Separation and Purication Technology 145 (2015) 104112

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Separation and Purication Technology

journal homepage: www.elsevier.com/locate/seppur

Treatment of thin lm transistor-liquid crystal display (TFT-LCD)

wastewater by the electro-Fenton process
James I. Colades a, Mark Daniel G. de Luna a, Chia-Chi Su b, Ming-Chun Lu b,
a
b

Department of Chemical Engineering, University of the Philippines, 1101 Diliman, Quezon City, Philippines
Department of Environmental Resources Management, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan

a r t i c l e

i n f o

Article history:
Received 23 August 2014
Received in revised form 20 January 2015
Accepted 26 February 2015
Available online 10 March 2015
Keywords:
TFT-LCD
Wastewater
Dimethyl sulfoxide
Response surface methodology
Electro-Fenton

a b s t r a c t
In this study, the electro-Fenton process was used to treat synthetic and actual TFT-LCD wastewaters.
TFT-LCD wastewater contains high amounts of organic solvents mainly dimethyl sulfoxide (DMSO). For
the simulated TFT-LCD wastewater, response surface methodology (RSM) was used to t experimental
data to empirical models with the responses, %DMSO removal and H2O2 efciency (D[H2O2]/
D[DMSO]). Among the studied independent variables that affect DMSO degradation efciency, Fe2+ loading was found to be the most dominant, then pH and, H2O2 loading being the least signicant. DMSO
removal and H2O2 efciency improved with high Fe2+ loading, low H2O2 loading and low solution pH.
The observed decrease in pH was attributed to the production of acidic degradation intermediates of
DMSO. At 5 mM DMSO loading, treatment efciency reached 100% DMSO removal. The electro-Fenton
technology was also applied to real TFT-LCD wastewater resulting in TOC and COD removals of 68%
and 79%, respectively.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Thin lm transistor-liquid crystal display (TFT-LCD), a technology widely known for producing more compact and energy-saving
display devices and producing images of higher quality than the old
cathode ray tube (CRT) display, has gained popularity during the
recent decade. Taiwan became the largest supplier of TFT-LCD in
2004 by producing more than 40% of the worlds TFT-LCDs [1].
The production of TFT-LCD panels requires large volumes of water
and contain large amounts of organics, mostly solvents [24].
Dimethyl sulfoxide (DMSO) is the primary solvent of the semiconductor industry not only because of its excellent solvent properties but also because it is relatively less toxic compared to
chlorinated solvents [2]. It is also very stable which offers an
advantage as an industrial chemical but several disadvantages if
it is considered a pollutant for treatment. The stability of DMSO
can be attributed to resonance structures which can be drawn by
moving pi electrons in the S@O bond toward the oxygen. A closer
look at the molecular structure (Fig. S1) of DMSO shows that it is
surrounded by an electron cloud making it difcult for oxidants,
which are electron rich, to approach DMSO for degradation. Some
studies have presented the problems that arise during the biological treatment of DMSO containing efuents. The formation of
Corresponding author. Tel.: +886 6 2660489; fax: +886 6 2663411.
E-mail addresses: mmclu@mail.cnu.edu.tw, mclu@ms17.hinet.net (M.-C. Lu).
http://dx.doi.org/10.1016/j.seppur.2015.02.039
1383-5866/ 2015 Elsevier B.V. All rights reserved.

dimethyl sulde (DMS), methyl mercaptan and hydrogen sulde,

both malodorous compounds, were observed during the anaerobic
and anoxic treatment of DMSO-containing wastewater [5,6]. The
stability of DMSO renders biological treatment incapable of complete removal of DMSO. In a recent study by Fukushima et al.,
DMSO was detected in the efuent at a concentration of 8 mg/L
even after subjecting TFT-LCD wastewater to biological treatment
[7]. Furthermore, incomplete DMSO degradation causes the accumulation of inhibitory intermediates (e.g. H2S and formaldehyde)
which are toxic to microorganisms [2,8]. The presence of DMSO
in natural environments causes adverse effects on many organisms
because it is readily absorbed and contributes to high osmotic
pressure in biological systems [9].
The complete oxidation and mineralization of recalcitrant compounds like DMSO to harmless inorganic compounds (e.g. CO2 and
salts) requires the use of advanced oxidation processes (AOP). The
electro-Fenton process is an AOP that generates hydroxyl radicals,
a powerful and a non-selective oxidant, via the reaction between
hydrogen peroxide and the ferrous ion.
The electro-Fenton process is an improvement of conventional
Fenton process by electrochemical regeneration of spent ferric ions
to ferrous ions. This reduces the amount of iron loading and the
sludge (mainly ferric hydroxide (Fe(OH)3)) produced during the
neutralization of the wastewater [1012]. Shown in Table 1 are
the reactions involved in the electro-Fenton process. Eqs. (1) and
(2) are the main reactions of conventional Fenton process which

J.I. Colades et al. / Separation and Purication Technology 145 (2015) 104112

produces hydroxyl radicals and regenerates the spent ferric ions to

ferrous ions, respectively. Eqs. (3) and (4) provides the mechanism
of how hydroxyl radicals degrade organic compounds. Eqs. (5)(8)
are undesirable side reactions that consumes the hydroxyl radicals
produced. Eqs. (9) and (10) takes place in the cathode of the electrochemical reactor [13].
Previous studies have investigated how contaminant degradation by the electro-Fenton process is affected by pH [1315], Fe2+
loading [12,16,17], and H2O2 loading [18,19]. Several other studies
that electrochemically-generated H2O2 in the cathode focused on
the effect of current density [2022] on pollutant degradation. In
a published study [12] done by the same authors and using the
same electro-Fenton set-up, the effect of current density on
DMSO degradation was already found to be insignicant.
In this study, the electro-Fenton process was used to treat TFTLCD wastewater. Dimethyl sulfoxide (DMSO) degradation and
D[H2O2]/D[DMSO] were modeled as a function of critical operating
variables namely: initial pH, Fe2+ loading, and H2O2 loading using
BoxBehnken design of experiment. The present study sources
H2O2 externally and the electric potential applied has its sole purpose of regenerating spent ferric ion catalyst to ferrous ion in the
cathode. Hence, pH, Fe2+ loading, and H2O2 loading were the chosen independent variables for optimization. It is important to optimize the H2O2 consumption since H2O2 contributes primarily to
the cost of treatment and is the most expensive reactant employed
[23]. The presence of H2O2 in semiconductor efuents provides
added advantage on the use of electro-Fenton in the treatment of
TFT-LCD wastewater [2]. The results of the optimization study
became the basis for the application of the electro-Fenton process
to treat real TFT-LCD efuent.

105

of H2O2 and Fe2+ concentration, respectively. TOC was determined

using Elementar liquiTOC analyzer.
2.2. Experimental apparatus
The cylindrical reactor (Fig. 1) used in this study had concentric
electrodes. The cathodes were made of stainless steel which had
diameters of 2 and 13 cm while the anode is an RuO2/IrO2-coated
titanium net with a diameter of 7 cm. The reactor has a working
volume of 4 L and was operated as a batch process. It was equipped
with a pH meter (TS-1, Suntex) to monitor changes in pH and a
centrifugal pump (MD-10-NL12, Iwaki) to facilitate recirculation
and thorough mixing within the reactor during treatment.
2.3. Electro-Fenton process
All experiments were performed at room temperature of 25 C.
Synthetic wastewater was prepared by adding reagent grade
DMSO unto deionized water with 50 mM of NaClO4 as background
electrolyte. For this study, initial DMSO loading was at 5 mM or
390.65 mg/L. A weighed amount of FeSO47H2O was added to the
solution. The pH of the wastewater was adjusted using 1 M
HClO4 and 1 M NaOH. Applied current was maintained at 1.5 A
which is equivalent to 11.3 mA/cm2. Initial conditions of the system were obtained from the sample taken before the simultaneous
addition of H2O2 and introduction of electric current into the system. Samples were taken at xed time intervals (0, 5, 10, 20, 40,
60, 90 and 120 min). Each sample (4 ml) was diluted with 15 ml
deionized water and 1-ml 1 N NaOH to stop the Fenton reaction
by precipitating ferrous and ferric ions as hydroxides. The mixture

2. Methodology
2.1. Chemicals and analytical methods
Solutions were prepared using deionized water (18.2 MX resistivity, Millipore system). Reagent grade chemicals dimethyl sulfoxide
(C2H6SO, 99.5%, Merck), hydrogen peroxide (H2O2, 35%, Merck), ferrous sulfate heptahydrate (FeSO47H2O, Merck) and sodium perchlorate monohydrate (NaClO4H2O, 99100%, Merck), sodium hydroxide
(NaOH, >99%, Merck) were used without further purication.
DMSO concentration was measured by High Performance
Liquid Chromatography (HPLC) with Spectra SYSTEM model
SN4000
and
Asahipak
ODP,
506D
column
(150 mm  6 mm  5 mm) using 40% acetonitrile as mobile phase.
Two mL of sample was injected and the absorbance was determined from the 254 nm output of UV1000. Closed-reux titration
method was used for COD analysis. Spectrophotometric analysis
of hydrogen peroxide concentration and ferrous ion concentration
was done by complexing samples with potassium titanium oxalate
(K2Ti(C2O4)) and 1,10-phenanthroline, respectively. Absorbances
were measured at wavelengths of 400 nm and 510 nm for analyses

Table 1
Reactions involved during electro-Fenton treatment.
H2 O2 Fe2 ! Fe3  OH OH
Fe3 H2 O2 ! Fe2 H HO2

OH RH !  R H2 O
Fe3  R ! Fe2 R
OH H2 O2 ! HO2 H2 O

Fe3 HO2 ! Fe2 O2 H




OH Fe2 ! Fe3 OH

OH H e ! H2 O

Fe3 e ! Fe2
2H 2e ! H2

(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)

Fig. 1. Schematic diagram of the electro-Fenton reactor. (a) Top view and position
of electrodes in concentric circles and (b) side view and DC power supply
connection and pump schematic.

J.I. Colades et al. / Separation and Purication Technology 145 (2015) 104112

was ltered using a 0.45 lm lter and the supernatant was kept for
12 h to remove excess H2O2 prior to analysis. All experiments were
performed in duplicates and the mean is presented in this study.
Optimization of signicant operating variables: initial pH, Fe2+
loading, H2O2 loading was conducted using the Box-Behnken
Method (Design Expert 7.00 software). Table 2 shows the factors
used in the experimental design along with the low, mean and high
levels of the variables for optimization.
3. Results and discussion
3.1. Optimization of operating variables
Table 3 summarizes the results of the optimization study.
DMSO removal, calculated using Eq. (11), ranged from 35.45% to
100%. Hydrogen efciency, calculated using Eq. (12), which is
moles of hydrogen peroxide consumed per mole of DMSO
degraded, ranged from 3.57 to 18.50. The independent un-coded
variables used in the empirical t are solution pH, [Fe2+] (initial
concentration of Fe2+ ions) and [H2O2] (initial concentration of
H2O2 loaded to start the Fenton reaction). The transformed
p
responses, ln(%DMSO removal) and DH2 O2 =DDMSO, were tted
empirically to quadratic models. Fig. 2a and b shows the predicted
vs actual responses ln(%DMSO removal) and square root of
D[H2O2]/D[DMSO], respectively. The resulting quadratic models
p
for % DMSO removal and DH2 O2 =DDMSO t the actual experimental data with adjusted R2 of 0.9373 and 0.9741, respectively.

% DMSO removal

DMSOinitial  DMSOfinal;t120min
 100%
DMSOinitial

DH2 O2
moles H2 O2 consumed

DDMSO moles DMSO degraded

Table 3
Summary of optimization results.
Run

pH

Fe2+ loading
(mM)

H2O2 loading
(mM)

DMSO removal
(%)

DH2 O2 
DDMSO

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

2.5
1.8
1.8
2.5
2.5
3.2
3.2
2.5
1.8
3.2
2.5
2.5
2.5
2.5
3.2
2.5
1.8

2
2
3
3
3
2
1
2
2
3
2
1
2
1
2
2
1

40
60
40
20
60
60
40
40
20
40
40
20
40
60
20
40
40

82.09
95.10
100.00
93.52
100.00
75.55
35.45
90.57
94.78
78.21
82.38
41.11
92.33
55.20
36.57
91.50
75.48

7.73
8.88
8.44
3.80
11.06
11.65
18.50
7.34
3.57
8.71
7.76
8.58
7.09
12.38
7.74
7.02
6.45

(a)

4.40

12

3.1.1. DMSO removal

The nal empirical equation which models %DMSO removal is
shown in Eq. (13) using un-coded independent variables. The magnitude of the coefcients of each term of the model indicates the
strength of how a particular independent variable or the interactions of two variables affect the response variable, which is in this
case, %DMSO removal. A positive or a negative term will indicate
a direct relationship or an inverse relationship, respectively, of
the associated independent variable with the response variable.

3.50
3.50

3.79

4.09

4.38

4.67

3.69

4.30

Actual

4.40

 pH

0:15132

 Fe2 
3

4:19014  10

 H2 O2 

3.75

 pH  Fe2 
 pH  H2 O2 

lnDMSO removal % 0:18211

0:01290

 pH2

0:22376

2 2

0:14961

 Fe 

2:65464  104

 H2 O2 2
13

Table 2
Summary of parameter ranges for optimization studies.

Predicted

0:45427

3.10

2.45

1.80

Levels
Actual low (1)

pH
Fe2+ loading (mM)
H2O2 loading (mM)

4.10

3.80

(b)

4:33215

Factor

4.70

11
Predicted

106

1.8
1
20

Mean (0)
2.5
2
40

Actual high (+1)

3.2
3
60

1.85

2.46

3.08

Actual
Fig. 2. Predicted vs actual values of the responses. (a) ln(%DMSO removal) and (b)
square root of D[H2O2]/D[DMSO].

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J.I. Colades et al. / Separation and Purication Technology 145 (2015) 104112

The rst-order term (Eq. (13)) that weighs the effect of pH on

DMSO degradation has a negative coefcient which means that
DMSO removal decreases with increasing pH. Studies have shown
a general reduction in electro-Fenton degradation efciency when
pH is raised beyond the value of 2 [13,24,25]. This effect is
observed on the surface response model graph and contour plots
shown in Fig. 3a and b. Increasing pH beyond 2 caused the precipitation of amorphous Fe(OH)3 which decreased the concentration
of dissolved iron and inhibiting Fe2+ regeneration by partially coating the cathode of the electro-Fenton reactor. This was a conclusion in the study of Ting et al. [13] on a study that employed
electro-Fenton for the degradation of 2,6-dimethylaniline. A further decrease in pH (<2.0), on the other hand, decreases the efciency of the Fenton process due to increased concentration of H+
ions which scavenges hydroxyl radicals (Eq. (8)). Furthermore,
increased rate of reduction of H+ ions to hydrogen gas (Eq. (10))
also reduces the current efciency and the active sites for catalyst
regeneration in the cathode [13,26].
The Fe2+-containing term (Eq. (13)) is positive indicating that
an increase of Fe2+ loading resulted in higher DMSO removal.
The positive contribution of Fe2+ loading was also observed by
Cruz-Gonzlez et al. [27] while treating dye wastewater using
electro-Fenton process. Among the rst order terms, the Fe2+-containing term has the highest magnitude indicating that it contributes the most weight among the other independent variables
studied. Previous Fenton studies that employed response surface
methodology also have the highest and positive rst-order

Fe2+-containing term in their nal empirical quadratic models

[28,29]. Increasing Fe2+ loading improves the degradation efciency of pollutants oxidized by the electro-Fenton process
[11,18] by increasing the production of hydroxyl radicals
(Eq. (1)) and also increasing the rate of regeneration of Fe2+ from
Fe3+ (Eq. (2)). Increasing Fe2+ loading beyond 2.0 mM exhibited
diminishing returns in DMSO degradation as observed in
Fig. 3(a) and (b). High concentration of dissolved Fe2+ results to
hydroxyl radical scavenging (Eq. (7)) which reduces the available
hydroxyl radicals for DMSO degradation.
Among the three parameters studied, H2O2 loading contributed
the least to DMSO removal for having the smallest coefcient
among the rst-order terms. This is further supported by the
ANOVA in Table 4 which shows that the p-value for the H2O2
rst-order term is the largest. Optimization studies involving
H2O2 loading as a variable to be optimized showed that the resulting quadratic model has H2O2 terms with coefcients having lower
magnitude compared with other terms [30,31]. Rodrigues et al.
[32], in their study on the degradation of an azo dye using the
Fenton reaction, found H2O2 concentration insignicant to degradation efciency and dropped the H2O2 containing term on the
nal empirical quadratic model. Hydrogen peroxide is introduced
to the reactor externally and unlike Fe2+, H2O2 concentrations used
in the Fenton degradation of aqueous pollutants are always beyond
the theoretical amount of H2O2 needed. Degradation efciency
thus becomes less affected of any changes in the initial H2O2 concentration beyond the theoretical amount.

(b)
(a)

3.00

2.50

90.75

Fe2+ (mM)

DMSO degradation (%)

110

71.5
52.25
33

96.6716
83.9776

2.00

71.2836
58.5897

1.50

3.00

1.80
2.50

2.15

1.50

2.85

pH
pH

45.8957

2.00

2.50

3.20

1.00
1.80

Fe2+(mM)
(mM)
Fe2+

1.00

2.15

2.50

2.85

3.20

pH

(d)
60.00

(c)

50.00

92.931

87.75

H2O2 (mM)

DMSO degradation (%)

104

71.5
55.25

40.00

82.1771

71.4233

39

60.6694

30.00

60.00

1.80

40.00

2.50

pH

49.9156

50.00

2.15

30.00

2.85
3.20

20.00

H2O2 (mM)

H2O2 (mM)

20.00
1.80

2.15

2.50

2.85

3.20

pH

Fig. 3. Surface and contour plots DMSO degradation (%) as a function of (a and b) pH and [Fe2+] with [H2O2] = 40 mM, (c and d) pH and [H2O2] with [Fe2+] = 2 mM.

108

J.I. Colades et al. / Separation and Purication Technology 145 (2015) 104112

Table 4
Analysis of variance for the optimization runs.
Source

Model
A: initial pH
B: Fe2+ (mM)
C: H2O2 (mM)
AB
AC
BC
A2
B2
C2
Residual
Lack of t
Pure error
*

DMSO degradation (%)

Mean
square

F
value

Signicance
level
(p-value)

Mean
square

F
value

Signicance
level
(p-value)

0.24
0.62
0.77
0.15
0.0650
0.13

30.89
76.39
99.20
19.05
8.33
16.71

<0.0001*
<0.0001*
<0.0001*
0.0024*
0.0203*
0.0035*

0.051
0.094
0.047
0.0078
0.0119
0.0034

6.49
12.08
6.08

0.0344*
0.0084*
0.0389*

0.55
1.23
0.58
1.70
0.74
0.053
0.15
0.090
0.41

67.99
150.25
71.39
208.28
90.25
6.46
18.98
11.05
49.93
4.90

<0.0001*
<0.0001*
<0.0001*
<0.0001*
<0.0001*
0.0386*
0.0033*
0.0127*
0.0002*
0.0624

3.54

0.1244

DH2 O2 
DDMSO

0.0008
0.014
0.0004

3.37

0.1356

Terms having p-value <0.05 are considered signicant.

1.0
pH = 1.8, [Fe2+] = 3 mM, [H2O2] = 40 mM, kapp = 0.0273
pH = 3.2, [Fe2+] = 1 mM, [H2O2] = 40 mM, kapp= 0.0021
pH = 1.8, [Fe2+] = 2 mM, [H2O2] = 60 mM, kapp = 0.0233
pH = 1.8, [Fe2+] = 2 mM, [H2O2] = 20 mM, kapp = 0.0247

(a)

0.6
0
-1

ln (C/CO)

DMSO degradation (C/CO)

0.8

0.4

-2

R2 = 0.9929
R2 = 0.7941
R2 = 0.9680
R2 = 0.9087

-3
0

0.2

40
80
Time (min)

120

0.0
0

20

40

60

80

100

120

little difference between the apparent rate constants of the two

runs. Comparing these two runs at t = 120 min, the run with
20 mM H2O2 loading performed better up to the rst 90 min of
treatment and was only surpassed by the run with 60 mM initial
H2O2 loading during the last 30 min of the run. The reduced performance of the run with higher H2O2 loading is caused by the inhibition of the Fenton treatment due to the scavenging effect of
hydrogen peroxide on the produced hydroxyl radical (Eq. (5))
[19,33]. However, after 90 min of treatment, the run with the lower
H2O2 loading (20 mM) already exhausted the H2O2 in the solution
(Fig. 4b) where the run with 20 mM initial H2O2 has only 5.50 mM
H2O2 in the solution while the run with 60 mM initial H2O2 still has
26.35 mM of H2O2. The low concentration of the remaining H2O2
limits the Fenton treatment due to reduced rate of hydroxyl radical
production (Eq. (1)) and slower rate regeneration of Fe2+ from Fe3+
(Eq. (2)), both requiring H2O2 as reactants.
Between the two-parameter interaction terms of Eq. (13), the
term containing pH and Fe2+ contributed more weight to the
response variable for having the highest magnitude of coefcient.
Fig. 4a shows the concentrationtime prole of DMSO degradation
of the extremes of pH and Fe2+ loading. At the low extreme
(pH = 3.2,
[Fe2+] = 1 mM)
and
high
extreme
(pH = 1.8,
[Fe2+] = 3 mM) the resulting DMSO removals, at a xed H2O2 loading of 40 mM, were 35.45% and 100% DMSO removal, respectively
after 2 h of treatment. This large difference (64.55%) in DMSO
removal supports what Eq. (13) implies that the combined effect
of pH and Fe2+ loading (pH  [Fe2+]) imparts a large effect on the
DMSO removal efciency. Furthermore, apparent rst-order rate
constant of the high extreme is approximately 13 times that of
the lower extreme which further supports that decreasing pH and
increasing Fe2+ loading increases DMSO removal efciency.
In this section, Fe2+ loading is the most signicant variable and
has strong and positive impact on the efciency of DMSO degradation. Increasing pH, on the other hand, reduces %DMSO degradation. Variance in H2O2 loading contributes little to the nal
DMSO concentration after 120 min of treatment. However, effect
of varying initial H2O2 loading was observed in the DMSO concentrationtime prole of the runs.

Time (min)
3.1.2. Hydrogen peroxide efciency

1.0

pH = 1.8, [Fe2+] = 3 mM, [H2O2] = 40 mM, k app= 0.0124

pH = 3.2, [Fe2+] = 1 mM, [H2O2] = 40 mM, k app= 0.0127
pH = 1.8, [Fe2+] = 2 mM, [H2O2] = 60 mM, k app= 0.0083
pH = 1.8, [Fe2+] = 2 mM, [H2O2] = 20 mM, k app= 0.0160

(b)

H2O2 (C/CO)

0.8

p
The nal equation for the response
DH2 O2 =DDMSO is presented by Eq. (14) with the un-coded independent variables
dened previously. Fig. 5 shows the surface response and contour
p
plots of the response variable DH2 O2 =DDMSO with the signicant interactions of two independent variables.

0.6

q
0.4

DH2 O2
DDMSO

0.0

0.2

ln (C/CO)

-0.5
-1.0
R2 = 0.9477
R2 = 0.9525
R2 = 0.9641
R2 =0.9125

-1.5
-2.0
-2.5

0.0
0

 pH

0:61985
0:37522

 Fe2 

0:043358

 H2 O2 
 pH  Fe2 

0:61303

40
80
Time (min)

20

0:56031

3

120

40

60

80

100

120

Time (min)
Fig. 4. Concentrationtime proles of (a) DMSO and (b) H2O2 for selected runs.

Fig. 4a shows that at [Fe2+] = 2.0 mM and pH = 1.8, a change in

H2O2 loading from 20 mM to 60 mM resulted DMSO removal of
94.78% and 95.10%, respectively after 120 min of treatment. This
is a small change (0.34%) in the nal DMSO degradation despite
a 200% increase in H2O2 loading. This is further supported by the

8:19775  10

 pH  H2 O2 

9:83949  103

 Fe2   H2 O2 

0:29868

 pH2

0:31109

 Fe2 

2:43683  103

 H2 O2 2

14

In Eq. (14), the rst-order terms containing pH and H2O2 have

positive coefcients which mean that increasing their value also
increases the value of the response. At low pH, the solubility of ferrous ions in solution is high thus promoting the production of
hydroxyl radicals (Eq. (1)) which is the stronger oxidant compared

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J.I. Colades et al. / Separation and Purication Technology 145 (2015) 104112

(b)
3.00

19

2.50

7.35973

15.75

Fe (mM)

12.5

2.00

6.53271

2+

[H2O2]/[DMSO]

(a)

9.25

8.53664

10.0731
1.50

1.00

3.20

12.1028
14.1047

1.50

2.85
2.00

2.50
2.50

2.15

pH

1.00

2+

Fe (mM)
(mM)
Fe2+

1.80

2.15

2.50

1.80 3.00

2.85

3.20

pH

(d)
60.00

12.3

50.00

10.0731
8.53664

10.025

H2O2 (mM)

[H2O2]/[DMSO]

(c)

7.75
5.475

40.00

7.14647

3.2

5.65818
30.00

3.20

60.00

4.38732

2.85

50.00
2.50

40.00
2.15

30.00
HH2O2
O (mM)
(mM)
2 2

20.00

pH

1.80

2.15

2.50

20.00 1.80

2.85

3.20

pH

(f)
60.00

10.0731

12.2

50.00

10.125

H2O2 (mM)

[H2O2]/[DMSO]

(e)

8.05
5.975

10.0731

8.53664

40.00

7.14647

3.9
60.00

1.00
50.00

1.50

Fe2+(mM)
(mM)
Fe

4.38732

40.00

2.00
2+

5.65818

30.00

30.00

2.50

H2O(mM)
(mM)
H2O2
2

3.00 20.00

20.00
1.00

1.50

2.00

2.50

3.00

2+

Fe (mM)
Fig. 5. Surface and contour plots of the response D[H2O2]/D[DMSO] as a function of (a and b) pH and [Fe2+] with [H2O2] = 40 mM, (c and d) pH and [H2O2] with [Fe2+] = 2 mM
and (e and f) [H2O2] and [Fe2+] with pH = 2.5.

with hydroperoxyradical produced via Eq. (2). It is preferred that

we produce the stronger hydroxyl radical to make better use of
the hydrogen peroxide and degrade DMSO more effectively. Thus,
low pH results to higher hydrogen peroxide efciency and hence,

we see the pH containing term of Eq. (14) having a positive and

the largest magnitude coefcient among the rst-order terms.
On the other hand, the Fe2+-containing term shows that an
increase in Fe2+ loading results to the decrease in the value the

110

J.I. Colades et al. / Separation and Purication Technology 145 (2015) 104112

response variable. Increasing Fe2+ loading will result to lower H2O2

consumption per mole of DMSO degraded. Higher Fe2+ concentration in the reactor promotes higher rate of production of hydroxyl
radicals. Eq. (1) makes better use of the H2O2 by producing more
powerful hydroxyl radicals compared to hydroperoxyradicals produced by Eq. (2).
Fig. 4b shows the H2O2 consumption during the course of the
Fenton treatment at different operating conditions. Minimizing
the value of this response would be one of the goals in electroFenton treatment to reduce H2O2 consumption and thus, reduce
the cost of treatment. Aside from the cost [23], high H2O2 loading
is known to inhibit the Fenton treatment due to its scavenging
effect on the produced hydroxyl radical [19,33]. The scavenging
effect (Eq. (5)) leads to the production of a less potent oxidant
hydroperoxyl radical O2H compared to the more powerful OH.
At xed H2O2 loading of 40 mM, running at operating conditions at the low extreme (pH = 3.2, [Fe2+] = 1 mM) and high
extreme (pH = 1.8, [Fe2+] = 3 mM) resulted to nal H2O2

Table 5
Model validation at optimum conditions.
Independent variables
pH
Fe2+ loading (mM)
H2O2 loading (mM)

1.95
2.11
26

Response

Observed

Predicted

% DMSO removal
D[H2O2]/D[DMSO]

100a
4.2

98.9
4.3

Undetected by HPLC.

4.0
2+

pH = 1.8, [Fe ] = 3 mM, [H2O2] = 40 mM

2+

3.5

pH = 3.2, [Fe ] = 1 mM, [H2O2] = 40 mM

pH

3.0

2.5

2.0

concentrations of 18.20% and 18.00% and DMSO degradation efciency of 35.45% and 100% DMSO removal, respectively (Fig. 4).
There is little difference (0.2%) between the nal H2O2 concentrations for the two runs despite the large difference (64.55%) in
nal DMSO degradation efciencies. For the run with lower degradation efciency, the H2O2 itself and hydroxyl radicals produced
from H2O2 were wasted on side reactions that do not promote
DMSO degradation. Hence, from these ndings and the negative
sign of the H2O2-containing term of Eq. (14), it can be induced that
increasing H2O2 loading will only increase H2O2 consumption per
mole of DMSO degraded.
3.1.3. Validation of optimum conditions
Optimum conditions were obtained numerically using the
Design Expert Software. Shown in Table 5, the suggested values
of the independent variable were 1.95, 2.11 mM and 26 mM for
pH, Fe2+ loading, and H2O2 loading, respectively. A run was performed to validate the optimum conditions. The HPLC was not able
to detect any DMSO after the 2-h run which indicates 100% DMSO
removal. The model predicted 99% removal given the optimized
operating conditions producing an error of 1.0%. The D[H2O2]/
D[DMSO] was also able to arrive near the predicted value of the
model with 2.4% experimental error.
3.2. pH changes during Fenton reaction
At the onset of the electro-Fenton reaction, a slight increase in
pH (Fig. 6) was observed because the H2O2 added to start the reaction was kept in a basic solution to prevent its reduction to water
at neutral pH. During the course of the run, pH gradually decreased
as shown in Fig. 6. The pH changes are more obvious for the run
with initial pH of 3.2 compared to the run that started at pH of
1.8 since pH is the negative logarithm of H+ molar concentration.
A study done by Lee et al. [26] showed the kinetics and mechanism of DMSO degradation via hydroxyl radicals produced from
activating H2O2 using UV light. However, the study did not monitor
pH changes in the solution during DMSO degradation. But they
detected the presence of formaldehyde and methanesulnate, an
intermediate of DMSO degradation, with a proton as co-product
which makes the solution acidic (Eq. (15)) [34]. Further degradation of formaldehyde by hydroxyl radicals produces formic acid
(Eq. (16) [35]. Acidic intermediates are common [3638] in the
degradation of organics which causes the decrease in the pH value
of the solution.

3
CH3 2 SODMSO  OH O2 ! HCHO CH3 SO2 HO2 H
2
k 6:6  109 M1 s1
15

1.5
0

20

40

60

80

100

120

HCHO  OH O2 ! HCOO HO2 H

Time (min)

k 1:0  109 M1 s1

16

Fig. 6. pH changes during the electro-Fenton reaction at different initial pH.

Table 6
Studies on the application of the Fenton process on real wastewaters.
Wastewater

Olive oil mill

Rayon industry
Landll leachate
Tannery
Livestock
Coking
Real dyeing
Textile

COD load (mg/L)

112,500
2400
2950
2810
50005700
176.0 13.2
1224
1705

Operating conditions
pH

Type of Fenton process

H2O2/Fe2+

5.44
3
25
37.2
3.57
35
24
2.8

Electro-Fenton with anaerobic digestion

Electro-Fenton with chemical precipitation
Electro-Fenton
Electro-Fenton
Fenton
Fenton and electro-Fenton
Electro-Fenton with activated carbon ber cathode
Fenton/photo-Fenton

11.2
0.21.8

18
13

41

% COD removal

Reference

68
88
94.04
70
8095
75 (Fenton), 55 (EF)
75.2
62.976.3

[39]
[40]
[41]
[42]
[43]
[30]
[24]
[44]

J.I. Colades et al. / Separation and Purication Technology 145 (2015) 104112
Table 7
TFT-LCD wastewater characteristics.
Parameter

Value

pH
COD (mg/L)
TOC (mg/L)
Conductivity (lS)
Total dissolved solids (ppm)
Oxidative reduction potential (V)

9.84
6481.72
1693.41
105.70
67.52
171.00

1.0

DMSO in wastewater were pH 1.95, Fe2+ loading of 2.11 mM and

H2O2 loading of 26 mM for an initial pollutant loading of 5 mM.
The resulting optimum conditions were validated and the error
between the predicted and actual value for DMSO removal and
D[H2O2]/D[DMSO] were 1.0% and 2.4%, respectively. Changes in
pH were observed during the electro-Fenton treatment of DMSOcontaining wastewater. Lowering of pH was caused by the dominant Fenton reactions that produce H+ ions. Finally, electroFenton process used in this system successfully reduced TOC and
COD of actual TFT-LCD wastewater by 68% and 79%, respectively.
Acknowledgements

TOC (mg/L)
COD (mg/L)

0.6

This research was nancially supported by the Ministry of

Science and Technology, Taiwan (Contract No. MOST 99-2221-E041-012-MY3) and the Department of Science and Technology,
Philippines.

0.4

Appendix A. Supplementary material

0.2

Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.seppur.2015.02.039.

0.8

C/CO

111

References
0.0
0

20

40

60

80

100

120

Time (min)
Fig. 7. Treatment of TFT-LCD wastewater [Fe2+] = 5.125 mM, [H2O2] = 325 mM,
current = 1.5 A, pH = 1.95.

3.3. Application to real TFT-LCD wastewater

The Fenton process has been modied in many ways and applied
to real wastewaters (Table 6). To test the feasibility of the electroFenton system on real wastewater, TFT-LCD wastewater was
obtained from Toppan CFI Co., Ltd. in Tainan, Taiwan. Table 7 shows
the characteristics of the real wastewater that underwent electroFenton treatment. From the results of the optimization studies,
the pH of the actual wastewater was adjusted to pH of 1.95.
Ferrous ion loading used was 2.5 times the optimum and H2O2 loading was estimated from the initial COD load of the wastewater.
Fig. 7 shows that treatment of the TFT-LCD wastewater by electro-Fenton reduced TOC and COD by 68% and 79%, respectively. The
performance of the set-up is comparable to the results of previous
studies (Table 6) that applied the Fenton process for the treatment
of real wastewater.

4. Conclusion
The results of the study demonstrate the effectiveness of the
electro-Fenton process in treating TFT-LCD wastewater. Empirical
quadratic models for the optimization of critical process parameters namely: pH, Fe2+ loading, and H2O2 loading were generated
from the BoxBehnken design of experiment. The high coefcients
of determination for %DMSO removal (R2 = 0.9686) and H2O2 efciency (D[H2O2]/D[DMSO]) (R2 = 0.9887) indicate that the models
are robust and exhibits a good t in predicting the responses.
Ferrous ion loading was found to be the most dominant variable
that affects DMSO removal while the least dominant was H2O2
loading. Increasing pH and H2O2 loading was shown to decrease
H2O2 efciency, while increasing Fe2+ loading increases H2O2 efciency. The optimum conditions obtained for 100% removal of

[1] S.-W. Hung, Competitive strategies for Taiwans thin lm transistor-liquid

crystal display (TFT-LCD) industry, Technol. Soc. 28 (2006) 349361, http://
dx.doi.org/10.1016/j.techsoc.2006.06.004.
[2] S.-J. Park, T.-I. Yoon, J.-H. Bae, H.-J. Seo, H.-J. Park, Biological treatment of
wastewater containing dimethyl sulphoxide from the semi-conductor
industry, Process Biochem. 36 (2001) 579589, http://dx.doi.org/10.1016/
S0032-9592(00)00252-1.
[3] J. Anotai, C.-M. Chen, L.M. Bellotindos, M.-C. Lu, Treatment of TFT-LCD
wastewater containing ethanolamine by uidized-bed Fenton technology,
Bioresour. Technol. 113 (2012) 272275, http://dx.doi.org/10.1016/j.biortech.
2011.11.100.
[4] C.-C. Su, C.-M. Chen, J. Anotai, M.-C. Lu, Removal of monoethanolamine and
phosphate from thin-lm transistor liquid crystal display (TFT-LCD)
wastewater by the uidized-bed Fenton process, Chem. Eng. J. 222 (2013)
128135, http://dx.doi.org/10.1016/j.cej.2012.08.063.
[5] C.-N. Lei, L.-M. Whang, P.-C. Chen, Biological treatment of thin-lm transistor
liquid-crystal-display (TFT-LCD) wastewater using aerobic and anoxic/oxic
sequencing batch reactors, Chemosphere 81 (2010) 5764, http://dx.doi.org/
10.1016/j.chemosphere.2010.07.001.
[6] T. Murakami-Nitta, K. Kirimura, K. Kino, Oxidative degradation of dimethyl
sulfoxide by Cryptococcus humicolus WU-2, a newly isolated yeast, J. Biosci.
Bioeng. 95 (2003) 109111, http://dx.doi.org/10.1016/S1389-1723(03)80158-5.
[7] T. Fukushima, L.-M. Whang, P.-C. Chen, D.W. Putri, M.-Y. Chang, Y.-J. Wu, et al.,
Linking TFT-LCD wastewater treatment performance to microbial population
abundance of Hyphomicrobium and Thiobacillus spp., Bioresour. Technol. 141
(2013) 131137, http://dx.doi.org/10.1016/j.biortech.2013.03.122.
[8] J.J. Wu, M. Muruganandham, S.H. Chen, Degradation of DMSO by ozone-based
advanced oxidation processes, J. Hazard. Mater. 149 (2007) 218225, http://
dx.doi.org/10.1016/j.jhazmat.2007.03.071.
[9] T. Murakami-Nitta, H. Kurimura, K. Kirimura, K. Kino, S. Usami, Continuous
degradation of dimethyl sulfoxide to sulfate ion by Hyphomicrobium
denitricans WU-K217, J. Biosci. Bioeng. 94 (2002) 5256. <http://www.ncbi.
nlm.nih.gov/pubmed/16233269>.
[10] E. Brillas, I. Sirs, M.a. Oturan, Electro-Fenton process and related
electrochemical technologies based on Fentons reaction chemistry, Chem.
Rev. 109 (2009) 65706631, http://dx.doi.org/10.1021/cr900136g.
[11] N. Masomboon, C. Ratanatamskul, M.-C. Lu, Kinetics of 2,6-dimethylaniline
oxidation by various Fenton processes, J. Hazard. Mater. 192 (2011) 347353,
http://dx.doi.org/10.1016/j.jhazmat.2011.05.034.
[12] M.D.G. de Luna, J.I. Colades, C.-C. Su, M.-C. Lu, Comparison of dimethyl
sulfoxide degradation by different Fenton processes, Chem. Eng. J. 232 (2013)
418424, http://dx.doi.org/10.1016/j.cej.2013.07.107.
[13] W.-P. Ting, M.-C. Lu, Y.-H. Huang, Kinetics of 2,6-dimethylaniline degradation
by electro-Fenton process, J. Hazard. Mater. 161 (2009) 14841490, http://
dx.doi.org/10.1016/j.jhazmat.2008.04.119.
[14] M.-C. Lu, Y.-F. Chang, I.-M. Chen, Y.-Y. Huang, Effect of chloride ions on the
oxidation of aniline by Fentons reagent, J. Environ. Manage. 75 (2005) 177
182, http://dx.doi.org/10.1016/j.jenvman.2004.12.003.
[15] M.D.G. de Luna, M.L. Veciana, J.I. Colades, C.-C. Su, M.-C. Lu, Factors that
inuence degradation of acetaminophen by Fenton processes, J. Taiwan Inst.
Chem. Eng. 45 (2014) 565570, http://dx.doi.org/10.1016/j.jtice.2013.05.020.
[16] A. El-Ghenymy, S. Garcia-Segura, R.M. Rodrguez, E. Brillas, M.S. El Begrani, B.A.
Abdelouahid, Optimization of the electro-Fenton and solar photoelectro-

112

[17]

[18]

[19]

[20]

[21]

[22]
[23]

[24]

[25]

[26]

[27]

[28]

[29]

[30]

J.I. Colades et al. / Separation and Purication Technology 145 (2015) 104112
Fenton treatments of sulfanilic acid solutions using a pre-pilot ow plant by
response surface methodology, J. Hazard. Mater. 221222 (2012) 288297,
http://dx.doi.org/10.1016/j.jhazmat.2012.04.053.
S. Garcia-Segura, J.a. Garrido, R.M. Rodrguez, P.L. Cabot, F. Centellas, C. Arias,
et al., Mineralization of umequine in acidic medium by electro-Fenton and
photoelectro-Fenton processes, Water Res. 46 (2012) 20672076.
H. Zhang, C. Fei, D. Zhang, F. Tang, Degradation of 4-nitrophenol in aqueous
medium by electro-Fenton method, J. Hazard. Mater. 145 (2007) 227232,
http://dx.doi.org/10.1016/j.jhazmat.2006.11.016.
J. Anotai, C.-C. Su, Y.-C. Tsai, M.-C. Lu, Effect of hydrogen peroxide on
aniline oxidation by electro-Fenton and uidized-bed Fenton processes, J.
Hazard. Mater. 183 (2010) 888893, http://dx.doi.org/10.1016/j.jhazmat.
2010.07.112.
E.J. Ruiz, A. Hernndez-Ramrez, J.M. Peralta-Hernndez, C. Arias, E. Brillas,
Application of solar photoelectro-Fenton technology to azo dyes
mineralization: effect of current density, Fe2+ and dye concentrations, Chem.
Eng. J. 171 (2011) 385392, http://dx.doi.org/10.1016/j.cej.2011.03.004.
H. Liu, X.Z. Li, Y.J. Leng, C. Wang, Kinetic modeling of electro-Fenton reaction in
aqueous solution, Water Res. 41 (2007) 11611167, http://dx.doi.org/10.1016/
j.watres.2006.12.006.
M. Panizza, G. Cerisola, Electro-Fenton degradation of synthetic dyes, Water
Res. 43 (2009) 339344, http://dx.doi.org/10.1016/j.watres.2008.10.028.
I. Carra, E. Ortega-Gmez, L. Santos-Juanes, J.L. Casas Lpez, J.A. Snchez Prez,
Cost analysis of different hydrogen peroxide supply strategies in the solar
photo-Fenton process, Chem. Eng. J. 224 (2013) 7581, http://dx.doi.org/
10.1016/j.cej.2012.09.067.
C.-T. Wang, W.-L. Chou, M.-H. Chung, Y.-M. Kuo, COD removal from real dyeing
wastewater by electro-Fenton technology using an activated carbon ber
cathode, Desalination 253 (2010) 129134, http://dx.doi.org/10.1016/
j.desal.2009.11.020.
M. Zhou, Q. Yu, L. Lei, G. Barton, Electro-Fenton method for the removal of
methyl red in an efcient electrochemical system, Sep. Purif. Technol. 57
(2007) 380387, http://dx.doi.org/10.1016/j.seppur.2007.04.021.
Y. Lee, C. Lee, J. Yoon, Kinetics and mechanisms of DMSO (dimethylsulfoxide)
degradation by UV/H(2)O(2) process, Water Res. 38 (2004) 25792588, http://
dx.doi.org/10.1016/j.watres.2004.02.028.
K. Cruz-Gonzlez, O. Torres-Lopez, A.M. Garca-Len, E. Brillas, A. HernndezRamrez, J.M. Peralta-Hernndez, Optimization of electro-Fenton/BDD process
for decolorization of a model azo dye wastewater by means of response
surface methodology, Desalination 286 (2012) 6368, http://dx.doi.org/
10.1016/j.desal.2011.11.005.
S. Garcia-Segura, L.C. Almeida, N. Bocchi, E. Brillas, Solar photoelectro-Fenton
degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid optimized
by response surface methodology, J. Hazard. Mater. 194 (2011) 109118,
http://dx.doi.org/10.1016/j.jhazmat.2011.07.089.
J. Virkutyte, E. Rokhina, V. Jegatheesan, Optimisation of electro-Fenton
denitrication of a model wastewater using a response surface methodology,
Bioresour. Technol. 101 (2010) 14401446, http://dx.doi.org/10.1016/
j.biortech.2009.10.041.
X. Zhu, J. Tian, R. Liu, L. Chen, Optimization of Fenton and electro-Fenton
oxidation of biologically treated coking wastewater using response surface

[31]

[32]

[33]

[34]

[35]

[36]

[37]

[38]

[39]

[40]

[41]

[42]

[43]

[44]

methodology, Sep. Purif. Technol. 81 (2011) 444450, http://dx.doi.org/

10.1016/j.seppur.2011.08.023.
I. Arslan-Alaton, G. Tureli, T. Olmez-Hanci, Treatment of azo dye production
wastewaters using Photo-Fenton-like advanced oxidation processes:
optimization by response surface methodology, J. Photochem. Photobiol. A
Chem. 202 (2009) 142153, http://dx.doi.org/10.1016/j.jphotochem.2008.11.019.
C.S.D. Rodrigues, L.M. Madeira, R.a.R. Boaventura, Optimization of the azo dye
Procion Red H-EXL degradation by Fentons reagent using experimental
design, J. Hazard. Mater. 164 (2009) 987994, http://dx.doi.org/10.1016/
j.jhazmat.2008.08.109.
Y.Y. Chu, Y. Qian, W.J. Wang, X.L. Deng, A dual-cathode electro-Fenton
oxidation coupled with anodic oxidation system used for 4-nitrophenol
degradation, J. Hazard. Mater. 199200 (2012) 179185, http://dx.doi.org/
10.1016/j.jhazmat.2011.10.079.
G. V Buxton, C.L. Greenstock, W.P. Helman, A.B. Ross, Critical review of rate
constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl
radicals (OH/O) in aqueous solution, At. Energy. 17 (1988) 513886. <http://
link.aip.org/link/JPCRBU/v17/i2/p513/s1/html>.
R. Flyunt, O. Makogon, M.N. Schuchmann, K.-D. Asmus, C. von Sonntag, OHradical-induced oxidation of methanesulnic acid. The reactions of the
methanesulfonyl radical in the absence and presence of dioxygen, J. Chem.
Soc. Perkin Trans. 2 (2001) 787792, http://dx.doi.org/10.1039/b009631h.
J.-H. Sun, S.-P. Sun, G.-L. Wang, L.-P. Qiao, Degradation of azo dye Amido black
10B in aqueous solution by Fenton oxidation process, Dyes Pigments 74 (2007)
647652, http://dx.doi.org/10.1016/j.dyepig.2006.04.006.
A.P. Murphy, W.J. Boegli, M.K. Price, D. Charles, A Fenton-like reaction to
neutralize formaldehyde waste solutions, Environ. Sci. Technol. 23 (1989)
166169, http://dx.doi.org/10.1021/es00179a004.
C.K. Duesterberg, S.E. Mylon, T.D. Waite, PH effects on iron-catalyzed oxidation
using fentons reagent, Environ. Sci. Technol. 42 (2008) 85228527, http://
dx.doi.org/10.1021/es801720d.
S. Khou, F. Aloui, S. Sayadi, Treatment of olive oil mill wastewater by
combined process electro-Fenton reaction and anaerobic digestion, Water Res.
40 (2006) 20072016, http://dx.doi.org/10.1016/j.watres.2006.03.023.
P. Ghosh, A.N. Samanta, S. Ray, Reduction of COD and removal of Zn2+ from
rayon industry wastewater by combined electro-Fenton treatment and
chemical precipitation, Desalination 266 (2011) 213217, http://dx.doi.org/
10.1016/j.desal.2010.08.029.
S. Mohajeri, H.A. Aziz, M.H. Isa, M.A. Zahed, M.N. Adlan, Statistical
optimization of process parameters for landll leachate treatment using
electro-Fenton technique, J. Hazard. Mater. 176 (2010) 749758, http://
dx.doi.org/10.1016/j.jhazmat.2009.11.099.
U. Kurt, O. Apaydin, M.T. Gonullu, Reduction of COD in wastewater from an
organized tannery industrial region by electro-Fenton process, J. Hazard.
Mater. 143 (2007) 3340, http://dx.doi.org/10.1016/j.jhazmat.2006.08.065.
H. Lee, M. Shoda, Removal of COD and color from livestock wastewater by the
Fenton method, J. Hazard. Mater. 153 (2008) 13141319, http://dx.doi.org/
10.1016/j.jhazmat.2007.09.097.
F. Torrades, J. Garca-Montao, Using central composite experimental design
to optimize the degradation of real dye wastewater by Fenton and photoFenton reactions, Dyes Pigments 100 (2014) 184189, http://dx.doi.org/
10.1016/j.dyepig.2013.09.004.