DESALINATION

ELSEVIER Desalination 168 (2004) 367-372

www.elsevier.com/locate/desal

Water desalination using ceramic membrane distillation

Andr6 Larbota*, Laetitia Gazagnes a, Sebastian Krajewski b, Malgorzata Bukowska b,
Wojciech Kujawski b
aInstitut Europ~en des Membranes, UMR 5635, CNRS-ENSCM-UM11,
1919, route de Mende, 34293 Montpellier C~dex 5, France
Tel. +33 (4) 67 61 33 88; Fax +33 (4) 67 04 28 20; email: larbot@iemm.univ-montp2.fr
bFaculty of Chemistry, Nicolaus Copernicus University, ul. Gagarina 7, 87-100 Torun, Poland

Received 16 February 2004; accepted 25 February 2004

Abstract
In order to avoid hydrophilic behaviour of ceramic membranes prepared with metal oxides, alumina and zirconia
membranes with 200 and 50 nm pore diameters were grafted with fluoroalkylsilanes. The grafting was controlled by
TGA, and the hydrophobicitywas characterised by water contact angle and permeability measurements. Results show
that surfaces have hydrophobic behaviour with high values of contact angle. Grafted membranes were characterised
by measuring the outlet pressure. The hydrophobic membranes were tested in a membrane distillation process. NaCI
solution was used as the salt solution. This is the first example of membrane distillation using ceramic membranes.

Keywords: Membrane distillation; Ceramic membrane; Hydrophobicity; Desalination

1. Introduction
Usually, ceramic membranes are made from
metal oxides such as alumina, zirconia, or titania
[ 1]. The nature o f these materials creates hydro-
philic behaviour due to the presence of hydroxy
groups on the surface, and therefore a naturally
great absorption o f water into the pores is easy
*Corresponding author.
[2-4]. In the field o f ceramic membranes, surface
modification is generally used to reduce the pore
size o f commercially available ceramic mem-
branes and to avoid hydrophilic behaviour in the
separation of gas mixtures or o f low-molecular-
weight liquids [5,6] or to change the properties of
adsorption o f the membranes [7]. Fluoroalkyl-
silanes are often used for modification [8-11]. A
membrane distillation process needs materials

Presented at the EuroMed 2004 conference on Desalination Strategies in South Mediterranean Countries: Cooperation
between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the European
Desalination Society and Office National de l'Eau Potable, Marrakech, Morocco, 30 May-2 June, 2004.
0011-9164/04/$- See front matter © 2004 Elsevier B.V. All rights reserved
doi; 10.1016/j.desal.2004.07.021
368 A. Larbot et al. / Desalination 168 (2004) 367-372
which are not wetted by a liquid feed. If the
liquid is water, the process needs hydrophobic
membranes. One of processes which can be used
to change the surface properties of ceramic
membranes is grafting [2,3]. It would be inter-
esting to change the hydrophilic character into a
hydrophobic one and thus to change the proper-
ties and selectivity of the membranes.
Grafting can be performed by a reaction
between surface hydroxy groups and reactive
functions. In this work ethoxy groups were
chosen and organosilane molecules used. Alu-
mina and zirconia were used as the membrane
material. Hydrophobic characteristics can be
obtained by using organosilane compounds
containing hydrophobic fluorocarbon chains. A
monomolecular layer of organosilane molecules
was linked to the membrane surface.
This work reports the results of the grafting
process that optimised organosilane compounds
on zirconia powders and membranes and an
alumina membrane. Preparation and characteri-
sation are described, and the results of the
desalination of sodium chloride solutions are
discussed.
2. Material and methods
2.1. Reagents
All grafting experiments were conduced in
chloroform using a 10-5 mol/dm3 solution of
1H, 1H,2H,2H-perfluorodecyltriethoxysilane,
noted C8, which corresponds to the length of the
fluoro chain. The formula is: CsF17CzH4Si(OEt)3.
C8 was supplied by Lancaster, whereas the
chloroform (stabilized with ~1% ethanol) was
supplied by Carlo Erba Reagenti. We also used
two other compounds with shorter fluoro alkyl
chains such as C6 (C6FI3CzH4Si(OMe)3)and C1
(CF3C2H4Si(OEt)3). The C1 and C6 compounds
were synthesized at the Macromolecular
Chemistry laboratory in Montpellier. To avoid
the polycondensation of these molecules, prepa-
ration of this grafting solution required an argon
atmosphere.
2.2. Powders and membranes
Tubular membranes, two from zirconia and
one from alumina, were used. A ZrO2 membrane
with pore diameters equal to 50 nm (noted Z1)
and an A1203 membrane, 200 nm in pore
diameters (noted AI), were produced by Pall
Exekia. A ZrO2 membrane, 200 nm in pore
diameters (noted Z2), was prepared in the labora-
tory. Zirconia powders from Cezus Chimie
possess a specific surface area of 8 and 43 m2/g
and allow the preparation of membranes with
pore diameters equal to 200 and 55 nm after
firing at 1050 and 700°C, respectively - - in good
agreement with those of the zirconia membranes
used [2].
2.3. Grafiing process
The grafting procedure proposed by Picard et
al. [3] consists of immersing a sample into the
fluoroalkylsilane solutions for different periods of
time at room temperature. The procedure was the
following: successive soakings of samples in the
grafting solution and drying at 100°C for 12 h
between each soaking. For this work, four succes-
sive soakings different in time - - 4 h (G1), 14 h
(G2), 25 h (G3), then 75 h (G4), i.e., 113 h
immersion - - were performed. This procedure
was used to characterise hydrophobicity and also
grafting kinetics.
The concentration ofsilane solution in chloro-
form (10 -5 mol/L) and the temperature (room
temperature) were maintained constant for all the
experiments.
2.4. Apparatus
The grafted powders were analysed by
thermogravimetrie analysis on a TGA (Texas
Instruments) apparatus in air atmosphere and in
 A. Larbot et al. / Desalination 168 (2004) 367-372 369

the temperature range o f 25°C to 1000°C. On the

100~~----~ ..... -~. . . . . . 4 - - . . . . .
basis o f the TGA results, it could be concluded
that the decomposition o f the fluoro chain occurs
at temperatures higher than 230°C.
Contact angle measurements were performed
by the water drop method using a Kruss apparatus
on samples with planar configuration.
Water permeability was measured with a view
to control the efficiency o f the grafting treatment . . . . . . . . . . . . . . . . .

and to compare it with this obtained before the

grafting. The tested membranes were dried at ~4
150°C before permeability measurements for so 1
12 h. If no water appeared on the surface of the 0 200 400 600 800 1000
membrane within 2 h, the membranes were con- Temperature (oC)

sidered hydrophobic under the applied working Fig. 1. TGA curves for different grafting conditions.
pressure. Water permeability was measured on
grafted ceramic membranes by crossflow filtra- ,.. 20
tion experiments, Measurements were performed
using a home-made pilot plant. 15
Rejection o f salt in permeate was measured o 10
using gas chromatography. Measurements were
performed on a Dionex DX-100 chromatograph. ._m 5

0 i ! f ] r i ! ] ~ ]

0 50 t O0 150
3. Results and discussion
Time (h)
3.1. Results o f TGA
Fig. 2. Weight loss as a function of grafting time.
It was assumed that amount o f the grafted
fluroalkylsilane was proportional to the loss of
Table 1
the sample mass in the temperature range 230-
Contact angles (+2 °) obtained with different
800°C. Results o f TGA analysis of the grafted
fluoroalkylsilanes
zirconia powder for the increasing o f C8 grafting
time are presented in Fig. 1.
Pore diameters, nm
It is obvious that weight loss increased when
the grafting time also increased. In Fig. 2 a 200 55
decrease o f weight loss was observed with an C1 123 116
increase o f time. A logarithm variation was C6 145 140
observed, which means that a period o f I 18 h for C8 143 145
grafting is enough.

powders were grafted. The two membranes were

3.2. Contact angle measurements and water
permeability
Distilled water was used for measurements
and planar membranes prepared from zirconia
respectively grafted by the three different fluoro-
alkylsilanes. The values of the water contact
angles were determined using several samples o f
the same type. Results are given in Table 1.
370 .4. Larbot et al. / Desalination 168 (2004) 367-372
It can be noted that contact angle values are
independent of pore diameter, but they are
dependent on the length o f the fluoro chains. For
the shorter fluoro chain, i.e,, C1, hydrophobicity
is less important than for longer fluoro chains
such as C6 and C8.
The high values o f contact angles show that
the grafted membranes are hydrophobic even
when C 1 silane was used. We chose to work with
the three types o f membranes grafted by the C8
silane for the tests in desalination, and therefore
we measured the water flux o f the grafted
membranes and determined the outlet pressure.
The filtration pilot plant used for permeability
measurements is a classical pilot plant except for
the membrane housing, which is transparent and
allows the observation o f the membrane surface
and determines the first water drop which appears
and thus, the outlet pressure. After an initial
experiment, and if a new value o f the permea-
bility was needed, the membrane was dried again.
Results are reported in Table 2.
We observe that:
• grafting is very efficienct; permeabilities are
drastically decreased after the treatment;
• the drying between the two experiments
Table 2
Outlet pressure of grafted membrane and permeability of
grafted (G) for 113 h and no grafted membranes
Membrane Outlet pressure, Permeability,
bar 1/h.m2.bar
Z1 -- 800
Z1-G 5 1.I0
Z2 -- 2700
Z2~3 1 2.10
Z2-G-D 2 1.05
A1 -- 2000
A1-G 4 0.5
Note: Intermediate drying, D. Z1 = ZrO2, 50 nm; Z2 =
ZrO2, 200 nm; A1 = A1203, 200 rim.
improves the hydrophobic behaviour: outlet
pressure is higher and permeability is lower;
this fact was verified by other experiments;
It seems that outlet pressure is more depend-
ent on the no-graft membrane permeability
than on pore diameter.
3.3. Distillation results
Membrane distillation consists o f applying a
difference in temperature between the feed side
and the permeate side. Water is vaporised at the
surface o f the membrane and the gaseous phase
can pass through the membrane. The feed flux is
tangential to the porous surface.
Tubular membranes have an inner diameter o f
7 mm and an outer one o f 10 mm. The inner
diameter was considered for the calculation of
permeability.
Firstly, the permeability for pure water was
measured using the A1 membrane by varying the
temperature difference. Results are reported in
Fig. 3. Table 3 reports the rejection rate and daily
flux for NaC1 solutions at different concentrations
as a function of the temperature difference. The
quality of water in the permeate whatever the
working conditions and the membrane used is
very good. Except for the lowest salt concentra-
tions, 0.001 and 0.01 M, for which the rejection
rate ranged from 90 up to 96, all the other values
are higher than 99%.
200
x
.n 150
r-
._~ 1 0 0
,O
"~
a 50
,I) O
0
0 50 100
Temperature difference
Fig. 3. Pure water flux vs. temperature difference for the
A1 membrane.
 A. Larbot et al. / Desalination 168 (2004) 367-372 371

Table 3 of membrane. A decrease was observed for mola-

Daily flux and rejection rate for different NaC1 solutions rity higher or equal to 1. The fluxes are the
and temperature differences for the three membranes highest for the Z2 membrane when the molarity
is 0.1 and when the temperature difference is
AI membrane 90°C.
NaC1 Feed/ Average daily Rejection
molarity permeate flux, 1/d.m2 rate, %
temp., °C 4. Conclusions
0.001 63/5 21.4 90 This work demonstrates that it is possible to
95/5 140.5 96 perform membrane distillation using grafted
0.01 63/5 19.8 95 ceramic membranes. These membranes are
95/5 156.1 99.5 hydrophobic, and transport o f water through the
0.1 63/5 20.9 100 membrane is only by transport ofvapour. The salt
95/5 163.2 100 rejection in this process is close to 100%. Values
1 63/5 18.2 100 o f water flux through the membrane in the mem-
95/5 129.5 100 brane distillation process depend strongly on
temperature differences. Values of water flux do
Z 1 membrane not depend on the salt concentration when it is
NaC! Feed/ Average daily Rejection lower or equal to 0.1 M.
molarity permeate flux, 1/d.m2 rate, % Solar energy could very much help this pro-
temp., °C cess in countries which are very sunny due to the
0.1 60/5 16.8 100 reduction o f energy costs; and thus membrane
90/5 95.3 100 distillation could become competitive relative to
other p r o c e s s e s - - reverse osmosis or distillation,
1 60/5 15.7 100
90/5 82.7 100 for instance. It would be also interesting for these
2.9 60/5 12.1 100 countries to prepare ceramic membranes from
clay at a low cost, as found in the literature
90/5 68.8 100
[12,13].
The use of ceramic hollow fibers would be
Z2 membrane
also very interesting for developing modules with
NaCI Feed/ Average daily Rejection high surface/volume ratio. This research is in
molarity permeate flux, I/d.m2 rate, %
progress in our laboratory.
temp., °C
0.1 60/5 28.2 99.0
95/5 202.3 99.5 References
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