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DOI:
doi:10.1016/j.memsci.2005.06.054
journal of
aCII!NCI!@OIAeCT-
ELSEVIER
MEMBRANE
SCIENCE
Instilut Europeen des Membranes, UMR 5635, IEMICNRS /9/9, Route de Mende. 34293 MOnIpellier Cedex 5, France
Lahora/oire de Chimie Ma cromo/ecu/aire. UPRESA 5076 CNRS, NSCM, 8 Rue de f'Eeole lIonna/e, 34296 Motllp ellier Cedex. France
Abstract
The potentia1 of hybrid organic- inorganic membranes for separaling organic molecules from air, based on solubility selective mechanism,
was evaluated. Alumina and titan a membranes with average pore size near 4 nm were surface modified using trimethoxysilane fluorinated
coupling reagent. The penneabilities to helium. nitrogen. methane. ethane. propane. butane and carbon dioxide were evaluated at feed
pressures lying between (1.5 x 10' and 3.5 x 10' Pal 1.5 and 3.5 bar and permeate outlet near I x 10' Pa (I bar). The permeabilities of the
grafted membranes generally decreased by about two to three orders of magnitude compared with the untreated membranes. The C0 21N 2
permselectivity increased significantly in the case of the Ti02 gmfted membrane. The membranes performances were compared and the
Ti02 grafteu. membrane exhibits highcr permselectivity and permeability, so that. it is a good candidate for CO2 to N l separation and CO2 to
hydrocarbon separation.
1. Introduction
During the few last years, special attention has been paid
to ceramic membranes for gas separation because of their
thermal and chemical stabilities compared to those of polymeric membranes [1.2]. Interesting application may include
the separation of C02 from gas mixtures. which is of particular interest for environmental protection. Unfortunately.
the mechanism for gas transport in commercially available
porous ceramic membranes with pores < I 0 nm is Knudsen
diffusion. Therefore. the separation efficiency between gases
having a small difference in molecular weights. such as C02
and N2. is quite low. Thus, many researchers have tried to
modify the surface of ceramic membranes in order to enhance
the C02/N2 separation factor by gas transport mechanisms
other than Knudsen diffusion [3-12].
Corresponding author.
E-mail addrn f>: bourret @criLuniv-montp2.fr ( D. Bo urret).
03767388/$ - see front matter () 2005 Elsevier B. V. All rights reserved.
doi: I 0.1OI6lj.memsci .2005.06.054
102
low-density polyethylene membranes was obtained by Randon and Paterson [15] using n-dodecylphosphate as coupling
reagent (C021N2 permselectivity of 4.5 for the modified
membrane compare to 2.5 or 12.6 for, respectively, high and
low-density polyethylene). The best C021N2 permselectivity
(10.2) was obtained [16] for a modified ,,{-A}z03 membrane
with a monolayer of polydimethylsilane on its surface. In
this case the transfer mechanism through the PDMS-aIumina
membrane was a solubility/diffusion one.
The coupling reagent used by Hyun et aI. [17] was phenyltriethoxysilane having a special functional group (phenyl
radical) with a high affinity for C02. The C021N2 permselectivity was 2.15 and a mixed Knudsen/surface diffusion
was deduced for C02 transfer mechanism through the modified membrane.
Mejean et al. [18] performed surface modification of
commercially available ,,{-Al203 membrane (mean pore
size 5 nm) with fluorinated triethoxysilane and dodecyltriethoxysilane. The C021N2 permselectivity were 4.0 for fluorinated triethoxysilane and 5.3 for dodecyltriethoxysilane.
A mixed Knudsen/surface diffusion was deduced for C02
transfer mechanism through the modified membranes.
More recently, Javaid et al. [19] modified commercially
available Membralox mesoporous alumina membranes
with an average pore size of 5 and 12 nm using solutions
of alkyl trichlorosilanes in toluene. Their approach seems to
be ideal for creating solubility-selective membranes because
of the ability to deliver a large number of desired chemical
groups while still remaining a relatively high free volume.
The main objective of this work was to synthesize
organic-inorganic hybrid membranes comprised of fluorinated triethoxysilane grafted to the surface of commercially
available mesoporous membranes, and evaluate their performance for C021N2 separation. Fluorinated coupling reagents
were preferred to alkyl ones because in each case C02 has a
high solubility, but alkanes have poor solubility in fluorinated
compounds [18]. Thus, for separation of a mixture .of C02,
alkanes and N2, ceramic membranes modified by fluorinated
coupling reagent will be more efficient due to large C021N2
and low C02/alkanes permselectivities. However, some large
C02/alkanes permselectivities were obtained due to the fact
that a multilayer surface diffusion can occurs for butane in
the case of ,,{-A}z03 modified membrane.
In this paper, commercially available mesoporous Ti02
and ,,{-Al203 membranes were surface-modified with fluorinated coupling reagent. The fluorinated-coupling reagent,
CsF 17C2~Si(OCH3h, was delivered in chloroform and .
grafted to the surface via SiOH groups formed by hydrolysis
of triethoxy groups with surface water. The membrane was
tested for permeance to methane, ethane, propane, butane,
carbon dioxide, helium and nitrogen. Helium was used in
order to test Knudsen flow for the membrane. Methane,
ethane, propane, butane and carbon dioxide were used to evaluate C021N2 and C02/alkanes permselectivities. Section 2
provides the details of the fluorinated coupling reagent synthesis, membrane elaboration and permeation testing. The
2. Experimental
103
(2)
V=
(:~r2
(3)
Fo = C3D,
(~;) rpl
(5)
"p
3. Transport mechanisms
The transpon of gas through a porous membrane can occur
by several mechanisms [20). When the mean free path of the
gas molecules is much smaller than the pore diameter, viscous
flow occurs and the penneability, Fo , is given by [21]:
(I)
where e is the porosity, q the gas viscosity, Tv the tonuosity factor for the viscous flow, rp the pore radius, R the gas
104
decreases due to the liquid transport contribution (the permeability for vapour flow is much higher than for liquid flow).
This qualitative picture was illustrated by Lee and Wang using
six possible modes for a cylindrical capillary in case of multilayer diffusion and capillary condensation [241
If the pore size is decreased (rp < 3 nm), the contribution
of the surface flow increases while the gas phase diffusion
contribution decreases. There will be a gradual change to
solution-diffusion type of transport as present in most of the
non-porous polymer membranes or to mechanisms like those
in microporous membranes where adsorption plays an important role [25,261.
Picture I. SEM surface analysis of the TiOz membrane (the straig hlline is
300 nm long).
as
as
..
'a,
'II! 6
.~
'0
..4
layers were one can see larger voids in the Ti02 membrane
(Picture I) than in the jI-AIz03 membrane (Picture 2). These
voids are not linked together so that, the overall permeability
is increased but the flow remains a Knudsen one (i.e., only
the tortuosity factor, T, decreases).
He(AI, O,)
N2(AI, O,)
x C02(AI,O,)
t,. C3H8(AI,O,)
<> He(TiOJ
o N2(TIO,'
+ C02(TiO,)
o C3H8(TiO~)
Fig. I. Penneabilities to He. N2. C02. C3Hg against Win (M: molec ular
weigh!) for TiOl and Al20 3 bare membranes.
Picture 2. SEM surface analysis of the A1203 membrane (the straight line
is 300 nm long).
surface and the gas molecules, but also by the condensabiljty of the gas. Here, only C4H to is to be considered.
(iv) FOp forthe gas transport through the pore necks and at tbe
surface ofTi02 grajns. This mechanism depends greatly
on the solubility of the gas in the fluorinated chain, so
that FOp(COz)>> FOp(alkanes) > FOp (N 2) > FOp(He). On
the other hand, the diffusion step of this mechanism
is improved by the higher mobility of the fluorinated
chains.
t05
..
":
10
o ClHI
b.C2H6
"e;
(;
S-
'b
..
~
:;;
....
E
..
f(;N2
";'''!
@!i"F@
xH.
1l!:tA#
oc ...
;t(;t(;t(;t(;t(
hM~~M 1:lCCC
0
0
Q.
106
l:
12
10
> 8
..
a; 8
E4
:.
15
.6"""" .....
._.-
14
13
(11]
X,. ....Mt27!
1Ill.........."'11
fj.
DIff....... [17]
Oflrl6l_1NJOlI
0:.:
O'* __ (lI:)2)
14
12
11
10
References
C~
permeability,
5. Conclusions
In previous work in the literature, the surface of inorganic
mesoporous membranes were chemically modified using different chains oftrichlorosilanes.ln this work. we have shown
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trimethoxy fluoro silanes. We further demonstrated that the
gas permeation properties of such membranes can be controlled through the nature of the substrate and oligomer
choice. This approach seems ideal for creating solubility
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