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DESALINATION

Desalination 168 (2004) 207-213

ELSEVIER

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Use of ultra- and nanofiltration ceramic membranes


for desalination
S. Condom a, A. L a r b o t b*, S a a d A l a m i Y o u n s s i b, M. P e r s i n a
aInstitut Europ~en des Membranes (IEM), UMR 5635 CNRS ENSCM UM II, CNRS,
1919 Route de Mende, 34293 Montpellier cedex 5, France
bLabratoire des Mat~riaux, Catalyse et Environnement FST de Mohammedia, BP 20650, Mohammedia, Maroc
Tel. +33 (4) 67 61 33 88; Fax +33 (4) 67 61 33 85; email: larbot@iemm@univ-montp2.fr

Received 13 February 2004; accepted 20 February 2004

Abstract

The filtration tests of electrolyte solutions performed with different ceramic membranes show that salt rejection
depends on pH, salt nature and concentration. A simple correlation between streaming potential and rejection rates exits
and confirms that streaming potential is a relevant parameter to characterize the surface charge of filtering material
during the filtration process.

Keywords: Membrane; Filtration; Electric interactions; Streaming potential

1. Introduction
Fresh water is very important for all aspects of
life. Wastewater, brackish water and seawater
treatment is a good solution as a source of fresh
water. Among all the techniques used for desalination, pressure-driven membrane processes have
an important position. If reverse osmosis is
known as a classical process for desalination,
*Corresponding author.

nanofiltration (NF) and even ultrafiltration (UF),


if membrane pore diameters are lower than
10 nm, can also be used. The interest in UF is due
to the important flux obtained. Desalination performances of ceramic membranes depend on the
concentration of ions and on the complexity of
the medium to be filtered, but also on the type of
membrane material. Ceramic membranes commonly used are generally made of metal oxides,
which have an amphoteric behaviour; then the
electric surface charge depends on the pH of the

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.2004.06.189

208

S. Condom et al. / Desalination 168 (2004) 207-213

filtered solution [1-4]. Thus, a phenomenon of


repulsion or attraction occurs between the ionic
species present in the solution and the charged
membrane. Besides the electrostatic effects, the
size of the filtered species is also another parameter which should be considered, particularly if
the solution contains complexed cations with
mineral or organic ligands.
In this work we discuss the effects from the
results obtained for the filtration of different
saline solutions using several ceramic membranes
prepared by the sol gel route We also present the
correlation of the membrane selectivity in terms
of rejection with the surface charge developed on
the material surface.

2. Experimental

2.1. Membrane description


The membranes tested were, respectively,
made of y alumina, CoAI204, and TiO2/ZnA1204
(Table 1). The conditions for the preparation of
the three membranes have been previously
discussed [5-7]. The filtering layers were created
using the sol gel route: the sols were deposited by
slip- casting on the surface of a tubular support in
c alumina (200 nm of pore diameter).

2.2. Filtration pilot


The filtration experiments were carried out on
a laboratory pilot scale. The capacity of the tank
was 2 L, the working pressure was fixed between
0 and 10 bars by means of a nitrogen gas bottle,
and the velocity rate of the fluid was around
2.5 m.s -~. The filtering module had a tubular
membrane 15 cm in length and 10 mm in outer
diameter for a 7 mm inner diameter; the active
layer (surface area 26 cm 2) was deposited in the
inner part of the support. Streaming potential
measurements made performed through the membrane by means of two silver wires covered with
silver chloride used as reference electrodes. One

Table 1
Main characteristics of the prepared membranes
y-alumina CoA1204 ZnAI204
Pore diameter, nm
Cut-off, D
Water permeability,
L.h-l.m-2.bar-l

3.2
2400
1.2

5
2000
5.7

5.6
1500
3.5

was positioned at the axis of the membrane tube


and the second near the opposite side of the tube.
The filtered solutions were prepared with analysis grade salts at a concentration between 10 -3
and 10 -2 mol.L-1 or other precise concentration.
The concentration of the permeate was obtained
by atomic absorption and ionic chromatography.
The pH of the solution was adjusted with concentrate acid (HC1) or base (NaOH) solutions.

3. Results and discussion

3.1. Membrane characterization


The different membranes tested were characterized by scanning microscopy and nitrogen
adsorption/desorption; their cut-off was evaluated
from the rejection rates obtained for the filtration
of soluble PEG polymers of calibrated molecular
weight. Fig. 1 shows the cross section and the
surface views of the CoAI204 membrane, which
is about 4 #m thick.

3.2. Size effect


The results obtained for the y-alumina membrane show that the rejection rates depend
strongly on the nature of the filtered salt
(Table 2). Under our experimental conditions, the
best rejections were observed for the MA z salt; on
the contrary, bad rejections were obtained with
M2A salts. These classical results are in agreement with the electrostatic model based on the
interaction between the ions and the charged

209

S. Condom et al. / Desalination 168 (2004) 207-213

Table 2a
Rejection of salts on a ,/-alumina membrane (C = 10-3 moLL-l)
Cations

K
Na +

pH

R, %
S042-

CI-

NO 3

36

55

5.6

20

50

70

5.5

Ca 2

40

95

95

5.6

Cu 2+

45

97

97

5.5

Cd 2+

40

97

97

5.6

Ni 2

40

97

96

5.6

Table 2b
Effect of complexation on the rejection of salts on a y-alumina membrane (C = 10-3 mol.L-1)
Metal sulfate

R%

Ligand

Without

NTA

Cu 2

45

Cd 2.

40

Ni2

40

pH
EDTA

o-phenantroline

Polycarboxylate

--

80

96

53

80

97

99

80

85

95

95

Fig. 1. SEM of spinel CoA1204 membrane: (a) cross section, (b) surface view.

filtering material [8,9]. At natural p H the yalumina m e m b r a n e is p o s i t i v e l y charged, and


then divalent coions M 2+ are repulsed m o r e than
a m o n o v a l e n t one (M+). T h e salts which are

associated with b o t h divalent ions present a


moderate rejection.
C o m m o n ligands can be used to improve the
rejection o f the salt after c o m p l e x a t i o n o f the

210

S. Condom et aL / Desalination 168 (2004) 207-213

.....~-:.
x3

100

80-~ Ni2NiX
~ 60-[ ~ W

ligand:o-Phenantroline

40

20
0 - ~ - - - ~ * ~ - ~

--'~-~-"1

10

pH
Fig. 2. pH effect on complexation of Ni~ with an ophenetrolineligand.

cation; nevertheless, the size of the ligand should


be enough and more important than the pore size
of the membrane to prevent the ligand to cross the
membrane. Table 2 shows the rejection increasing
of MSO4 salts from 40% to more than 90% after
complexing the cation with different ligands.
Generally the rejection rate also depends on the
pH according to the stability of the complex,
which is more important for the high pH value in
Fig 2.

3.3. Streaming potential and salt rejection


The surface charge of the material, which
depends on the pH of the filtering material, is an
important parameter which governs the efficiency
of a membrane process, especially for removing
ionic species. Unfortunately, the direct determination of the surface charge is not easy and only
indirect methods exist. Among these, the zeta
potential determination that is linked to the surface charge can be used to approach the surface
charge of the material. In the past the authors
have determined the zeta potential from electrophoretic measurements performed with fine
powder suspensions of the membrane material
dispersed in an electrolyte solution. This tech-

nique leads sometimes to an uncorrected charge


of the material in the filtration condition, probably because the texture of the powder and of the
membrane is quite different. This is why different
authors have suggested using others methods
[10,11 ] for the surface charge measurement such
as the streaming potential, which is also in
relation with the surface charge and seems more
representative of the real charge developed on the
membrane surface in the filtration condition. The
streaming potential (SP) depends on the zeta
potential according to the Smoluchowsky relation
(1), but in fact the conductivity ~. must include
the surface conductivity, which can become important for low pore size membranes.
s e - g ' (p..~.

(1)

In order to correlate the experimental rejections of ionic species with the membrane surface
charge, we present the results obtained for the
rejection of classical neutral salts (NaC1, Na2SO4)
and also for sodium phosphates at different pH by
means of the three prepared membranes. The
experimental measurement of the SP is relatively
easily obtained by the relation SP = AE/AP,
which is the slope of the curve AE vs. applied
pressure in the dynamic filtration conditions.
Fig. 3. shows that the SP values depend on the pH
of the filtered solutions, and this behavior is
expected because the SP given by the Smoluchowsky relation depends on the zeta potential,
which also depends on surface charge of the
membrane. The variation of the surface charge of
the membrane can be explained by the amphoteric properties of the material used to prepare the
membrane. In Fig. 4 we also report the electrophoretic mobility of the CoA1204 powder material
in the presence of the same salts. The comparison
of the SP and mobility variations are quite different, which confirms the surface charge determined from powder mobility and SP measurements are not similar for the same material.

211

S. Condom et al. / Desalination 168 (2004) 207-213


3.4. p H effects on salt rejection
* NaC1

CaCI2

Na2SO4 CaSO4
3

(a)

"~1

-2

pH
6
cNaC1 nC~J2 AI'4t2SO eC~04

pH

9 ~

-2

(b)
.4

Fig. 3. Evolution of the streaming potential measured


through the membranes vs. pH for different electrolytes
(C = 10-3 moLL-l). (a) COA1204,membrane, (b) TiO2 +
ZnA1204 membrane.
[]

.7 1

The variation of the rejection rates of the different salts is reported in Fig 5 where we also
observed that it depends on the pH of the filtered
solution; this is the consequence of the electrical
interactions developed between the ions and the
surface charges of the membrane. For the
CoAI204 and TiOz/ZnAI204 membranes, the
rejection rates of the neutral salts associating a
monovalent anion and a cation (mono or divalent)
decrease when the pH values increase; nevertheless, no great changes of R was observed for
CaC1a between pH 4 and pH 8. On the contrary,
the rejection rates of Na2SO4 were very low in
acid medium, but they increase for higher pH
values. Those behaviours may be explained
taking into account the evolution of the SP
measured for the filtered salts. For the positive
values of the SP, the rejection of the salts is
relatively high and it decreases as the SP value
decreases. When the pH of the solution reaches
the pH value where the charge of the membrane
is zero (SP = 0), the rejection becomes very low
and then increases for the pH values where now
the membrane is negatively charged. In the case
of the filtration of CaC1z solutions, we observed
only the decrease of the rejection, which is also in
agreement with the SP variations. This proves
that the surface charge of the membrane remains
120
10o

.,.,
-3

20
-4

0
-5

12

pH
Fig. 4. E l e c t r o p h o r e t i c m o b i l i t i e s o f C o A l 2 0 4 particles vs.
p H for d i f f e r e n t e l e c t r o l y t e s ( C = 10 -3 mol.L-~).

Fig. 5. Evolutionof the rejection of salts (C = 10-3M) vs.


p H for t h e TiOffZnA1204 m e m b r a n e .

212

S. Condom et aL / Desalination 168 (2004) 207-213

positive in the pH range studied. This phenomenon is probably due to the strong specific
adsorption of the Ca 2+ ion at the surface of the
membrane whatever the pH of the solution
according to the surface equilibria complexation:
Acid pH:
MOH~ + C a 2+ -* MO-,Ca 2+ + 2H +
Basic pH:
M O - + Ca 2+ -. MO-, Ca 2+
Generally the correlation between the rejection values and the SP determinations are more
satisfying than with the mobilities obtained from
the electrophoretic measurements performed with
the powder suspension (Figs. 3 and 5).
For the filtration of salts that are not neutral, it
is necessary to consider their acid-base properties. This is the case of the phosphate salts where
the charge of the anion depends on the pH of the
filtered solution. The results of the experiments
performed with the COA1204 membrane are
reported in Fig. 6. The rejection of the sodium
phosphate is very low at pH under 5, and the
corresponding SP of the membrane is also weakly
negative. The comparison with the SP obtained
with the NaCI salt for the acid pH proves the
adsorption of the phosphate ion on the surface,

60

o~

sodiu
p h

-1 >~

n~ 40

-2 u~

20

-3

0
2

10

-4
12

pH

Fi 8. 6. Evolution o f the SP and o f the rejection o f sodium


phosphate (C = 10 -3 mol.L -I) vs. pH for the CoAI204
membrane.

which then decreases its charge according to the


complexation equilibrium.
MOH2+ + H2PO4 -

(MOH;, H2PO4)

Between pH 5 and 8, an increase of the rejection can be observed whereas the SP becomes
more and more negative. These results are in
agreement with the change of H2PO4 to HPO4zanion bearing two negative charges and the
development of strong interactions between the
divalent anion phosphate and the negative surface
charge of the membrane.

4. Conclusions

The efficiency of a filtration process depends


on the complexity of the filtered solution. In the
case of an ionic solution, the steric and electrical
interactions are the two main parameters which
must be considered. The steric effect depends on
the stability of the formed complex between the
cation and the ligand. For simple electrolytes, the
rejection depends on the electrical interactions,
which are controlled by the surface charge
developed on the filtering material. Generally, the
streaming potential measurement across the membrane seems to be a good parameter to predict the
rejection rates of the salt instead of electrophoretic powder mobility, which sometimes is not
in agreement with salt rejection.

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S. Condom et al. / Desalination 168 (2004) 207-213

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