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ELSEVIER
www.elsevier.com/locate/desal
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.
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.
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
2. Experimental
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
209
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.
210
.....~-:.
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.
(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
CaCI2
Na2SO4 CaSO4
3
(a)
"~1
-2
pH
6
cNaC1 nC~J2 AI'4t2SO eC~04
pH
9 ~
-2
(b)
.4
.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-~).
212
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
(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
References
[1] T. Tsuru, Hirohiko Takezoc and Masashi Asaeda,
Ion separation by porous silica zirconia nanofiltration
membranes, AichE J., 44 (1998) 765.
[2] A.E. Yaroshchuk, Rejection mechanisms of nano-
213