parallel model)

Maxwell model [2]

Minimum (series model)

[2] Bonhomme, F., CO2 selectivity and lifetimes of high silica ZSM-5 membranes. Microporous and Mesoporous Materials, 2003. 66(2-3): p. 181-188. * Measured Result 9

Maxwell Model : Permeability of CO2 as function of ZSM-5 Content

2

*

Maxwell Model : Permeability of CO2 as function of Zeolite Content

3000

5000

7000

9000

11000

13000

15000

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1

Pe

rme

ab

ilit

y /

[b

arr

er]

Zeolite mass fraction / [-]

Maximum (parallel model)

Maxwell model [2]

Minimum (series model)

Experimental results [3]

[2] Bonhomme, F., CO2 selectivity and lifetimes of high silica ZSM-5 membranes. Microporous and Mesoporous Materials, 2003. 66(2-3): p. 181-188. [3] Hussain, M, Data from measured and collected gas permeability values, Lehrstuhl fur Thermische Verfahrenstechnik, Erlangen, 2010.

10

Interfacial Inorganic-Organic Void

[4] Mahajan, R. and W.J. Koros, Mixed Matrix Membrane Materials With Glassy Polymers Part 1. Polymer Engineering & Science, 2004. 42(7): p. 1421. [3]Hussain, M, Data from measured and collected gas permeability values, Lehrstuhl fur Thermische Verfahrenstechnik, Erlangen, 2010.

Zeolite Polymer Interfacial Void Zeolite Interfacial Void Polymer

Fig. a) : SEM image showing the interfacial gap ‘sieve in cage morphology’[4] b) : SEM image showing the interfacial Void [3]

a b

11

Continuous polymer phase

Pc

Zeolite particles as dispersed phase Pd ;

Volume fraction of the dispersed phase

Pc/d Permeability of continuous/ dispersed phase

12

Filling of Interfacial Organic Inorganic Void: Concept

Filling of Interfacial Organic Inorganic Void: Concept

Continuous polymer phase

13

IL coated zeolite particles as dispersed phase Pd

Membrane Preparation : Concept

Zeolite particle

14

Membrane Preparation : Concept

Filled in PDMS

IL-layer after coating

Zeolite particle

15

Zeolite particle

IL-layer after coating

1.) Dispersing in Acetonitril

2.) Adding IL

3.) ~3h mixing at 60°C & 100 mbar

until solvent has evaporated

Filled in PDMS

1.) Dispersing in PDMS 2.) Adding Crosslinker 3.) Membrane Casting 4.) ~5 h Curing

Membrane Preparation

16

Porosity Camparison (Pycnomatic)

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

16% 38% 56%

Po

rosi

ty (ε)

/ [

-]

Filling level

Without IL-coating

20 wt-% TF2N in Filler

17

• Due to small atomic size of Helium, it could penetrate into the pores like 10-10 m in diameter. • Solid density of the sample • could be measured.

• Porosity = 1- (ρb / ρs)

Fig. 4.2: Permeability decrease with increasing filling level in [TF2N-allwt%-allwt%-all gases]

0

100

200

300

400

500

600

700

800

900

10wt% 20wt% 30wt%

Pe

rme

ab

ilit

y /

[B

arr

er]

Coating level

[EMIM TF2N-allwt%-56wt%-CO2][EMIM TF2N-allwt%-56wt%-CH4][EMIM TF2N-allwt%-56wt%-N2]

Varying Coating Level With Constant Filling Level

18

CO2

CH4

N2

56 wt% IL coated Zeolite in PDMS

Fig. 4.2: Permeability decrease with increasing filling level in [TF2N-allwt%-allwt%-all gases]

0

500

1000

1500

2000

2500

3000

3500

4000

16wt% 38wt% 56wt%Coating level

[EMIM TF2N-20wt%-allwt%-

CO2]

[EMIM TF2N-20wt%-allwt%-CH4]

0

200

400

600

800

1000

16wt% 38wt% 56wt%

Pe

rme

abil

ity

/ [B

arre

r]

Filling level

[EMIM TF2N-20wt%-allwt%-CO2]

[EMIM TF2N-20wt%-allwt%-CH4]

[EMIM TF2N-20wt%-allwt%-N2]

Varying Filling Level With Constant Coating Level

19

CO2

CH4

N2

20 wt % IL Coated Zeolite

Modeling Part: Modified Maxwell Model

= f(Pc ;Pd ;Φ)

Pd = PIL

Pc = PPDMS

IL-Polymer-model

Poverall= f(Pc=PPDMS; Pd=PIL;ΦFil)

20

Modeling Part: Modified Maxwell Model

P[EMIM]TFO [5] P[EMIM]TF2N[5]

PZSM-5 [6]

PPDMS[7]

*PPDMS

Units [Barrer]

[Barrer]

[Barrer]

Barrer [Barrer]

CO2 1171 1702 17622 3800 3500

N2 29 74 4182 400 325

CH4 63 139 9558 1200 1000

Table 1: Permeability values for CO2, N2 and CH4 in pure components

21

[5] Scovazzo, P., Determination of the upper limits, benchmarks, and critical properties for gas separations using stabilized room temperature ionic liquid membranes (SILMs) for the purpose of guiding future research. Journal of Membrane Science, 2009. 343(1-2): p. 202. [6] Bonhomme, F., CO2 selectivity and lifetimes of high silica ZSM-5 membranes. Microporous and Mesoporous Materials, 2003. 66(2-3): p. 181-188. [7] Merkel, T .C. et al. Gas sorption, diffusion, and Permeation in Poly (dimethylsiloxane). Journal of Polymer Science , 2000 :p . 415-434.

*Measured Results

IL-Polymer Model : CO2

22

16% 38% 56%

Coated Zeolite In PDMS

+25%

-25%

Pd = PIL

Pc = PPDMS

IL-Polymer-model

IL-Polymer Model : N2

23

16% 38% 56%

Coated Zeolite In PDMS

+25%

-25%

Pd = PIL

Pc = PPDMS

IL-Polymer-model

IL-Polymer Model : CH4

Pd = PIL

Pc = PPDMS

IL-Polymer-model

24

16% 38% 56%

Coated Zeolite in PDMS

+25%

-25%

Conclusion

• Successful coating of IL on zeolite surface has been achieved.

• Permeabilty of CO2, N2 and CH4 has been reduced by either increasing the coated level of IL on zeolite particals or by increasing the filling level of IL coated zeolite in PDMS.

• Modified Maxwell Model Results are in good conformance with the experimental results.

25

Our Group

26

Axel König

Thank you For Your Attention

27

TGA Analysis of IL-Coated Zeolite

60

65

70

75

80

85

90

95

100

0 100 200 300 400 500 600 700 800 900

We

igh

t L

oss

/

(%

ag

e)

Temperature / (oC)

10%[EMIM]TF2N &ZSM-5

20%[EMIM]TF2N &ZSM-5

30%[EMIM]TF2N &ZSM-5

Pure Zeolite ZSM-5

Decomposition Or Boiling Temperature(oC)

Water

100

Zeolite (ZSM-5)

> 1000

EMIM[TF2N]

~ 440

28

Fig. 4.2: Permeability decrease with increasing filling level in [TF2N-allwt%-allwt%-all gases]

0

200

400

600

800

1000

16wt% 38wt% 56wt%

Pe

rme

ab

ilit

y /

[B

arr

er]

Filling level

[EMIM TFO-20wt%-allwt%-CO2]

[EMIM TFO-20wt%-allwt%-CH4]

[EMIM TFO-20wt%-allwt%-N2]

Varying Filling Level With Constant Coating Level

29

CO2

CH4

N2

20 wt % IL Coated Zeolite

30

EMIM TF2N 1-Ethyl-3-methylimidozolium bis(trifluoromethanesulfonyl)imide

EMIM TFO 1-Ethyl-3-methylimidozolium trifluoromethanesulfone