Journal of Cleaner Production 175 (2018) 145e154

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Journal of Cleaner Production

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

Removal of chemical oxygen demand from thin-film transistor liquid-

crystal display wastewater using chitosan-coated bentonite: Isotherm,
kinetics and optimization studies
Mayzonee Ligaray a, Cybelle M. Futalan b, Mark Daniel de Luna c, Meng-Wei Wan d, *
a
School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of Korea
b
National Research Center for Disaster-Free and Safe Ocean City, Busan 49315 Republic of Korea
c
Department of Chemical Engineering, University of Philippines, 1101 Diliman, Quezon City, Philippines
d
Department of Environmental Resources Management, Chia Nan University of Pharmacy and Science, Tainan 71710, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: In this study, real thin-film transistor liquid-crystal display wastewater with an initial chemical oxygen
Available online 22 December 2017 demand (COD) concentration of 1348.00 ppm was treated using chitosan-coated bentonite (CCB).
Characterization analysis of the CCB adsorbent was performed using Brunauer-Emmett-Teller surface
Keywords: area analysis, scanning electron microscopy, and Fourier-transform infrared spectrometer. The effect of
Central composite design parameters such as contact time, CCB dosage, pH and temperature on the COD removal was examined.
Chitosan-coated bentonite
Results show that increasing the contact time and CCB dosage increases COD removal efficiency while no
Chemical oxygen demand
considerable change was observed in removal efficiency with varying temperature and pH. Adsorption
Optimization
TFT-LCD wastewater
experiments showed that the removal of COD using CCB best fits the Langmuir isotherm (R2
0.9821)
Thermodynamics while kinetic data was best described by the pseudo-second order equation (R2
0.9980), which implies
that chemisorption is the rate-determining step. Thermodynamic studies revealed that adsorption of
COD onto CCB was spontaneous, exothermic (DH ¼ 5.95 kJ/mol) and decreased randomness in the
system (DS ¼ -0.88 J/mol$K). Optimization studies using response surface methodology with central
composite design was performed to determine the operating parameters that would yield the maximum
COD removal. It was determined that the optimum conditions of 20.32 h, 0.8 g CCB, pH 4.0, and 30  C
would yield a maximum removal of COD of 73.34%.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction produced by the TFT-LCD industry is comprised of high-strength

Thin-film transistor liquid crystal display (TFT-LCD) is one of the
largest and fast-growing technologies in Korea, Japan and Taiwan
(Lei et al., 2010). Currently, the TFT-LCD industry is worth more
than 100 billion dollars due to the growing demand in electronic
products (Yang et al., 2012). Panel devices that are compact, energy
efficient and produces high quality images are manufactured and
utilized as a component in monitor, notebook PCs, and mobile
phones (Anotai et al., 2012; Colades et al., 2015). The processes
involved in the manufacture of the display panels include photo-
lithography, etching and deposition, which generate large volumes
of wastewater (Lu and Liu, 2010). About 33% of the total wastewater
* Corresponding author.
E-mail address: peterwan@mail.cnu.edu.tw (M.-W. Wan).
organic-containing wastewater, which is characterized by its low
ratio of biological oxygen demand (BOD) to chemical oxygen
demand (COD) and low biodegradability (Fukushima et al., 2013;
Park et al., 2001). The contaminants, which are both organic and
inorganic in nature, contained in TFT-LCD wastewater are the
following: acetone, ethanol, ethyl acetate, toluene, isopropyl
alcohol, propylene glycol monomethyl ether (PGME), mono-
ethanolamine (MEA), dimethyl sulfoxide (DMSO), tetra-methyl
ammonium hydroxide (TMAH), ammonium (NHþ 
4 ), nitrate (NO3 ),

nitrite (NO2 ), and heavy metals such as gallium (Ga), indium (In)
and molybdenum (Mo) (Chang et al., 2010; Fukushima et al., 2013;
Lee et al., 2016). Wastewater with high COD concentration would
be detrimental when discharged into surface waters and ground-
water. High amount of organic-containing compounds present in
water bodies would lead to reduced dissolved oxygen levels and
development of anaerobic conditions. Various environmental

https://doi.org/10.1016/j.jclepro.2017.12.052
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
146 M. Ligaray et al. / Journal of Cleaner Production 175 (2018) 145e154
regulations have been implemented to maintain non-toxicity of
water bodies, where COD standards are set to 100 mg/L by the
Taiwan Environmental Protection Agency for electronic industries
and 60e300 mg/L by the Philippine Department of Environment
and Natural Resources for discharge into inland, coastal and
protected waters.
Previous studies have evaluated different technologies in the
treatment of TFT-LCD wastewater using membrane bioreactor in
the removal of nitrogen (Whang et al., 2012), electro-Fenton
process in the removal of DMSO, phosphate and MEA (Colades
et al., 2015; Su et al., 2013), fluidized-bed Fenton technology in
the removal of MEA (Anotai et al., 2012; Su et al., 2013), anaerobic
sludge blanket followed by aerobic bioreactor in the removal of
TMAH (Hu et al., 2012), combined membrane bioreactor and
reverse osmosis in the removal of COD, BOD5 and total organic
carbon (Chen and Chen, 2004), airlift bioreactor in the removal of
DMSO (He et al., 2011), and hybrid precipitation-microfiltration in
the removal of phosphate and fluoride (Lu and Liu, 2010). However,
biological treatment such as activated sludge in COD removal
would require several months to stabilize due to microbes utilized
in treating the wastewater are sensitive to slight changes in the
environment (Urakami et al., 1990). On the other hand, Fenton
technology is an expensive treatment method, wherein operators
are required to have a certain degree of expertise in the area of
advanced oxidation process (Mohajerani et al., 2010). Moreover,
Fenton process is typically combined with biological treatments,
which translates into higher capital costs (Lei et al., 2010).
Adsorption is an attractive and efficient treatment technology
that can be operated under ambient pressure and temperature,
incurs relatively low cost, and requires simple operation. Most
importantly, adsorption can remove contaminants from waste-
water effluents that are present in high loading or dilute concen-
tration (Popuri et al., 2009). Various adsorbents have been
developed for the removal of organic contaminants and COD which
includes chitosan flakes (Dionisi et al., 2014), nano-CaO2-coated
clinoptilolite (Zhou et al., 2017), activated carbon derived from
banana stem (Ghani et al., 2017) and coffee-waste (Poblete et al.,
2017), rice hull/MnFe2O4 composite (Lv et al., 2009), and carbon-
mineral composite (Halim et al., 2010).
In recent years, chitosan-clay beads present to be a promising
class of adsorbent materials since it combines the physical, chem-
ical and structural properties of both organic and inorganic mate-
rials (El-Korashy et al., 2016). Clay materials are characterized by
their abundance in nature, low cost, availability, relatively large
surface areas and easy surface functionalization (Rekik et al., 2017;
Wu et al., 2009). Meanwhile, chitosan has several excellent prop-
erties such as non-toxicity, biodegradability, hydrophilicity, and
ease of modification (Elwakeel and Atia, 2014; Zhang et al., 2016). In
addition, chitosan has an abundance of reactive functional groups
such as amino and hydroxyl groups that easily interacts with
contaminants present in wastewater (Kumar et al., 2004). Most
importantly, clay and chitosan are considered to be sustainable
materials. Clay refers to geologically available minerals found in
natural soils and sediment (Yu et al., 2017). Moreover, clay could be
derived from overburden or waste rock, which is a type of waste
generated by the mining industry (Lu and Cai, 2012). On the other
hand, chitosan is commercially extracted from exoskeletons of
crabs, shrimps, and crayfish (Arancibia et al., 2015; Kong et al.,
2010; Kumari et al., 2017). Globally, the shrimp industry produces
solid waste where 40e50% of the total weight are composed of
shells, tails and heads (Ogawa et al., 2007). Above all, utilization of
chitosan and bentonite that could be derived from solid wastes
generated by a variety of industries would help in the protection of
the environment as well as waste disposal and management.
Moreover, the distinct characteristics of both chitosan and clay
materials suggest that chitosan-clay beads present an attractive,
cost-effective option for wastewater treatment. Several previous
studies on chitosan-clay beads have been carried out where chi-
tosan coated montmorillonite was utilized in the removal of
tungsten (Gecol et al., 2006) and tannic acid (An and Dultz, 2007);
N,O-carboxymethyl-chitosan/montmorillonite nanocomposite in
the adsorption of Congo red (Wang and Wang, 2008); chitosan
intercalated montmorillonite in the removal of basic dyes (Chang
and Juang, 2004) and adsorption of humic acid, tannic acid, basic
and reactive dyes using the chitosan/activated clay composite
(Monvisade and Siriphannon, 2009). Currently, several studies have
been made on the removal of various contaminants such as Ni(II)
(Futalan et al., 2011), Pb(II) (Futalan et al., 2011), Cu(II) (Dalida et al.,
2011; Futalan et al., 2011), In(III) (Calagui et al., 2014), As(V) (Arida
et al., 2016), and dibenzothiophene sulfone (Lu et al., 2016) using
chitosan-coated bentonite (CCB) and its crosslinked derivatives.
However, there are no reports regarding the treatment of real TFT-
LCD wastewater using CCB.
The present work aims to investigate the applicability of CCB in
removing COD from real TFT-LCD wastewater obtained from a
semiconductor industry located in Tainan, Taiwan. The effect of
operating parameters namely initial pH, temperature, CCB mass,
and contact time on COD removal efficiency was investigated.
Isotherm studies were carried out using Langmuir, Freundlich and
Dubinin-Radushkevich models. Moreover, kinetic studies utilized
pseudo-first order, pseudo-second order and intra-particle diffu-
sion equations in evaluating the rate-determining step of the
system. Thermodynamic studies were performed to determine
parameters such as DG , DH and DS . Optimization studies were
carried out by the response surface methodology (RSM) using
central composite design (CCD) with four independent variables
such as temperature, pH, contact time and mass of CCB.
2. Materials and method
2.1. Chemicals and reagents
Low molecular weight chitosan (C12H24N2O9, 75%e85% deace-
tylation) and bentonite (Al2O3$4SiO2$H2O) were procured from
Sigma-Aldrich. Hydrochloric acid (HCl, 37% fuming) was acquired
from Merck while sodium hydroxide pellets (NaOH, 99%) was ob-
tained from Formosa-F.
Real TFT-LCD wastewater was obtained from a semi-conductor
industry located in Tainan, Taiwan. The characteristics and back-
ground composition of the wastewater is illustrated in Table 1.
2.2. Synthesis of chitosan-coated bentonite
The synthesis method of CCB utilized was similar to the process
of Wan et al. (2004) (Wan et al., 2004). Chitosan (5 g) was dissolved
in 300 mL 5% (v/v) HCl was stirred at 300 rpm for 2 h. Bentonite
(100 g) was added to the mixture and stirred for 3 h. Then, 1 N
NaOH was added in a dropwise method until pH of the mixture was
Table 1
Characterization of TFT-LCD wastewater obtained from Tainan, Taiwan.
Parameter Unit Value
pH 11.00
Turbidity NTU 241.67
SS mg/L 74.00
PSD nm 142.65
Color Absorbance 2.94
%Transparency 0.10
COD mg/L 1383.00
 M. Ligaray et al. / Journal of Cleaner Production 175 (2018) 145e154 147

neutralized (pH 7e7.5). In a precision oven (DV452, Channel), the 2.7. Adsorption thermodynamics
CCB beads were dried at 105  C for 24 h. The CCB beads with
particle size ranging 0.21e0.50 mm were utilized throughout the For thermodynamics experiments, TFT-LCD wastewater (30 mL)
study. with pH 4.0 and 1.00 g CCB in an Erlenmeyer flask was agitated
using a reciprocal shaker bath at 50 rpm for 24 h. The temperature
2.3. Characterization method of chitosan-coated bentonite of the water bath was varied from 25  C to 45  C. Then, the treated
effluent was filtered using Whatman #40 filter, where filtrated was
Characterization in determining the surface morphology of CCB analyzed for COD residual concentration.
was carried out using scanning electron microscope (SEM)
(TM-1000, Hitachi) using a tungsten filament running at 20.0 kV 3. Results and discussion
under vacuum of 1.33  106 mBar. The surface area and pore
diameter were determined using Brunauer, Emmett, Teller (BET) 3.1. Characterization of chitosan-coated bentonite
analyzer (ASAP 2010, Micrometrics) by N2 adsorption at 77 K. The
functional groups involved in the COD adsorption using CCB were Fig. 1 illustrates the surface morphology of chitosan and CCB as
identified using Fourier transform infrared (FTIR) spectrometer well as the FT-IR spectra of CCB before and after adsorption. In
(4100, JASCO) with KBr pellets that operated within the range of Fig. 1a and b, chitosan displays a relatively smooth, continuous
4000e400 cm1. surface while CCB shows an irregular surface characterized by
cavities and small pores represented by the black regions in the
2.4. Optimization studies image. The water content was determined to be 5.91% for bentonite,
11.64% for chitosan and 5.73% for CCB. Table 3 illustrates the physical
The optimization study was comprised of a total of 30 runs, properties of bentonite, chitosan and CCB, where the BET surface
where a five-level central composite design (CCD) was carried out area can be arranged in the order of: chitosan < CCB < bentonite. In
(Table 2) using Design Expert 7.1.4. The significance of the param- terms of total pore volume, chitosan has the smallest total pore
eters such as contact time, CCB mass, pH and temperature was volume, followed by CCB and bentonite. Based on the average pore
determined using CCD. A second-order polynomial was utilized to diameter values, chitosan is categorized to be mesoporous while
correlate the mathematical relationship of the COD removal effi- bentonite and CCB are macroporous. When compared to bentonite,
ciency with the four independent variables and its interactions (Eq. both CCB and chitosan have inferior properties such as surface area
(1)): and pore volume. This indicates that individual bentonite particles
are not coated by chitosan. Instead, aggregates of bentonite particles
X
4 X
4 X
4 X
4 were coated by the chitosan polymer. The results agree with the
Y ¼ b0 þ bi Xi þ bij Xi Xj þ bii Xi2 (1) study of Monvisade and Siriphannon (2009), where the decrease of
i¼1 i¼1 j¼1 j¼4
the micropore area of CCB could be due to the bentonite pores that
were blocked upon coating of chitosan (Monvisade and
where Y is the predicted response (COD removal efficiency); bi, bii
Siriphannon, 2009). Based from Fig. 1c, the FT-IR spectrum of CCB
and bij represents the parameters of linear, quadratic and
before adsorption is a combination of the peaks present in chitosan
interactions effects; b0 is the model constant; and Xi and Xj refer to
and bentonite. The bands in 3636 cm1 and 3449 cm1 indicate the
the independent variables (Bezerra et al., 2008). The optimum
stretching vibration of the OeH bonds of chitosan and vibrations of
operating conditions were determined using analysis of variance
the amine groups, respectively. The band at 1641 cm1 refers to the
and 3D surface response plots.
bending vibrations of the amide (-N-H) bonds. After adsorption,
bands at 3636 cm1 and 1641 cm1 shifted to lower peaks at
2.5. Adsorption kinetics
3634 cm1 and 1638 cm1, respectively. This implies the involve-
ment of amine groups of CCB in the removal of COD from
Kinetic studies were carried out by placing 1.0 g CCB and 30 mL
wastewater.
TFT-LCD wastewater into a 125-mL Erlenmeyer flask. The flask was
agitated at 50 rpm using a reciprocal shaker bath (BT-350, YIH-DER)
3.2. Effect of contact time, pH, temperature and adsorbent mass
at pH 4.0 for predetermined time intervals (5e1440 min). After
adsorption, effluent was filtered using Whatman #40 filter and the
In Fig. 2a, the % COD removal was observed to rapidly increase
residual COD of the filtrate was determined using chemical
from 49.16% to 70.54% when contact time was increased from 5 min
analysis.
to 4 h, respectively. As the contact time was further increased from
4 h to 24 h, only a slight increase in COD removal was observed from
2.6. Adsorption isotherm
70.54% to 76.66%. At the start of the adsorption process, functional
groups of CCB were readily available for uptake of COD that resulted
About 30 mL of wastewater was placed in an Erlenmeyer flask
to the rapid and instantaneous removal of COD during the first few
containing predetermined mass of CCB (0.10e2.00 g) and was
minutes. When the binding sites started to get saturated, the
agitated at 50 rpm for 24 h and 25  C. The effluent after adsorption
adsorption of COD was observed to slow down due to repulsive
was filtered using Whatman #40 filter paper, where filtrate was
forces existing between COD compounds attached to the CCB surface
subjected to chemical analysis.
and unbound CCB compounds. After adsorption, the pH of the so-
lution was observed to shift from pH 11.0 to pH range from 6.8 to 8.5.
Table 2
Results show that increasing the CCB mass from to 0.1 ge0.7 g
The parameters and levels in the central composite design.
leads to an increase in COD removal from 19.52% to 73.66%,
Parameter 2 1 0 þ1 þ2 respectively (Fig. 2b). The significant increase in COD removal with
Contact time (h) 6 12 18 24 30 increase in CCB mass implies that there is higher amount of binding
CCB mass (g) 0.2 0.4 0.6 0.8 1.0 sites available. However, dosage from 0.7 g to 2.0 g, there was only
pH 3 4 5 6 7 slight increase in removal observed from 73.66% to 76.66%. This
Temperature ( C) 25 30 35 40 45
implies that the remaining COD compounds in the effluent do not
148 M. Ligaray et al. / Journal of Cleaner Production 175 (2018) 145e154

(a) (b)

18
(c)
15
% Transmission

12

3 FTIR CCB
FTIR after adsorption

0
4000 3550 3100 2650 2200 1750 1300 850 400

Wavelength (cm-1)
Fig. 1. Characterization analysis such as SEM micrographs of (b) chitosan and (c) CCB, and (c) Fourier transform infrared (FT-IR) spectra of CCB before and after adsorption.

Table 3 atom that is easily accessible. In general, both DMSO and TMAH
Physical property of bentonite, chitosan and CCB. have positively charged groups that would interact via electrostatic
Chitosan Bentonite CCB attraction with the negatively-charged surface area of CCB
2
BET surface area (m /g) 2.12 28.17 8.10 (Tanaskovi
c et al., 2014).
Micropore area (m2/g) 0.38 7.25 2.10  104
Average pore diameter (nm) 11.61 57.64 67.80
3.3. Isotherm, thermodynamics and kinetics study
Total pore volume (cm3/g) 0.032 0.088 0.042

Adsorption isotherms in the COD removal using CCB from TFT-

show any affinity to the available functional groups of CCB. Mean-
while, the pH of the system was observed to be within the range
from 6.5 to 9.1 after adsorption.
Fig. 2c shows that varying the pH from 3.0 to 7.0 did not show
any apparent trend on the COD removal, wherein the values of COD
removal range from 74.55% to 77.46%. The isoelectric point of CCB is
pH ¼ 2.8, which implies that under the pH range studied from 3.0 to
7.0, the surface charge of CCB is negative (Calagui et al., 2014) and
that the COD compounds removed are characterized by their pos-
itive charges. Therefore, varying the pH would have no significant
effect on the removal of COD. The main organic compounds present
in the real TFT-LCD wastewater are DMSO and TMAH compounds
(Lin et al., 2011). The contaminant DMSO has two functional groups,
which are the eCH3 group and eSO group. An individual DMSO
molecule present in water would have its S atom bear a partial
positive charge while TMAH contains a positively charged nitrogen
LCD wastewater were obtained using various models such as
Langmuir, Freundlich and Dubinin-Radushkevich (D-R). In the
Langmuir isotherm, the adsorbent surface is assumed to be
comprised of sites with homogenous energy levels, where each
adsorption site can only accommodate one adsorbate molecule.
Moreover, there are no interactions occurring between adsorption
sites (Langmuir, 1918). The linear form of Langmuir isotherm is
provided in Eq. (2):
Ce Ce 1
¼ þ (2)
qe qmax KL qmax
where Ce is concentration of COD at equilibrium (mg/L), KL is the
Langmuir constant, qe and qmax are the equilibrium and maximum
adsorption capacities of CCB (mg/g), respectively.
The Freundlich isotherm is used to describe the adsorption of
organics from aqueous streams onto activated carbon. It is assumed
 M. Ligaray et al. / Journal of Cleaner Production 175 (2018) 145e154 149

100 100
(a) (b)
80 80

% COD Removal
% COD Removal

60 60

40 40

20 20

0 0
0.083
0.167

1
2
4
6
12
18
24
0.5

0.1 0.3 0.5 0.7 0.9 1.2 1.6 2.0

Time (h) CCB dosage (g)

m = 1.0 g, pH = 4, T = 298 K t = 24 h, pH = 4, T = 298 K

100 100
(c) (d)
80 80
% COD Removal
% COD Removal

60 60

40 40

20 20

0 0
3 4 5 6 7 298 303 308 313 318
pH Temperature (K)

t = 24 h, m = 1.0 g, T = 298 K t = 24 h, m = 1.0 g, pH = 4

Fig. 2. Effect of (a) contact time, (b) CCB dosage, (c) pH, and (d) temperature on the percent removal of COD of the TFT-LCD wastewater after adsorption (volume ¼ 30 mL,
speed ¼ 50 rpm).

that the materials adsorbed on the adsorbent surface are propor- where qmax is the maximum adsorption capacity (mg/g), b is the D-
tional to the concentration of aqueous phase at low adsorbate R constant (kJ2/mol2) and ε is the Polanyi potential. The Polanyi
concentrations. The equation is given in Eq. (3) (Freundlich, 1906): potential can be computed using Eq. (5):

1  
log qe ¼ log KF þ log Ce (3) 1
n ε ¼ RT ln 1 þ (5)
Ce
where KF and n are Freundlich constants that refer to the adsorption
where R is the universal gas constant (kJ/mol$K) and T is the ab-
capacity (mg/g) and adsorption intensity of the solute on the
solute operating temperature (K). The mean energy of adsorption
adsorbent, respectively.
(E, kJ/mol) can be calculated by Eq. (6):
The D-R model is commonly used to describe the adsorption
equilibria of organic compounds in porous solids (Febrianto et al.,
2009). It is represented in Eq. (4) (Dubinin, 1960): E ¼ ð2bÞ1=2 (6)
Table 4a lists the isotherm constants obtained from Langmuir,
ln qe ¼ ln qmax  bε2 (4)
Freundlich and D-R models. Based on the values of correlation
150 M. Ligaray et al. / Journal of Cleaner Production 175 (2018) 145e154

Table 4a surfaces (Ferreiro and de Bussetti, 2007). The DG values for COD
Langmuir, Freundlich and D-R isotherm parameters for the adsorption of COD using adsorption at 25  Ce35  C were observed to be negative, which
CCB from TFT-LCD wastewater.
suggests that the adsorption is a spontaneous and feasible process.
Isotherm Parameter Unit Value R2 The values of DG become more negative with increase in tem-
Langmuir KL L/mg 0.048 0.9821 perature, implying that adsorption using CCB is more feasible at
qmax mg/g 47.62 higher temperature. However, only slight changes were observed
Freundlich KF mg/g 28.05 0.2960 with the values of DG as the temperature was varied from 25  C to
1/n mg/L 0.075
35  C.
D-R b kJ2/mol2 0.002 0.4925
qmax mg/g 28.18 Kinetics study of the adsorbent would determine how fast the
E kJ/mol 15.81 adsorbate uptake on the solid surface would take place. The
pseudo-first order or Lagergren equation is given by Eq. (10):

k1t
Table 4b logðqe  qtÞ ¼ log qe  (10)
Thermodynamic parameters of COD adsorption onto CCB from TFT-LCD wastewater. 2:303
Temperature (K) DG (kJ/mol) DH (kJ/mol) DS (J/mol$K) where qe and qt are the amount of COD adsorbed by the adsorbent
298 2.66 5.95 0.88 (mg/g) at equilibrium and at time t, and k1 is the pseudo-first order
303 2.63 kinetic rate constant (1/h).
308 2.55
The pseudo-second order equation is expressed as Eq. (11):

t 1 t
coefficient, Langmuir isotherm (R2
0.9821) can adequately
¼ þ (11)
qt k2qe2 qe
describe the adsorption of COD from TFT-LCD wastewater using
CCB. This indicates that removal of COD occurs in monolayer where k2 is the kinetic rate constant (g/mg$h).
adsorption that involves one type of functional group, which is the Intraparticle diffusion equation is in the form of Eq. (12):
amine group of CCB.
The important thermodynamic aspects were determined such qt ¼ kit 0:5 þ Ci (12)
as change in free Gibbs energy (DG ), change in enthalpy (DH ) and
change in entropy (DS ). The change in free Gibbs energy could be where ki is the intraparticle diffusion rate constant (mg/g$h0.5) and
computed using Eq. (7) (Ferreiro and de Bussetti, 2007): Ci is the thickness of the boundary layer.
Based on Table 4c, pseudo-second order has the highest corre-
DG0 ¼ RT ln Kc (7) lation coefficient value (R2
0.9980) when compared to pseudo-
first order (R2 ¼ 0.8611) and intra-particle diffusion model
where DG0 is the change in free Gibbs energy (kJ/mol) and Kc is the (R2 ¼ 0.8980; R2 ¼ 0.8091). This indicates that chemisorption is the
thermodynamic equilibrium constant. The value of Kc could be rate-determining step of the removal of COD from TFT-LCD
calculated using Eq. (8): wastewater using CCB, where covalent bonds are formed be-
tween the amine functional groups of CCB and COD compounds
Cads present in the TFT-LCD wastewater. The experimental qe value
Kc ¼ (8) (26.78 mg/g) was compared to the theoretical qe values generated
Ce
by the kinetic models. The experimental qe is in good agreement
where Cads is the amount solute adsorbed by the adsorbent (mg/L) with the theoretical qe data generated by the pseudo-second order
at equilibrium. equation. Moreover, in Fig. 3bed, the plot of pseudo-second order
The following thermodynamic parameters (DH , DS ) can be equation shows a good agreement between the predicted and
computed using Eq. (9): experimental kinetic values, which further validates that pseudo-
second order equation would best describe the kinetics of the
DH0 DS0 adsorption system.
log Kc ¼  (9)
2:303R 2:303RT

where DH0 is the change in enthalpy (kJ/mol) and DS0 is the change
in entropy (J/mol$K) shows the natural logarithm of Kc plotted
against the inverse of temperature (K1).
Table 4b summarizes the values of DG , DH and DS , which
were obtained from the slope and intercept of the plot of ln Kc
against 1/T (Fig. 3a). The negative value of DH indicates that the
adsorption of COD using CCB is exothermic in nature. Moreover, the
negative DS value denotes that there was a decrease in entropy
after the adsorption of COD onto CCB. This implies that after
adsorption, a low state of disorder exists where COD adsorption
occurred involving liquid/solute interactions with hydrophilic
3.4. Optimization studies
Central composite design (CCD) was utilized in the selection of
the four independent variables in 5 levels. Table 5 illustrates the
thirty runs generated by CCD characterized by different combina-
tions of the four independent variables and corresponding actual
responses. The coefficients of the quadratic polynomial equation
were derived from the experimental data using RSM. The proposed
quadratic polynomial equation, which would adequately describe
the mathematical relationship between the dependent response
(Y) and independent variables, is as follow (Eq. (13)):

Y ¼ 4:46  13:14X1 þ 0:62X2 þ 1:41X3 þ 198:26X4 þ 0:21X1 X2 þ 0:08X1 X3 þ 6:29X1 X4

(13)
0:01X2 X3  0:92X2 X4  0:44X3 X4  0:01X12  0:01X22  0:03X32  110:96X42
 M. Ligaray et al. / Journal of Cleaner Production 175 (2018) 145e154 151

1.09 3
(a) (b)
1.07
2

ln(qe-qt)
1.05

ln Kc
1
1.03

0
1.01

0.99 -1
0.0032 0.00325 0.0033 0.00335 0.0034 0 5 10 15 20
1/T (K-1) Time (h)

0.8 30

25
0.6
20

qt (mg/g)
t/qt

0.4 15

10
0.2
5 (d)
(c)
0.0 0
0 5 10 15 20 0 2 4 6
Time (h) Time1/2 (h1/2)
Fig. 3. Removal of COD using CCB from TFT-LCD wastewater using (a) Vant Hoff plot; (b) pseudo-first order; (c) pseudo-second order; and (d) intraparticle diffusion equation.

Table 4c Table 5
Kinetic constants of the adsorption of COD onto CCB from TFT-LCD wastewater. Responses for the actual and coded variables used in central composite design.

Kinetic Model Parameters Value R2 Std Actual variables Response (%)

Pseudo-first order k1 (1/h) 0.17 0.8611 pH T ( C) t (h) m (g) Actual Predicted

qe (mg/g) 21.12
1 5 35 18 0.6 67.47 65.33
Pseudo-second order k2 (g/mg$h) 0.09 0.9980
2 5 35 18 0.6 62.21 61.73
qe (mg/g) 27.15
3 4 40 24 0.8 71.65 72.28
Intraparticle diffusion ki1 (mg/g$h0.5) 5.69 0.8980
4 5 35 18 0.2 26.02 24.96
ki2 (mg/g$h0.5) 0.69 0.8091
5 4 30 12 0.4 49.67 48.33
qe (mg/g) 25.26
6 6 30 12 0.8 72.75 70.31
7 4 30 12 0.8 68.29 65.77
8 6 40 24 0.4 55.02 53.36
where Y represents the predicted response as COD removal effi- 9 4 30 24 0.8 72.08 70.46
10 5 35 18 0.6 61.67 62.41
ciency; X1, X2, X3 and X4 are the independent variables namely pH,
11 3 35 18 0.6 69.32 68.08
temperature, contact time and CCB mass, respectively. 12 6 30 12 0.4 39.69 40.91
The analysis of variance (ANOVA) was utilized to evaluate the 13 6 40 12 0.8 70.65 71.24
statistical significance of the model equation, independent vari- 14 4 40 12 0.8 69.45 71.21
ables and its interactions. The F-value is a measure of the variance 15 5 35 18 1.0 70.97 72.97
16 5 25 18 0.6 63.32 64.08
associated to the residual variance and factor. It is also equivalent to 17 4 30 24 0.4 52.82 54.16
the mean square of the factor divided by the mean square of the 18 5 35 6 0.6 59.22 60.17
residual (Jalali and Sobati, 2017). A large F- value would indicate 19 7 35 18 0.6 63.21 64.51
that the factor is significant. Moreover, factors with p-value less 20 4 40 24 0.4 49.76 50.60
21 5 35 18 0.6 68.37 69.85
than 0.05 are considered to be statistically significant to the
22 6 30 24 0.8 74.01 75.53
response with 95% confidence level. Based from Table 6, the 23 5 35 30 0.6 64.95 66.15
quadratic polynomial equation has a large F-value (37.40) and small 24 5 35 18 0.6 68.64 69.84
p-value (<0.0001), which implies that the model is significant. 25 6 40 12 0.4 47.69 48.75
Based on the determination coefficient value (R2 ¼ 0.9722), this 26 5 35 18 0.6 67.69 68.90
27 5 45 18 0.6 66.90 68.58
implies that only 2.88% of the removal of COD using CCB cannot be 28 4 40 12 0.4 48.94 50.12
explained by the quadratic model. Moreover, the adjusted corre- 29 6 30 24 0.4 46.66 48.21
lation coefficient value of 0.9462 implies high degree of fitness of 30 6 40 24 0.8 72.63 73.12
the model to predict the true variation of the adsorption system.
152 M. Ligaray et al. / Journal of Cleaner Production 175 (2018) 145e154

Table 6 made on these two parameters will have no considerable effect on

Results of analysis of variance (ANOVA) for the response surface quadratic model in adsorption of COD using CCB. The optimum COD removal of 73.34%
terms of sulfur removal.
can be attained at the following conditions: pH 4.0, temperature of
Run Sum of squares df Mean square F-value p-value 30  C, 20.32 h and 0.8 g CCB.
Model 3762.60 14 268.76 37.40 <0.0001 The correlation between predicted and experimental data of
X1 11.11 1 11.11 1.55 0.2327 COD removal is illustrated in Fig.4a, where the plot showed satis-
X2 12.80 1 12.80 1.78 0.2019 factory agreement between the actual and predicted values
X3 65.01 1 65.01 9.05 0.0088
generated by the model. This implies that the design space of CCD
X4 3047.14 1 3047.14 424.10 <0.0001
X1X2 17.00 1 17.00 2.37 0.1448 can be satisfactorily navigated by the predicted values (Ghani et al.,
X1 X3 4.14 1 1.14 0.58 0.4596 2017). In Fig. 4bed, the 3D surface plots generated by RSM illustrate
X1 X4 25.33 1 25.33 3.52 0.0800 the effect of interaction between CCB mass and contact time, CCB
X2 X3 0.7303 1 0.73 0.10 0.7543
mass and pH, and CCB mass and temperature. It can be observed
X2 X4 13.61 1 13.61 1.89 0.1889
X3 X4 4.48 1 4.48 0.62 0.4422
that COD removal increases with increase in CCB mass whether it
X21 0.0010 1 0.0010 0.0001 0.9905 interacts with pH, temperature or contact time. Increasing the mass
X22 2.38 1 2.38 0.33 0.5736 of CCB increases the surface area exposed for adsorption as well as
X23 30.28 1 30.28 4.21 0.0580 increase in the availability of the functional group, which results to
X24 540.35 1 540.35 75.21 <0.0001
an increase in the adsorption of COD onto CCB.
Residual 107.78 45 7.19
Lack of Fit 57.04 10 5.70 0.56 0.7952
Pure Error 50.74 5 10.15
Cor Total 3870.37 29 4. Conclusion
R squared 0.9722 Adjusted R squared 0.9462
In the present work, removal of COD from real TFT-LCD waste-
water using CCB was evaluated. The equilibrium data agreed well
Also, the lack of fit is considered not significant relative to pure with the Langmuir isotherm, indicating occurrence of monolayer
error due to small F-value (0.56). Based on the ANOVA results with adsorption of COD using CCB. Kinetic studies revealed that COD
large F-values and p-values of less than 0.0500, the following model removal using CCB can be adequately described using the pseudo-
terms are considered significant: X3 (contact time), X4 (CCB mass) second order equation, which implies that chemisorption is the
and X24. Results show that CCB mass, with the highest F-value rate-determining step. Moreover, the removal of COD is determined
(424.10) and lowest p-value (<0.0001), is the most significant to spontaneous, exothermic and results to a low disorder in the
parameter affecting the adsorption of COD from TFT-LCD waste- adsorption system. Based on the F-value (37.40) and p-value
water using CCB. Meanwhile, variables such as pH (X1) and tem- (<0.0001), the acquired quadratic polynomial model shows satis-
perature (X2) are not significant, which implies that any variation factory goodness of fit. Optimization studies show that CCB mass

Fig. 4. The correlation of predicted and actual values of response for (a) % COD removal and three-dimensional surface plots of two-parameter interaction of (b) mass and contact
time; (b) mass and temperature and (c) mass and pH on % COD removal.
 M. Ligaray et al. / Journal of Cleaner Production 175 (2018) 145e154
and contact time are significant factors affecting the COD removal
using CCB from TFT-LCD wastewater. The design of experiments
determined that maximum COD removal of 73.34% can be attained
at the following conditions: pH 4.0, 20.32 h, temperature of 30  C
and 0.8 g CCB. Results of the present work show that CCB is an
effective and low-cost adsorbent that can be utilized in the removal
of COD from real TFT-LCD wastewater.
Acknowledgements
The authors would like to thank the Taiwan Ministry of Science
and Technology (MOST 105-2221-E-041-002-MY3) and National
Research Foundation (NRF) of Korea through Ministry of Education
(No. 2016R1A6A1A03012812) for the financial support of this
research undertaking.
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