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6 authors, including:
Karel Ghyselbrecht
Boudewijn Meesschaert
University of Leuven
University of Leuven
SEE PROFILE
SEE PROFILE
Laboratory for Microbial and Bio-Chemical Technology, Faculty of Engineering Technology, KU Leuven e Kulab, Zeedijk 101, B-8400 Oostende, Belgium
Instituto Superior de Engenharia do Porto, Mestrado em Engenharia Qumica, Rua Dr. Antnio Bernardino de Almeida 431, 4200-072 Porto, Portugal
Department of Chemical Engineering, ProcESS e Process Engineering for Sustainable Systems, KU Leuven, W. de Croylaan 46, B-3001 Leuven, Belgium
d
Umicore NV, Watertorenstraat 33, B-2250 Olen, Belgium
e
Department of Microbial and Molecular Systems, Cluster for Bio-engineering Technology, KU Leuven, Kasteelpark Arenberg 23, B-3001 Leuven, Belgium
f
Laboratory for Chemical Process Technology, Faculty of Engineering Technology, KU Leuven e KAHO St.-Lieven, Gebroeders De Smetstraat 1,
B-9000 Gent, Belgium
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 31 October 2013
Received in revised form
24 February 2014
Accepted 6 March 2014
Available online 12 April 2014
The industrial implementation of alternative technologies in the processing of saline efuent streams is a
topic of growing importance. In this technical feasibility study, the desalination of an industrial saline
stream containing about 75 g L1 NaCl contaminated with some organic matter using bipolar membrane
electrodialysis (EDBM) was investigated on lab-scale. Bipolar membranes of two different manufacturers
(PCA e PolymerChemie Altmeier GmbH and FuMA-Tech GmbH) were tested and compared in terms of
electrical resistance, current efciency and purity of the produced acid and base stream. In both cases,
almost complete desalination (>99%) was achieved and simultaneously HCl and NaOH were produced
with a concentration between 1.5 and 2 M with a relatively good purity. The Fumasep bipolar membranes scored slightly better for electrical resistance and current efciency. On the other hand, slightly
higher current densities were achieved with PCA bipolar membranes. Simultaneously, some information
was obtained on the transport behavior of the organic matter present in the saline stream. It was
observed that a transport competition occurred between the organic matter and the accompanying
chlorides. From this lab-scale study it was concluded that EDBM is a promising and attractive technology
in the area of saline efuent reclamation and reuse.
2014 Elsevier Ltd. All rights reserved.
Keywords:
Desalination
Feasibility
Bipolar membrane electrodialysis
Organic matter
Efuent reclamation
1. Introduction
Contamination of natural waters by industrial saline efuents is
an important environmental problem in industrialized nations.
This is caused by the rapid industrial expansion especially in the
petrochemical, pharmaceutical, food and chemical industries
(Lefebvre and Moletta, 2006). Therefore, efuent reclamation and
reuse have received much attention lately, owing to diminishing
natural water resources, wastewater disposal costs, and stricter
environmental regulations, guidelines and policies that ensure
acceptable discharge of such efuents (IWMI, 2006; Mann and Liu,
1999; Miller, 2006).
70
Table 1
Summary of the experimental conditions.
Purpose
Acid e base
Electrode rinsing
solution
Limiting currenta
Desalination exp.b
a
b
71
4L initial diluate.
2L initial diluate.
hA
DmA t=MA zF
100%
nIDt
(1)
Fig. 1. Schematic diagram of the EDBM setup and one cell trio conguration. BM
stands for one of the two types of bipolar membranes; SK stands for standard cationexchange membrane and Acid 60 for anion-exchange membrane suitable for the
production of HCl.
(Adapted from Ghyselbrecht et al., 2013).
Table 2
Characteristics of the saline feed water.
pH ()
Conductivity
(mS cm1)
Cl
(g L1)
Na
(g L1)
Ca2
(mg L1)
TOC
(mg C L1)
TIC
(mg C L1)
12.6
101.9
41
33
<DL
132
10
72
Fig. 2. Determination of the limiting current density for the various desalination degrees using the membrane combination (A) Acid 60/PBM/SK and (B) Acid 60/FBM/SK.
value is found for 99% and 95% desalination. For the membrane
combination Acid 60/PBM/SK (Fig. 2A) the limiting current density
is 0.016 and 0.031 A cm2, respectively. For the membrane combination Acid 60/FBM/SK (Fig. 2B) the limiting current density is
0.015 and 0.023 A cm2, respectively. The slightly higher current
densities, obtained with the membrane combination Acid 60/PBM/
SK, offer a slight advantage for the bipolar membranes of PCA.
Nevertheless, it is noted that the electrical resistances that are
obtained using the membrane combination Acid 60/FBM/SK are
slightly lower than those using the membrane combination Acid
60/PBM/SK. As both experiments were performed under analogous
circumstances (Table 1), the cause should be related to the use of
different types of bipolar membranes.
Secondly, a desalination experiment was carried out for both
membrane combinations under analogous circumstances. The
objective was to desalinate the saline feed water as much as
possible and to simultaneously produce an acid and a base as
concentrated and pure as possible. Therefore, an initial acid and
base concentration of 0.5 M HCl and 0.6 M NaOH, respectively, were
chosen. In this way, both of these circuits were sufciently
conductive at the start and it should be possible to produce HCl and
NaOH with a nal concentration of 2 M. The concentration prole of
chloride in the diluate and acid compartment and the concentration prole of sodium in the diluate and base compartment are
given in Figs. 3 and 4, respectively. After 270 min, the concentration
reduction of Cl in the diluate for the desalination experiment with
the Fumasep and PCA bipolar membranes is 99.7% and 99.8%,
respectively; while the concentration reduction of Na is 99.7% and
99.9%, respectively. The desalination rate was thus for both membrane combinations similar; in both cases almost complete desalination was already achieved after 180 min.
From Figs. 3 and 4, it is clear that almost all the chloride and the
sodium were removed from the diluate. As expected, the chloride
ions ended up in the acid compartment whereas the sodium ions
ended up in the base compartment. After 270 min, the concentration of the HCl and NaOH produced with the Fumasep bipolar
membranes reached 1.8 M and 2 M, respectively. With the PCA
bipolar membranes HCl and NaOH were produced with a concentration of 1.6 M and 1.7 M, respectively. Despite the concentration
difference between both membrane combinations the maximum
concentration of acid and base was achieved as complete desalination of the diluate was realized in both cases. So, in terms of acid
and base production the performance of both membrane combinations is considered to be similar.
Fig. 3. Concentration prole of chloride in diluate and acid as a function of time during
a desalination experiment carried out with two different types of bipolar membranes.
73
Table 4
Average current efciencies and mean current densities for the rst 180 min and for
the entire desalination experiment for both membrane combinations.
Fig. 4. Concentration prole of sodium in diluate and base as a function of time during
a desalination experiment carried out with two different types of bipolar membranes.
Acid 60/FBM/SK
Acid 60/PBM/SK
Cl
Na
iaverage (A m2)
Cl
Na
iaverage (A m2)
108
79
104
84
689
523
89
61
93
69
769
572
Table 3
Impurities in the HCl and NaOH produced during the desalination experiment for
both membrane combinations.
Membrane combination
Na in HCl
produced (mol/mol %)
Cl in NaOH
produced (mol/mol %)
Acid 60/FBM/SK
Acid 60/PBM/SK
3.1
3.1
0.5
0.6
74
Fig. 6. Concentration proles of TOC in acid and base as a function of time during a
desalination experiment carried out with two different types of bipolar membranes.
examined during a short-term batch experiment using a comparison of concentration proles. It was observed that in the
beginning the organic fraction (expressed as TOC) was retained
in the diluate. However, when the chlorides were depleted in the
diluate the TOC concentration started to decrease signicantly in
the diluate and migrated mainly towards the acid compartment
meaning that the organic matter was negatively charged in this
case. However, further research needs to be addressed to detect
organic adsorption rates onto the anion-exchange membranes
and their inuence on the overall EDBM performance by means
of long-term investigations. In conclusion, EDBM is an attractive
technology that has an environmental value in saline efuent
reclamation and reuse. It is a good combination of brine minimization through water desalination and valuable ion recovery
through chemical production (acids and bases).
Acknowledgements
The authors acknowledge nancial support through the InToBiMem project (MIP-ICON Project 110293) from the Environmental
and Energy Innovation Platform (Het Milieu-en energietechnologie Innovatie Platform, MIP e Flemish Government).
Mieke Ghyselbrecht is acknowledged for her efforts on the English
grammar check.
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