Influence of ionic liquid

content on properties of
dense polymer membranes
M. Kohoutov

, A. Sikora b , . Hovorka c , A. Randov c,

M. Timad, P. Izk a

Department of Separation Process, Institute of Chemical Process

Fundamentals, Rozvojov 135, 165 02 Prague 6, Czech Republic
b
Institute of Macromolecular Chemistry, Heyrovskho nm. 2, 162 06 Prague
6, Czech Republic
c
Institute of Chemical Technology, Technick 5, 160 00 Prague 6, Czech
Republic
d
Faculty of Food Technology Osijek, University of Osijek, F. Kuhaa 18, 31 000
Osijek, Croatia
http://www.icpf.cas.cz/
a

Supported ionic liquid membranes offer a range of

possible advantages:
Molecular

diffusion - higher in liquids

than in solids, allowing high fluxes;
The selectivity of the separation can be
influenced by variation of the liquid especially ionic liquids offer the
advantage of a wide variety of properties;
Ionic liquids as liquid membranes allow three-phase systems due to their
special mixing behavior;

 Due

to their good thermal stability, reactive processes - at

high temperatures (up to around 250 C), which leads to faster
kinetics in the case of endothermic reactions;

The use of nano-, ultra- and micro-filtration ceramic

modules - diminish concentration polarization due to rough
liquid-membrane surface;

Contrary to the extraction,

only small amounts of liquids
are necessary to form the liquid
membrane, thus allowing the
use of more expensive materials.

The only problem is long time stability of the liquid in the pores.

Stability of the hydrophobic ILs inside the pores (in hours)

ceramic module
pore size (nm)

200
60
5
0.9

IL
C14H24N+BF4- C4mim+PF6- C8H26N2+B(CN)4- C27H54F6N2O4S2
0.1
0.5
1.2

1.3
2.4

1.9
3.5

0.15

Experimental
Membranes preparation :
PDMS Elastosil M4601 (base & crosslinking
catalyst) (Wacker Silicones, Germany)

IL benzyl-3-butylimidazolium
tetrafluoroborate (Chemada Fine Chemicals,
Israel)
10, 20, 30 wt. % of IL
Average thickness 0.3 0.017 mm
Conditions :
37C, 5 wt.% butan-1-ol, N2 flow rate 0.9 ml/s,
48 hours
Analysis : Finnigan GC Trace Ultra GC TCD;

Compatibility of PDMS and

[BBIM][BF4]
Tg,IL appeard only
in the blend with
30wt.% IL when the
sample was cooled
and heated slowly
PDMS and [BBIM]
[BF4] are not
compatibile; blend
contains amorphous
and crystalline
phases of PDMS
and dispersed
phases of [BBIM]
[BF4]

Temperature dependences of DSC heat flow of the blend

containing 30% of [BBIM][BF4]
(a) heating mode (10C/min) preceded by cooling (10C/min)
(b) heating mode (10C/min) preceded by cooling (1C/min)
(c) heating mode (5C/min) preceded by cooling (1C/min

Sorption of binary mixture water

butan-1-ol

Dependence of preferential and total sorption i , Q respectively of butan-1-ol from 5 wt.% butan-1
ol aqueous solution on [BBIM][BF4] content in PDMS membrane (sorption from liquid solution)

Butan-1-ol is sorbed preferentially

Preferential sorption is a linear function of IL content (30wt.%)
Total sorption increases with the amount of IL in the blend

Pervaporation set-up
Retentate
Thermostat

Feed
Permeate

Reaction vessel

Vacuum
pump

Cold trap
Permeate

Pervaporation
experiment
standard laboratory
pervaporation set-up
with effective
membrane area of
5 cm2 ; downstream
pressure
p = 60 Pa

Pervaporaton of binary mixture

water butan-1-ol
Total permeation
flux and
separation factor
increases with the
[BBIM][BF4]
concentration in
membrane

Dependence of separation factor

PDMS membrane

bw and total permeation flux J on [BBIM][BF4] content

Experimental
As a support matrix for the polymer-IL membrane the ceramic
ultrafiltration module made from TiO2 with pore size 60 nm was
used.
The PDMS was prepared by mixing a solution of RTV 615A and
RTV 615B (General Electric) in 10:1 ratio at 60C for 0.5 hour.
15 wt% of tetrapropylammonium tetracyano-borate ionic liquid and
85 wt% polydimethylsiloxane (IL1).
50 wt% of 1-ethenyl-3-ethyl-imidazolium hexafluorophosphate ionic
liquid was mixed with 50 wt% polydimethylsiloxane - (IL2).

 The ternary system - practical application in

biotransformation processes, where the
fermentation broth from Clostridium
acetobutylicum is normally used
The compound of interest is biofuel, namely
BIObutanol
It is the main product of butan-1-ol fermentation
and it is also the primary inhibitory product
affecting the bioconversion

Dependence of permeate permeation flux

on feed concentration at 37C

Dependence of enrichment factor of

permeate on feed concentration at 37C

 The enrichment factor of butan-1-ol increased from 2.2 (PDMS) up to 10.9 (IL2-PDMS) (Izk P, Ruth W, Dyson P, Kragl U (2007) Selective
Removal of Acetone and Butan-1-ol from Water with Supported Ionic Liquid - Polydimethylsiloxane Membrane by Pervaporation, Chem. Eng. J., 139/2 (2008) 318-321 )
Fermentation was carried out at 37C and pH 4.5.
Firstly, a continuous fermentation with removal of ABE by pervaporation was measured without any butan-1-ol addition to
test, if the SILM was selective and stable.

Experiment
C. Acetobutylicum ATCC 824 was grown under
anaerobic phosphate-limited conditions.
In the chosen fermentation system, especially the
phosphate concentrations as well as the dilution rates
were responsible for the amount of produced solvents.

dilution rate
-1
(h )
0.05
0.075
0.075
0.09

phosphate
(mM)
0.75
0.75
0.5
0.75

OD600
7.12
7.1
8.52
6.25

acetone
-1
(g l )
3.82
2.82
5.00
3.18

butan-1-ol
-1
(g l )
7.12
5.44
10.38
7.07

acetate
-1
(g l )
0.97
0.98
1.62
0.93

butyrate
-1
(g l )
0.64
0.65
0.44
0.69

ethanol
-1
(g l )
0.67
0.50
0.94
0.77

solvent
productivity
-1 -1
(g l h )
0.66
0.78
1.38
1.14

Retentate

Feed

3
Permeate

Vac

Schema of continuous culture fermentation connected with

pervaporation
1.Waste tank; 2. Tank with substrate; 3. Culture vessel; 4.
Pervaporation cell; 5. Cold trap; 6. Vacuum pump

Dependence of permeate concentration on fermentation

time at 37C, at dilution rate 0.075 h-1, 0.5 mM
Butan-1-ol
addition
Pervaporation
phosphate concentration
in supplying
vesseloffand pH 4.5.

Butan-1-ol (summary of the produced and added butan-1-ol);

Acetone; Ethanol; Acetate; x Butyrate

Dependence of optical density and butan-1-ol

concentration on time of fermentation
Butan-1-ol addition

Butan-1-ol concentration;
Optical density

Pervaporation off

 After successful tests, the concentration of butan1-ol was several times increased to test the SILM
under more stringent conditions and to study the
effect of pervaporation on the cells.
After 3 months of the experiment we did not
observe any change of mass or selectivity of IL in
the pores of the ultrafiltration membrane.

Dependence of butan-1-ol and acetone permeation

flux on its culture vessel concentration.

Butan-1-ol; Acetone

Dependence of butan-1-ol and acetone enrichment

factor on its culture vessel concentration.

Butan-1-ol; Acetone

Conclusions
To get more effective ABE removal from
fermentor we used pervaporation with IL-PDMS
nonporous membrane.
Using this membrane we were able to remove
ABE from the culture supernatant more effectively
than it was described by others (Qureshi et al.
(1992), Soni et al. (1987), Liu et al. (2004)).

Conclusions
The supported ionic liquid membranes were weighted
after all experiments and no weight changes were
observed stable SILM.
Higher diffusion coefficient is most probably
responsible for higher permeation flux and
enrichment factors of butan-1-ol in IL-PDMS
membrane.
If we would run pervaporation with continuous and
complete removal of butan-1-ol from the culture
supernatant, it would lead to more stable
fermentation process with higher production of
BIObutanol.

Acknowledgement

Thank you for your attention

This research was supported partially by grant
No. 104/08/0600 from Czech Science
Foundation and Marie Curie Reintegration
Fellowships within the 6th European
Community Framework Programme.