Environmental Engineering and Management Journal August 2012, Vol.11, No.

8, 1485-1491
http://omicron.ch.tuiasi.ro/EEMJ/

“Gheorghe Asachi” Technical University of Iasi, Romania

ELECTROCOAGULATION TREATMENT OF SULFIDE WASTEWATER

IN A BATCH REACTOR: EFFECT OF ELECTRODE MATERIAL ON
ELECTRICAL OPERATING COSTS

Marius Sebastian Secula, Igor Creţescu, Stelian Petrescu

“Gheorghe Asachi” Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection,
73 Prof. Dr. Docent Dimitrie Mangeron, 700050 Iasi, Romania

Abstract

An experimental study on the separation of sulfides from aqueous solution by electrocoagulation is described in this work. Two
types of anode materials, aluminum and mild steel, were investigated in relation to anodic dissolution, removal efficiency and
energy consumption. Experiments were carried out under galvanostatic regime at different values of current density. During the
experiments, the pH was monitored and adjusted in order to maintain near neutral pH values. By weighing the anodes before and
after electrocoagulation and based on Faraday’s law, electrochemical and chemical dissolved weights were determined. Specific
energetic consumptions related to sulfide ions and electrical operating costs were calculated. In comparison with aluminum, iron-
based anode provides higher removal efficiencies, lower energy requirements and electrical operating costs. The complete
removal of sulfide ions from the treated solution was achieved after 45 min of electrocoagulation at a current density of 65.79
Am-2 using mild steel as anode.

Key words: anodic dissolution, batch reactor, electrical operating cost, electrocoagulation, sulfide wastewater

Received: September, 2010; Revised final: September, 2011; Accepted: October, 2011

1. Introduction shown that electrocoagulation-generated flocs are

In the last few decades, electrocoagulation has
regained the interest of scientists especially due to its
“green technology” characteristics and a more
thorough understanding of the mechanisms standing
at the basis of electrocoagulation processes
(Bayramoglu et al., 2007; Dermentzis et al., 2011;
Poulton et al., 2002) .
At present, the increase of electrocoagulation
efficiency by the substantial reduction of energy
consumptions has led to electrocoagulation processes
that are faster and more economical than the classical
chemical coagulation process (Bayramoglu et al.,
2007; Can et al., 2006; Canizares et al., 2007;
SenthilKumar et al., 2010). Likewise, it has been
relatively bigger, have less water and are more stable
than those obtained by the classic chemical method
of coagulation (Holt et al., 2002).
Leather and paper industries are known to
produce heavily polluted wastewater containing
important loading of sulfide ions. The acute toxicity
of hydrogen sulfide and its effects on the respiratory,
cardiac and nervous systems have been stated (NRC
Canada, 1981).
Hydrogen sulfide-polluted wastewaters are
generally treated by oxidation methods. With this
aim, several oxidants such as molecular oxygen
(Tomar and Abdulah, 1994), hypochlorites, chlorine,
potassium permanganate (Cadena and Peters, 1988)
and hydrogen peroxide (Millero et al., 1989) have


Authors to whom all correspondence should be addressed: E-mail: mariussecula@ch.tuiasi.ro; icre@ch.tuiasi.ro; Phone: +40 - 232 278683;
Fax: +40 - 232 271311
 Secula et al./Environmental Engineering and Management Journal 11 (2012), 8, 1485-1491
been used. Nevertheless, removal of sulfide ions
from seawater was found to be adequate by using
Fe(III) oxides (Poulton et al., 2002).
In literature, a very limited number of papers
approaching the study of sulfide-polluted wastewater
treatment by electrochemical methods have been
reported so far. Among these, a category is based on
the anodic oxidation of sulfide ion to sulfate ion
(Waterson et al., 2007), since the environmental
regulation are more restrictive as regards sulfides,
and a second category is related to the
electrocoagulation of tannery wastewaters (Apaydin
et al., 2009; Feng et al., 2007; Murugananthan et al.,
2004).
According to our knowledge, there has not
been reported yet any study approaching the sulfide
removal by electrocoagulation processes conducted
under controlled optimal pH conditions. Moreover,
though the electrical energy consumption is a
fundamental economical parameter in
electrocoagulation processes, only a single work
(Apaydin et al., 2009) reported the specific energy
consumptions for sulfide removal by
electrocoagulation using iron-based electrodes.
In the present work, an experimental study
approaching the electrocoagulation of sulfide
wastewater in batch reactor using aluminum or iron-
based anodic electrodes, operated under galvanostatic
regime, is presented. The main purpose of this study
is to point out the influence of electrode material and
current density on the removal efficiencies, specific
energy consumption and electrical operating costs of
this electrocoagulation process.
2. Experimental
The 4.4 mM S2- aqueous solutions were
prepared by dissolving sodium sulfide (A.R. Fluka,
Buchs, Switzerland.) in ultrapurified water. This was
obtained by means of a Barnstead Easypure II
Thermo Scientific water purifier. The pH of the
synthetic sulfide wastewater was adjusted by means
of 0.1 N H2SO4 and NaOH solutions. To improve the
conductivity, NaCl (A.R. Lach-Ner, Neratovice,
Czech Republic) was dissolved into sulfide synthetic
solutions.
Preliminary tests performed to determine the
optimal concentration of the support electrolyte lead
to the conclusion that 3.42 mM NaCl represent the
minimum optimal concentration in relation to the
conductivity conditions. Though higher
concentrations might lead further to the enhancement
in conductivity, one has to take also into account the
final chloride load of the treated solution.
The investigations were carried out with the
experimental set-up described in Fig. 1.
The experimental set-up consists in an
electrolytic cell composed of two electrodes
connected to a DC STR 404 power supply, able to
provide an adjustable voltage in the range of 040 V.
The solution homogeneity was ensured using a
magnetic stirrer.
1486
The solution pH was monitored by means of a
glass pH electrode connected to a pH-meter. Also,
the pH was adjusted continuously during
electrocoagulation. The electrical circuit consists in a
STR 404 voltage regulator supply, an ammeter and
the electrical cell in series with a high value resistor
(2.5 kOhm) in order to maintain a current of constant
intensity. All of the runs were carried out at room
temperature.
Fig. 1. Experimental set-up
The electrocoagulation cell consisted in a
glass recipe having a length of 0.11 m, a width of
0.10 m, and a height of 0.19 m. A stainless steel plan
plate was used as cathode. The anode was either an
aluminum plan plate or a mild steel plan plate with
an effective surface of 7.586103 m2. The distance
between electrodes was of 7 mm for all tests. The
electrodes were thoroughly cleaned before each
experiment.
In order to estimate the sulfide (S2−) content,
the spectrophotometric method was used (SR ISO
10530, 1997).
The pH measurements of treated solutions
were performed by means of a CONSORT C831
Multi-parameter analyzer. Gravimetric measurements
of electrodes were performed with a Precisa XT 22A
digital balance (0.1 mg accuracy) before and after
electrocoagulation tests.
Equipment and method used to determine the
polarization curves was described in detail in our
previous work (Petrescu et al., 2009).
3. Results and discussion
Polarization curves obtained at aluminum and
iron dissolution respectively in aqueous solutions of
sodium chloride and sulfide solutions are shown in
Fig. 2. Compred to aluminum anode, the increase of
current density is accelerated especially at higher
values of overpotential in case of iron dissolution.
This is due to the formation of a passivating film on
the aluminum anode at overpotential values higher
than approximately 3 V. However, the investigations
discussed herein further were carried out at
overpotential values lower than 0.5 V so that the two
 Electrocoagulation treatment of sulfide wastewater in a batch reactor
anode materials to be compared within the range of
similar polarization behavior.
-2
i, A m
Fe
1000
Al
500
0
0 1 2 3 4 5 ,
Fig. 2. Variation of current density with anodic
overpotential at iron and aluminum dissolution respectively
in aqueous solution of 3.42 mM NaCl and 4.4 mM S2- at
neutral pH
3.1. Aluminum anode and stainless steel cathode
electrode configuration
Using this electrode configuration, several
experiments were carried out at three different values
of current density (9.31, 26.37 and 65.79 A.m-2).
Taking into consideration that the generation of
Al(OH)3 is favored within the pH range from 6 to 8.5,
it was aimed at maintaining the pH value near the
neutral value. This parameter increases during
electrocoagulation process. Therefore, the pH value
was adjusted by adding appropriate volumes of 0.1 N
H2SO4 solution during each run. In Fig. 3 is shown
the variation of pH and cell voltage during
electrocoagulation using an aluminum anode under
the specified conditions.
Fig. 3. Evolution of pH and cell voltage during
electrocoagulation using aluminum anode
(i = 26.37 Am-2)
The voltage of electrochemical cell decreases
during the process. Thus, for maintaining the current
in order to apply a current density of 26.37 Am-2, the
cell voltage was adjusted from a starting value of
4.85 to 3.8 V near the end of process.
Leading to a reduction of the cell voltage, the
increase in conductivity is partly explained by the
metal anodic dissolution process and by the addition
of sulfate ions for the pH control.
Fig. 4 shows the evolution of removal
efficiency related to sulfide ion by electrocoagulation
using aluminum anode.
V
Fig. 4. Variation of removal efficiency at the
electrocoagulation of sulfide synthetic solution, 3.42 mM
NaCl, aluminum electrode, at different current densities
An enhanced increase of the removal
efficiency of sulfide ion with current density can be
noticed. After 60 min, the removal efficiencies are
15.66 % for a density current value of 9.21 Am-2,
28.86 % for 26.37 Am-2, and 49.71 % in case of
65.79 Am-2.
At the aluminum dissolution in neutral
medium, it was observed the formation of white
flocs. This is in agreement with the chemical
mechanism described in literature (Murugananthan et
al., 2004). At a density current of 9.21 A m-2, the
formed white flocs are separated by sedimentation,
while at 26.37 A m-2, the resulted flocs separate in a
considerable ratio by flotation. When a 65.79 Am-2
density current was applied, it was noticed that the
flotation became the main separation process of the
generated flocs.
3.2. Mid steel anode and stainless steel cathode
electrode configuration
In Fig. 5 are shown the variations of pH and
cell voltage at different values of current density
during the electrocoagulation of 4.4 mM S2- solution
using mild steel anode.
As shown in Fig. 5a, the pH of synthetic
sulfide solution was adjusted during
electrocoagulation in order to maintain the pH values
in the range of 5 and 7 where the precipitation of FeS
is favored. However, in selecting the optimal range
of the pH parameter, the potential development of
hydrogen sulfide at acid values of pH was also
1487
 Secula et al./Environmental Engineering and Management Journal 11 (2012), 8, 1485-1491
considered. Thus, in the experimental runs the pH
value was adjusted to near neutral values.
(a)
(b)
Fig. 5. Evolution in time of pH (a) and cell voltage (b) for
iron dissolution in aqueous sulfide solution, at different
current densities
Similar to the case of aluminum anodes, the
cell voltage decreased during iron dissolution in
sulfide solution (Fig. 5b). The higher the current
applied, the steeper the decrease of cell voltage. Fig.
6 shows the removal efficiencies of sulfide ions in
solution by electrocoagulation based on mild steel
anode.
Fig. 6. Variation of removal efficiency during
electrocoagulation of sulfide synthetic solution, using mild
steel anode, for different values of current density
1488
Compared to electrocoagulation using
aluminum anode, higher values of removal efficiency
related to sulfide ion were obtained in case of mild
steel anode. Thus, applying currents of 9.21 and
26.37 Am-2 removal efficiencies of 42.85 and 59.49
respectively were achieved. The highest removal
efficiency of 100 % was obtained after approximately
45 min for a current density of 65.79 Am-2.
Iron dissolution in sulfide aqueous solutions
results mainly in iron sulfide that precipitates in the
pH range of 5-7 (Zaharia, 2006). Before
sedimentation, it was noticed that the treated
solutions with mild steel anode are black colored due
to the FeS formed.
3.3. Electrochemical vs. chemical dissolution of
anodes
The mass of metal dissolved through
electrochemical mechanism can be calculated
according to Farraday’s law by means of Eq. (1):
w  I  t  M / n  F  (1)
where: w is the weight of metal dissolved through
electrochemical mechanism, g; I - current intensity,
A, t – time, s; M – relative molar mass of electrode
material, gmol-1; n – number of electrons involved in
oxidation/reduction reaction; F – Faraday’s constant,
Cmol-1.
Taking into account that the values of anode-
mass dissolved were found to be considerable higher
than those predicted by Faraday’s law (Table 1), the
mass difference was assigned to chemical dissolution
process (Donini et al., 1994). These super-faradaic
efficiencies have already been reported in the
literature (Canizares et al., 2005) and explained in
terms of chemical dissolution.
However, especially at high current densities,
the electrochemically dissolved mass is lower than
that calculated by means of Faraday’s law due to an
important part of the measured current is consumed
in water electrolysis leading to the development of
oxygen bubbles. Hence, the contribution of the
chemically dissolved mass might be slightly higher
than the values presented in Table 1. The ratio of
electrochemical dissolution, f, was considered in
order to approximate the total consumption of
electrode material during electrocoagulation.
3.4. Energy consumption and electrical operating
costs
The energy consumption related to the amount
of removed sulfide, named herein further as unit
energy demand (UED), was determined. Since the
current intensity was kept constant and cell voltage
varied during electrocoagulation process, the
following relationship was used (Eq. 2):
 Electrocoagulation treatment of sulfide wastewater in a batch reactor

Table 1. Electrochemical and chemical mass dissolved after 60 min of electrocoagulation of 4.mM sulfide and 3.42 mM NaCl
solutions

Total dissolve Electrochemical Chemical

Run Anode Mean i
mass dissolved mass dissolved mass f
No. material pH
Am2 g g % g %
1 6.8 9.21 0.146 0.073 50 0.073 50 0.50
2 Mild steel 6.4 26.37 0.240 0.208 87 0.032 13 0.87
3 6.4 65.79 0.623 0.521 84 0.102 16 0.84
4 6.7 9.21 0.028 0.023 82 0.005 18 0.82
5 Aluminum 6.8 26.37 0.085 0.067 79 0.018 21 0.79
6 6.5 65.79 0.199 0.168 84 0.031 16 0.84

(a) (b)

Fig. 7. Evolution of UED during electrocoagulation of sulfide solutions using mild steel (a) or aluminum (b) anode, at different
current densities, CNaCl = 3.42 mM

t
 Y 
UED  I   U  dt
(2)
1000  V  C0  t 
 100 
0 anode. After 60 min of electrocoagulation applying a
where: UED is the unit energy demand, kWhkg-1; I –
U –cell voltage, V, I - current intensity, A, t – time,
h, C0 – the initial concentration of sulfide, kgm-3, V –
volume of treated solution, m-3; Yt – removal
efficiency at time t, %.
Fig. 7a describes the influence of current
density over the unit energy demand when iron-based
anode is employed.
Energy consumption related to sulfide
removed increases with the increase of current
density. However, at 65.79 Am-2, UED presents a
minimum value of 23.36 kWhkg-1 that corresponds
to a removal efficiency of approximately 95 % after
40 min of electrolysis.
Apaydin et al. (2009) reported recently a UED
value of 108.75 kWhkg-1, after 30 min at the
electrocoagulation of a tannery wastewater
containing 440 mgL-1 of sulfides with a removal
efficiency of 97 %. The considerable improvement of
UED value reported in the present work might be
attributed to the distance between the electrodes. In
this study, the interelectrode distance was of 0.7 cm
compared to that of 6 cm reported in the study of
Apaydin et al. (2009).
Fig. 7b pinpoints an important increase of
UED value with the increase in current density. Also,
it can be noted that the highest values of UED were
recorded for the cell configuration using aluminum
current density of 26.37 Am-2, UED values of 10.35
kWhkg-1 for Fe and 32.05 kWhkg-1 for Al anode
were obtained.
The operational cost of any effluent treatment
method is an important criterion to evaluate its
applicability at industrial scale. The electrical
operating costs of the electrocoagulation of synthetic
sulfide wastewater can be calculated by considering
the amount of energy consumption and anode
material consumed (Eq. 3). Material consumed can
be estimated by means of Eq. (4).
EOC  EEC  MC  UED  EEP  MC (3)
where: EOC is the electrical operating cost, $kg-1 of
sulfide removed; EEC –electrical energy
consumption, $kg-1 of sulfide; EEP – electrical
energy price, $kWh-1.
MC  I  t  A  AMP  f  n  F  V  C0  Yt 100  (4)
where: MC is the cost of anode material consumed
during electrocoagulation, ($kg-1 of sulfide
removed); AMP – anode material price, $g-1, f – ratio
of electrochemical dissolution.

1489
 Secula et al./Environmental Engineering and Management Journal 11 (2012), 8, 1485-1491

Table 2. Electrical operating costs of sulfide removal by electrocoagulation after 60 min

Run Anode Mean i Y EEC MC EOC

No. material pH Am2 % $kg-1 $kg-1 $kg-1
1 Mild steel 6.8 9.21 42.85 0.43 7.48 7.91
2 6.4 26.37 59.49 1.04 8.65 9.69
3 6.4 65.79 100.00 3.16 18.69 21.84
4 Aluminum 6.7 9.21 15.67 0.58 12.56 13.13
5 6.8 26.37 28.86 3.20 14.24 17.45
6 6.5 65.79 49.71 8.51 21.32 29.83

Electrical operating costs can also be
expressed in relation to the volume of wastewater
treated by removing C0  Yt 100 term in the
expressions of UED (2) and MC (4).
In order to determine these electrical
operational costs, economical data were gathered
from the EU market in 2011. Thus the electrical
energy price for industrial use is averaged to 0.1
$kWh, while mild steel and aluminum were
estimated at 1.0 $kg-1 and 2.0 $kg-1 respectively.
Values of the electrochemical dissolution
ratio, f, were considered from Table 1.
Data of electrical operational costs for sulfide
removal by electrocoagulation for 60 min for
aluminum or iron dissolution are presented in Table
2. It can be noticed that electrical energy cost is much
higher in case of aluminum anode material compared
to mild steel material. The cost of electrode material
dissolved during the process is significantly higher
than electrical energy cost. As shown, electrical
energy costs related to the amount of sulfide removed
are relatively lower in case of iron-based anode
material.
In Fig. 8 is illustrated the evolution in time of
removal efficiency and EOC expressed in relation to
the volume of wastewater treated under the specified
experimental conditions.
min of electrolysis which corresponds to EEC = 0.34
$m-3, MC = 0.76 $m-3, EOC = 1.10 $m-3.
4. Conclusions
An experimental study on sulfide wastewater
treatment by electrocoagulation in a batch reactor
was presented. The influences of anodic materials on
the removal efficiency, energy and material
consumptions, and electrical operating costs were
investigated for the separation of sulfide ion from
aqueous solutions under neutral pH and galvanostatic
conditions, at several current densities.
The maximum removal efficiency (100 %)
related to sulfide ion was achieved after 45 min of
electrocoagulation using mild steel anode, for a
density current of 65.79 Am-2.
It was pointed out that iron-based anode
provides higher removal efficiencies, and presents
lower values of specific energy consumption and
electrical operating costs compared to aluminum
anode.
The removal of sulfide ions from aqueous
solution by means of electrocoagulation using iron-
based anode, under the optimal pH conditions,
proved to be an efficient and cheap technology.
Aknowledgments
This work was supported by CNCSIS-UEFISCSU, project
number PN II-RU 52/2010, COD 44.

References

Apaydin Ö., Kurt U., Gönüllü M.T., (2009), An

Fig. 8. Variation of electrical operating costs during
electrocoagulation (anode: mild steel, i = 65.79 Am-2,
CNaCl = 3.42 mM)
Working at 65.79 Am-2 for 60 min, the
operational cost for the electrocoagulation reactor
with mild steel anode increases up to 1.45 $m-3. The
complete removal of sulfide was achieved after 45
investigation on the treatment of tannery wastewater
by electrocoagulation, Global NEST Journal, 11, 546-
555.
Bayramoglu M., Eyvaz M., Kobya M., (2007), Treatment
of the textile wastewater by electrocoagulation
Economical evaluation, Chemical Engineering
Journal, 128, 155–161.
Cadena F., Peters R.W.J., (1988), Evaluation of chemical
oxidizers for hydrogen sulfide control, Journal of the
Water Pollution Control Federation, 60, 1259-1263.
Can O.T., Kobya M., Demirbas E., Bayramoglu, M.,
(2006), Treatment of the textile wastewater by
combined electrocoagulation, Chemosphere, 62, 181–
187.
Canizares P., Carmona M., Lobato J., Martinez F., Rodrigo
M.A., (2005), Electrodissolution of aluminum
electrodes in electrocoagulation processes, Industrial
& Engineering Chemistry Research, 44, 4178-4185.

1490
 Electrocoagulation treatment of sulfide wastewater in a batch reactor
Canizares P., Martınez F., Jimenez C., Saez C., Rodrigo
M.A., (2009), Technical and economic comparison of
conventional and electrochemical coagulation
processes, Journal of Chemical Technology &
Biotechnology, 84, 702–710.
Dermentzis K., Marmanis D., Valsamidou E.,
Christoforidis A., Ouzounis K., (2011),
Electrochemical decolorization treatment of nickel
phthalocyanine reactive dye wastewater,
Environmental Engineering and Management Journal,
10, 1703-1709.
Donini J.C., Kan J., Szynkarczuk J., Hassan T.A., Kar
K.L., (1994), Operating cost of electrocoagulation,
The Canadian Journal of Chemical Engineering, 72,
1007-1012.
Feng J.W., Sun Y.B., Zheng Z., Zhang J.B., Li S., Tian
Y.C., (2007), Treatment of tannery wastewater by
electrocoagulation, Journal of Environmental
Sciences, 19, 1409-1415.
Holt P.K., Barton G.W., Wark M., Mitchell C.A., (2002),
A quantitative comparison between chemical dosing
and electrocoagulation, Colloids and Surfaces A, 211,
233–248.
Millero F.J., Le Ferriere A., Fernandez M., Hubinger S.,
Hershey J.P., (1989), Oxidation of hydrogen sulfide
with hydrogen peroxide in natural waters,
Environmental Science & Technology, 23, 209-213.
Murugananthan M., Raju G.B., Prabhakar S., (2004),
Removal of sulfide, sulfate and sulfite ions by
electrocoagulation, Journal of Hazardous Materials,
109, 37-44.
NRC, (1981), Hydrogen sulfide in the atmospheric
environment: scientific criteria for assessing its effects
on environmental quality, NRCC NO 18467,
Associate Committee on Scientific Criteria for
Environmental Quality, Ottawa.
Petrescu S., Secula M.S., Cretescu I., Nemtoi G., (2009),
Study on metal anodic dissolution, Revista de Chimie
(Journal of Chemistry, Bucharest), 60, 462-467.
Poulton S.W., Krom M.D., Van Rijn J., Raiswell R.,
(2002), The use of hydrous iron (III) oxides for the
removal of hydrogen sulphide in aqueous systems,
Water Research, 36, 825-834.
SenthilKumar P., Umaiyambika N., Gayathri R., (2010),
Dye removal from aqueous solution by
electrocoagulation process using stainless steel
electrodes, Environmental Engineering and
Management Journal, 9, 1031-1037.
SR ISO 10530, (1997), Water quality. Determination of
dissolved sulfides. Photometrical method with
methylene blue.
Tomar M., Abdulah T.H.A., (1994), Evaluation of
chemicals to control the generation of malodorous
hydrogen sulfide in wastewater, Water Research, 28,
2545-2552.
Waterston K., Bejan D., Bunce N.J., (2007),
Electrochemical oxidation of sulfide ion at a boron-
doped diamond anode, Journal of Applied
Electrochemistry, 37, 367-373.
Zaharia C., (2006), Chemical Wastewater Treatment,
Performantica Press, Iaşi, Romania.
1491