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
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