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Corresponding author. Tel.: +90 262 6053174; fax: +90 262 6053200.
E-mail address: abdakyol@gyte.edu.tr (A. Akyol).
Separation and Purication Technology 112 (2013) 1119
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processes as compared to the conventional methods are easy to
operate, less retention time, lower operating costs, reduction (in
the EF process) or absence of adding chemicals (in the EC process),
rapid sedimentation of the electrogenerated ocs and less sludge
production and requires a simple equipment.
Aim of the present study was to investigate the removal of LOF
manufacturing wastewater (LFW) by the electrocoagulation (EC)
and electro-Fenton (EF) processes using iron electrodes in a batch
mode operation. The effects of operating parameters such as pH
i
,
current density, operating time and dosage of H
2
O
2
for EC and EF
processes on the removal efciencies of LFWwere studied to deter-
mine the optimum operating conditions. Operating costs and char-
acterizations of anode sludge from the EC and EF processes were
also performed.
2. Removal mechanisms of electrocoagulation and electro-
Fenton
The electrocoagulation (EC) process involves generation of
coagulants in situ by dissolving sacricial anodes such as alumi-
num or iron upon application of a direct current. When iron elec-
trode is used as anodes upon oxidation in an electrolytic system,
it produces iron hydroxide, Fe(OH)
n
where n = 2 or 3 [25,26]:
Fe !Fe
2
2e
anode 1
2H
2
O 2e
!H
2
2OH
cathode 2
Fe
2
2OH
!FeOH
2
in bulk solution 3
2Fe
2
5H
2
O1=2O
2
!2FeOH
3
4H
in bulk solution 4
Fe
3
3OH
!FeOH
3
in bulk solution 5
Ferric ions generated by the EC process may form monomeric
and polymeric hydroxyl complexes (i.e., hydrolysis products)
namely, FeOH
2
; FeOH
2
; FeOH
4
2
; FeOH
4
; FeH
2
O
3
2
; Fe
H
2
O
3
6
; FeH
2
O
5
OH
2
; FeH
2
O
4
OH
2
; FeH
2
O
8
OH
4
2
; Fe
2
H
2
O
6
OH
2
4
, etc. depending on pH of the aqueous medium. The com-
plexes have a pronounced tendency to polymerize at pH 3.57.0.
Fe(OH)
n
remains in the aqueous stream as a gelatinous suspension
and may be removed from the wastewater by coagulation, adsorp-
tion, co-precipitation and sweep occulation [27].
In the EF process, the EC and Fenton processes are combined to-
gether to increase the degradability of organic compounds present
in wastewaters [28]. In the conventional Fenton process, both H
2
O
2
and Fe
2+
are externally applied, whereas in the EF process, H
2
O
2
is
added from outside and Fe
2+
is provided from sacricial cast iron
anodes [29]. The EF process based on the employment of a sacri-
cial iron anode delivers Fe
2+
ions into the solution (Eq. (1)) whilst
simultaneously occurs the reduction of water at the cathode (Eq.
(2)); then the hydrogen peroxide is added in order to provide con-
ditions for the Fenton reactions (Eqs. (6) and (8)). Moreover, Fe
2+
according to Eq. (9) may be continuously regenerated at the cath-
ode depending on the electrolytic cell setup [30].
Fe
2
H
2
O
2
!Fe
3
OHOH
in bulk solution 6
Fe
2
OH !Fe
3
OH
in bulk solution 7
Fe
3
H
2
O
2
!Fe
2
H
HO
2
in bulk solution 8
Fe
3
e
!Fe
2
cathode 9
3. Materials and methods
3.1. Wastewater source and characteristics
The wastewater was collected from organic and organic-min-
eral liquid organic fertilizer manufacturing plant in Turkey (Istan-
bul) producing approximately 250 m
3
of wastewater per month.
LFW contained organic (humic and fulvic acids, dark brown color)
and inorganic compounds (nitrogen, phosphorus and potassium,
etc.). The wastewater was ltered using a screen lter to remove
large suspended solids before being used for the subsequent stud-
ies. Characteristics of LFW were shown in Table 1.
3.2. Experimental apparatus and procedure
The experimental set-up containing the specications of elec-
trode, reactor and power supply was reported elsewhere [16].
The EC and EF reactors were made of Plexiglas with dimension of
120 mm 110 mm 110 mm. Four plate electrodes (two anodes
and two cathodes) with dimension of 45 mm 53 mm 3 mm
(purity P99.5%) were used in the study. The total effective elec-
trode area was 143 cm
2
and the spacing between electrodes was
10 mm. The electrodes in monopolar connection mode were con-
nected to a digital dc power supply (Agilent 6675A model; 120V,
18A) and operated at galvanostatic mode.
The chemicals (H
2
O
2
, H
2
SO
4
, NaOH) were obtained from Merck.
In each experiment, approximately 800 mL of LFW was placed in
the electrolytic reactor. pH of the solution was adjusted to 3 prior
to the experiment and agitated with a magnetic stirrer at 200 rpm
(Heidolp 3600 model) in the EF process. A desired amount of H
2
O
2
(mM) was added to the electrolytic reactor before the electrical
current was turned on. A batch study was conducted to optimize
parameters such as concentration of H
2
O
2
and current density. Be-
fore each run, organic impurities and oxide layer on electrode sur-
faces were removed by dipping for 2 min in a solution freshly
prepared by mixing HCl solution (35%) and
Nomenclature
LFW liquid organic fertilizer manufacturing wastewater
EC electrocoagulation processes
EF electro-Fenton processes
TOC total organic carbon (mg/L)
COD chemical oxygen demand (mg/L)
TP total phosphate (mg/L)
TN total nitrogen (mg/L)
FTIR Fourier transform infrared spectroscopy
EDX energy dispersive X-ray instrument
XRD X-ray diffraction
C
energy
consumption of energy (kW h/m
3
)
C
electrode
consumption of electrodes (kg/m
3
)
U average cell voltage (V)
i current (A)
M
Fe
molecular weight of iron (g/mol)
OC operating cost (/m
3
)
F Faradays constant (C/mol)
12 A. Akyol et al. / Separation and Purication Technology 112 (2013) 1119
hexamethylenetetramine aqueous solution (2.8%). The electrodes
were then dried and weighed and placed into the reactor.
The voltage or current density of the EC reactor was set to a de-
sired value through adjustment of the direct current power supply
and the run was started at room temperature. The duration of the
experiment was 45 min and samples were taken every 5 min inter-
vals. The collected samples were ltered using a 45 lm Millipore
membrane paper. COD, TOC, TP, TN and turbidity (NTU) including
conductivity, initial and nal pH for every sample were measured.
At the end of the experiment, the electrodes were washed thor-
oughly with water to remove any solid residues on the surfaces,
dried and reweighed.
3.3. Analytical procedures
All analyses were carried out in accordance with the Standard
Methods of the APHA (APHA, 1998). COD was measured by closed
reux titrimetric method [31]. TOC levels were determined
through combustion of the samples at 680 C using a non-disper-
sive IR source (Tekmar Dohrmann Apollo 9000). The total phospho-
rus was determined with the optical emission spectrometer (ICP,
PerkinElmer Optima 7000 DV). TN analyses were carried out by
Hach Lange IL 550 TOC-TN analyzer. Turbidity, pH and conductiv-
ity (Mettler Toledo 7100e) of sample were measured with a turbi-
dimeter, a pH meter (Hach Lange HQ 40d) and a conductivity
meter (Hach 2100AN), respectively.
The analysis of H
2
O
2
was done by the permanganometric meth-
od. Residual H
2
O
2
was also measured in the supernatant to evalu-
ate possible interference with COD. The obtained H
2
O
2
concentrations (0.8 mg/L) increased only the total COD of the trea-
ted wastewater by about 0.5 mg/L [32] and the interference was
found to be negligible.
In addition, sludge generated by the EC and EF processes was
dried in the oven at 105 C for 24 h. XRD of the sludge was mea-
sured with an automated Rigaku X-ray diffractometer D-Max Rint
2200 Series instrument using Cu Ka radiation at 40 kV and 40 mA
over the range (2h of 570). Fourier transform infrared spectros-
copy (FTIR) can be used to identify chemicals from the sludge. FTIR
is perhaps the most powerful tool for identifying types of chemical
bonds (functional groups). FTIR for the samples were recorded in
the range 4000400 cm
1
on a Bio Rad FTS 175 C spectrophotom-
eter for detecting the changes of compounds after the removal pro-
cess. Experiments were conducted in triplicate under identical
conditions to conrm the results and the mean values were pre-
sented. The maximum experimental error was below 3%.
The electrode (C
electrode
, kg/m
3
) and energy (C
energy
, kW h/m
3
)
consumptions in the EC and EF processes were calculated using
the following equations:
C
energy
Uit
EC
m
10
C
electrode
it
EC
M
Fe
zFm
11
where U is the average cell voltage (V), i is the current (A), t
EC
is the
operating time (h), M
Fe
is the molecular weight of Fe (55.86 g/mol),
F is the Faradays constant (96,487 C/mol), z is the number of elec-
trons involved in the oxidation/reduction reaction and v is the vol-
ume of the treated solution (m
3
).
One of the most important parameters that affect the applica-
tion of any method of water and wastewater treatment greatly is
the operating cost which determines cost of the treatment process.
The OCs of the EC and EF processes were calculated by including
the material cost (mainly electrodes), utility cost (mainly electrical
energy), chemicals, as well as labor, maintenance and other xed
costs. In this study, the energy, electrode material and chemicals
costs were taken into account as major cost items in the calcula-
tion of the OC as /m
3
for the treatment of LFW [16]:
OC aC
energy
bC
electrode
cC
chemicals
12
where C
chemicals
is consumption quantities of chemicals (kg/m
3
) of
the wastewater treated. a, b and c constants in Eq. (12) provided
by the Turkish market in May 2012 were values of electrical energy
price (0.072 /kW h), electrode price (0.85 /kg) and chemical costs
(1.22 /kg for H
2
O
2
, 0.73 /kg for NaOH and 0.29 /kg for H
2
SO
4
),
respectively.
0
20
40
60
80
100
EC process
T
O
C
r
e
m
o
v
a
l
e
f
f
i
c
i
e
n
c
y
(
%
)
Operating time (min)
j (A/m
2
)
25
50
75
100
0 10 20 30 40 50
0 10 20 30 40 50
0
20
40
60
80
100
Operating time (min)
T
o
t
a
l
p
h
o
s
p
h
o
r
o
u
s
r
e
m
o
v
a
l
(
%
)
EC process
j (A/m
2
)
25
50
75
100
(a)
(b)
Fig. 1. Effect of current density on (a) TOC and (b) TP removal efciency of the EC
process.
Table 1
Characterization of efuents of the LFW.
Parameter Unit
pH 7.80
Conductivity (mS/cm) 2.28
Color Dark brown (Abs. 476 nm)
Turbidity (NTU) 104
SS (mg/L) 65
COD (mg/L) 1010
TOC (mg/L) 435
TN (mg/L) 68
TP (mg/L) 488
A. Akyol et al. / Separation and Purication Technology 112 (2013) 1119 13
4. Results and discussion
4.1. Effect of the current density on the removal efciency
Current density is an important parameter for controlling the
reaction rate in most electrochemical processes such as the EC
and EF processes. Current density determines the rate of coagulant
and bubble generation, its ocs size and distribution, and hence af-
fects the growth of ocs (Fe(OH)
2(s)
or Fe(OH)
3(s)
coagulate parti-
cles) in the EC process. In the EC and EF processes, the OH
4
ions
may be present at high pH, which lacked a removing capacity
[35]. The protons in the solution at lower pH
s
were reduced to H
2
at the cathode and existence of hydroxide ions was very low [35].
The amount of TN at pH
i
410 in the EC process was decreased
from 68 to 64 mg/L in 45 min which corresponded to the removal
efciency of 6% and could not be removed further successfully with
the present both EC and EF processes. The energy and electrode
consumptions for the EC process were 3.074.02 kW h/m
3
and
0.670.11 kg/m
3
. OCs for the EC process at pH
i
410 were varied
from 0.79 to 0.38 /m
3
. There was also hardly any differences ob-
served for OCs at pH 46 (Table 3).
In this study, three major interaction mechanisms of the EC pro-
cess were co-precipitation, adsorption and sweep coagulation [27].
Each of these mechanisms was to be thought of being for a differ-
ent pH range. At low pH values, metal species like Fe
3+
generated at
Table 3
Experimental results of LFW at different pH in the EC process.
pH TOC (%) pH
f
a
() W
s
(kg/m
3
) ELC (kg/m
3
) ENC (kW h/m
3
) OC (/m
3
)
4.0 76 8.5 2.07 0.67 3.07 0.79
6.0 79 8.9 2.42 0.64 2.72 0.74
8.0 31 9.9 0.60 0.16 3.91 0.42
10.0 7 11.4 0.56 0.11 4.02 0.38
a
pHf: Values of nal pH.
0 10 20 30 40 50
0
20
40
60
80
100
EC process
T
O
C
r
e
m
o
v
a
l
e
f
f
i
c
i
e
n
c
y
(
%
)
Operating time (min)
Initial pH
4
6
8
10
0 10 20 30 40 50
0
20
40
60
80
100
EC process
T
o
t
a
l
p
h
o
s
p
h
o
r
o
u
s
r
e
m
o
v
a
l
(
%
)
Operating time (min)
Initial pH
4
6
8
10
(a)
(b)
Fig. 3. Effect of pH
i
on the (a) TOC and (b) TP removal efciencies in the EC process.
A. Akyol et al. / Separation and Purication Technology 112 (2013) 1119 15
the anode binding to the anionic species, thus neutralizing their
charge and reducing their solubility. This process of removal was
named as precipitation. Second mechanism, adsorption operated
at a higher pH range (>6.0) and involved adsorption of organic sub-
stances on amorphous metal hydroxide precipitates. Under the
optimum operating conditions, the initially formed colloidal pre-
cipitate at nal pH 46 was positively charged and colloidally sta-
ble suggesting that co-precipitation played a vital role in the EC
process. The low pH range was explained as co-precipitation while
the higher pH range (>6) was adsorption and sweep coagulation
[36,37]. At pH > 6, formed amorphous M(OH)
3(s)
(sweep ocs) with
the minimum solubility within the pH range of 67 had a large
specic surface area that could absorb some soluble organic com-
pounds such as humic acid onto its surface [23]. The EC process in
the pH range 46 was explained as co-precipitation. Therefore, an
effective color removal of LFW was realized between these pH
ranges in the previous study [27].
4.3. Effect of H
2
O
2
concentration on the removal efciency
Determination of the optimum H
2
O
2
concentration in the EF
process is very important for both the removal efciency and par-
ticularly economic applicability related to the cost of H
2
O
2
. The ef-
fect of initial H
2
O
2
concentration on removal efciencies of LFW
was studied in the range of 550 mM at the optimum conditions
(50 A/m
2
and pH 3). The removal efciencies of TOC and TP were
found to be directly proportional to H
2
O
2
concentration when the
current density applied to the EF process was the high enough
(P50 A/m
2
).
TOC removal efciency increased from 59% to 84% with increas-
ing initial H
2
O
2
concentration from 5.0 mM to 25.0 mM in 10 min
and the removal efciency at 25 mM was reached to 87% at
45 min (Fig. 4a). But TOC removal efciency decreased to 80% at
50 mM of initial H
2
O
2
concentration due to the undesired OH scav-
enging reactions effect. This circumstance depended on Eqs. (12
and 13) leading to the formation of less reactive radicals from
the hydroxyl radical. The similar results were reported and the
optimum H
2
O
2
concentration was 30 mM [38]. Among these
0
20
40
60
80
100
EF process
T
O
C
r
e
m
o
v
a
l
e
f
f
i
c
i
e
n
c
y
(
%
)
Operating time (min)
Dosage of H
2
O
2
(mM)
None
5
10
25
50
0 10 20 30 40 50
0 10 20 30 40 50
0
20
40
60
80
100
EF process
Operating time (min)
T
o
t
a
l
p
h
o
s
p
h
o
r
o
u
s
r
e
m
o
v
a
l
(
%
)
Dosage of H
2
O
2
(mM)
None
5
10
25
50
(a)
(b)
Fig. 4. Effect of initial H
2
O
2
concentration on the (a) TOC and (b) TP removal
efciencies by EF process.
0 10 20 30 40 50
0
20
40
60
80
100
C
o
l
o
r
r
e
m
o
v
a
l
e
f
f
i
c
i
e
n
c
y
%
Operating time (min)
EF
EC
Fig. 5. Effect of operating time on color removal efciencies by EC and EF processes.
Table 4
Experimental results of LFW at different H
2
O
2
dosages in the EF process.
H
2
O
2
dosage (mM) TOC (%) pH
f
() W
s
(kg/m
3
) ELC (kg/m
3
) ENC (kW h/m
3
) OC (/m
3
)
5 81 7.1 0.84 0.11 0.54 0.35
10 81 7.5 0.65 0.12 0.52 0.58
25 87 7.1 0.65 0.12 0.47 1.23
50 80 7.8 0.78 0.12 0.51 2.33
Table 5
Comparison values of LFW before and after treated by EC and EF processes.
Parameter LFW EC process
a
EF process
b
pH 7.80 8.9 7.1
Conductivity (mS/cm) 2.28 1.93 2.05
Color Dark brown Almost clear Almost clear
Turbidity (NTU) 104 2 1
SS (mg/L) 65 4 2
COD (mg/L) 1010 168 87
TOC (mg/L) 435 76 58
TN (mg/L) 68 64 64
TP (mg/L) 488 130 18
a
The optimum operating conditions for EC process: 50 A/m
2
, 45 min and pHi 6.
b
The optimum operating condition for EF process: 50 A/m
2
, 45 min 25 mM H
2
O
2
and pHi 3.
16 A. Akyol et al. / Separation and Purication Technology 112 (2013) 1119
reactions, the production of hydroperoxyl radicals occurred in the
cycle of Fe
3+
to Fe
2+
and the quenching of
OH by Fe
2+
and H
2
O
2
.
Oxidation potentials of hydroperoxyl radicals (1.25 eV) was lower
than that of H
2
O
2
(1.3 eV) [21].
Fe
2
OH !Fe
3
OH
12
H
2
O
2
OH !H
2
O HO
2
13
Fig. 4a also indicated that the removal efciencies of LFW at 10,
25 and 50 mM H
2
O
2
concentrations increased rapidly for the rst
10 min which resulted in removal efciencies of 78%, 84% and
77% for TOC, respectively. There was also no noticeable differences
observed for the removal efciencies of TOC between 10 and
45 min except for 5 mM H
2
O
2
concentration due to the batch addi-
tion of H
2
O
2
at the beginning. Yavuz [13] added H
2
O
2
continuously
to maintain the effect of Fenton reaction in the experiment because
the batch addition caused quenching of hydroxyl radicals which
were shown in the following reactions:
HO
H
2
O
2
!H
2
O HO
2
14
HO
HO
!H
2
O 1=2O
2
15
whose rates competed with the degradation reactions of more re-
calcitrant compounds:
HO
RH !R
H
2
O
Fig. 4b indicated that the removal efciencies of TP in 20 min
were nearly completed. After that, it remained almost the same un-
til the operating time of 45 min. The optimum H
2
O
2
concentration
for the rest of the study was selected as 25 mM due to decrease in
OC with respect to the higher removal efciency. TP removal ef-
ciency was obtained as 98.5% at the optimum H
2
O
2
concentration.
The EF process was found to be more suitable for TP removal due to
faster removal efciency (Fig. 4a and b).
Efuent pH
s
of the treated water were changed as 7.1, 7.5, 7.1,
7.8, respectively when inuent pH
i
was 3.0 at 45 min in the EF pro-
cess. All nal efuent pH
f
fell into limit values set by discharge
standards of water pollution control regulations (pH
f
69).
Table 4 showed that values of energy consumptions were calcu-
lated by considering for concentration of H
2
O
2
(550 mM) varied
from 0.54 to 0.51 /m
3
in the EF process. In addition, values of en-
ergy consumption almost remained with increasing H
2
O
2
concen-
tration. The electrode consumptions were almost the same as
0.12 kg/m
3
. The OC of the treated LFW depended on initial H
2
O
2
concentration because the OCs increased from 0.35 to 2.33 /m
3
at 550 mM H
2
O
2
. The OC at the optimum initial H
2
O
2
concentra-
tion was almost twice lower than the OC at 50 mM. The OC in the
EF process (1.23 /m
3
) was higher than that of EC process (0.74 /
m
3
) due to additional cost of H
2
O
2
in the EF process. The EF process
seemed to be more expensive but, LFW was removed with higher
removal efciency and lower operating time with the EF process
as compared to the EC process.
0
25
50
75
100
Current density (A/m
2
)
T
O
C
r
e
m
o
v
a
l
e
f
f
i
c
i
e
n
c
y
(
%
)
EC (10 min)
EF (10 min)
0 25 50 75 100
0 25 50 75 100
0
20
40
60
80
100
T
o
t
a
l
p
h
o
s
p
h
o
r
o
u
s
r
e
m
o
v
a
l
(
%
)
Current density (A/m
2
)
EC (10 min)
EF (10 min)
(a)
(b)
Fig. 6. Effect of current density on (a) TOC and (b) TP removal efciencies in the EC
and EF processes at 10 min.
0.0
0.5
1.0
1.5
2.0
2.5
3.0
A
b
s
o
r
b
a
n
c
e
Wavelength (nm)
LFW
5 min EC
10 min EC
15 min EC
20 min EC
30 min EC
45 min EC
200 300 400 500 600 700 800
200 300 400 500 600 700 800
0.0
0.5
1.0
1.5
2.0
2.5
3.0
A
b
s
o
r
b
a
n
c
e
Wavelength (nm)
LFW
5 min EF
10 min EF
15 min EF
20 min EF
30 min EF
45 min EF
(a)
(b)
Fig. 7. Absorbance spectra of LFW for (a) EC and (b) EF processes at 545 min.
A. Akyol et al. / Separation and Purication Technology 112 (2013) 1119 17
4.4. Comparisons of removal efciencies for EC and EF processes
The optimum experimental conditions (50 A/m
2
and pH 6 for
the EC, and 50 A/m
2
and 25 mM of H
2
O
2
concentration for the
EF) were applied for removal of color from LFW (Fig. 5). As seen
in Fig. 5, the EF process gave a better color removal efciency
(99%) at 45 min than the EC process with removal efciency of
95% and the efuent became almost visually clear. The color spec-
trum bands (400700 nm) of LFW degraded uniformly in 45 min
during the EC and EF removal processes (Fig. 7). As seen in the g-
ure, there was some oxidation observed for the EF process in
Fig. 7b between 200 and 300 nm whereas there was very low per-
centage oxidation present for the EC process in Fig. 7a.
TOC removal efciencies in 10 min were obtained as 83% for the
EF process at 50 A/m
2
and 62% for the EC process at 100 A/m
2
.
Moreover, the removal efciencies of TP were 51% for the EC and
90% for the EF processes in 10 min at 100 A/m
2
(Fig. 6)).
The results in Table 2 showed that the EF process consumed ve
times less electrode and energy consumptions but the OC in the EF
process was 1.7 times higher as compared to the EC process. How-
ever, the EF process can be envisaged as an effective removal pro-
cess for LFW in terms of better removal efciencies of TOC and TP
in the wastewater. Table 5 also showed the comparison of efuents
of LFW for treated by EC and EF processes.
The different electrochemical processes in the degradation of
alcohol distillery wastewater was studied and the Fenton process
was the best for COD and TOC removal efciencies which re-
moved 92.6% for an initial COD of 4985 mg/L and 88.7% for an ini-
tial TOC of 1507 mg/L. In addition, the EC process was not
successful at all experimental conditions studied [13]. Martins
et al. also investigated with removal efciencies of nonylphenol
polyethoxylate (NP9EO) by the EC and EF processes. More than
95% of NP9EO removal was achieved by both treatments in
5 min of the EF and 15 min of the EC. The organic load removal
of COD reduction had not surpassed 55% in both the EC and EF
processes [30].
4.5. Characterization of the sludge
The amount of sludge produced during LFW treatment was an
important problem due to disposal of the solid waste. The sludge
production was proportional to characteristics of raw wastewater
settable solids and matter destabilized by coagulation and concen-
tration occulent and was also proportional to current density and
2
.
9
1
9
6
.
7
4
2
8
.
6
2
3
1
3
.
2
6
2
1
9
.
5
1
9
3
5
.
8
4
1
5
7
.
8
4
0
0
10
20
30
40
50
I
n
t
e
n
s
i
t
y
(
C
o
u
n
t
s
)
10 20 30 40 50 60 70
00-030-0662> Vivianite - Fe 3 (PO 4 ) 2 8H 2 O
3
.
6
5
9
9
.
2
1
7
1
2
.
3
9
9
2
8
.
7
9
2
3
5
.
4
0
2
4
0
.
7
0
4
5
3
.
4
3
9
6
3
.
3
5
8
0
25
50
75
100
I
n
t
e
n
s
i
t
y
(
C
o
u
n
t
s
)
10 20 30 40 50 60 70
00-030-0662> Vivianite - Fe 3 (PO 4 ) 2 8H 2 O
00-001-1106> Lawrencite - FeCl 2
Two-Theta (deg)
Fig. 8. XRD analyses of the sludges (a) EC and (b) EF processes.
500 1000 1500 2000 2500 3000 3500 4000 4500
70
75
80
85
90
95
100
105
EF
EC
T
r
a
n
s
m
i
t
a
n
c
e
(
%
)
Wavenumber cm
1-
Sludge after EF process
Sludge after EC process
Fig. 9. FTIR of sludges from the EC and EF processes.
18 A. Akyol et al. / Separation and Purication Technology 112 (2013) 1119
residence time [39]. The sludge was collected by vacuum ltration
after the EC and EF processes and dried at 105 C for 24 h in the
oven. Amounts of the sludge produced in the EC and EF processes
increased from 0.85 to 4.61 kg/m
3
for the EC process and from 0.62
to 1.88 kg/m
3
for the EF process at 25100 A/m
2
(Tables 24).
Characterizations of the sludge samples were carried out by XRD
and FTIR. Fe
3
(PO
4
)
2
8H
2
O (vivianite) in the sludge was detected
from both processes by XRD (Fig. 8). FeCl
2
(Lawrencite) was ob-
served from the sludge in the EF process.
FTIR spectra of the sludge samples from both processes were
shown in Fig. 9. FTIR spectra of sludge indicated a broad and in-
tense band at 3364 cm
1
and 3224 cm
1
attributed to stretching
vibrations of AOH. The bands at 1632 cm
1
, 1581 cm
1
and
1383 cm
1
referred to the presence of C@O, C@C and CAH. The
strong bands at 1009 cm
1
and 1019 cm
1
showed CAOAC stretch-
ing vibrations. FTIR spectra depicted hardly any signicant spectro-
scopic changes in the sludge samples.
5. Conclusions
In this study, effect of the operational parameters on the EC and
EF processes were evaluated based on removal efciency and oper-
ating cost. The optimum operating conditions for LFW were deter-
mined as 50 A/m
2
and pH 6 for the EC process, and 50 A/m
2
and
25 mM of H
2
O
2
concentration for the EF process at 45 min. The
EF process resulted in higher removal efciencies (81% of TOC in
10 min, 96% of TP and 99% of color in 45 min) than that of the EC
process (79% of TOC, 73% of TP and 95% of color efciency in
45 min). Amount of the sludge produced was higher in the EC pro-
cess (2.42 kg/m
3
) than that of the EF process (0.65 kg/m
3
). How-
ever, the operating cost for the EC process was found to be 1.7
times lower than that of the EF process since price of H
2
O
2
was af-
fected the cost drastically. The obtained results indicated clearly
that the EC and EF processes were very effective for the removal
of LFW. Overall, the EF process was more successful for achieving
higher removal efciencies in terms of TOC, TP and color than
the EC process and the EF process is a promising technology for
applications in wastewater treatment.
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