Bioresource Technology Reports 3 (2018) 127–137

Contents lists available at ScienceDirect

Bioresource Technology Reports

journal homepage: www.journals.elsevier.com/bioresource-technology-reports

Use of banana trunk waste as activated carbon in scavenging methylene blue T

dye: Kinetic, thermodynamic, and isotherm studies
⁎
Mohammed Danisha, , Tanweer Ahmadb, Shahnaz Majeedc, Mehraj Ahmadd, Lou Ziyange,
Zhou Pine, S.M. Shakeel Iqubalf
a
Bioengineering Technology Section, Universiti Kuala Lumpur Malaysian Institute of Chemical and Bioengineering Technology (MICET), Lot 1988, Kawasan Perindustrian
Bandar Vendor, Taboh Naning, 78000 Alor Gajah, Melaka, Malaysia
b
Department of Chemistry, College of Natural and Computational Science, Madda Walabu University, Bale Robe, Ethiopia
c
Faculty of Pharmacy and Health Sciences, Universiti Kuala Lumpur, Royal College of Medicine, Perak 30450, Malaysia
d
School of Food Science & Bioengineering, Zhejiang Gongshang University, 18 Xuezheng Street Xiasha, Hangzhou, Zhejiang 310018, China
e
School of Environmental Science and Engineering, 800 Dongchuan Road, Shanghai Jiao Tong University, Shanghai 200240, China
f
Department of Basic Science (Chemistry), Ibn Sina National College, Jeddah, Saudi Arabia

A R T I C LE I N FO A B S T R A C T

Keywords: Activated carbon (BTAC) derived from the banana trunk was utilized in this experiment to scavenge the me-
Activated carbon thylene blue (MB) dye from synthetic dye solution. The optimized large surface area (1173.16 m2/g) BTAC was
Banana trunk prepared with phosphoric acid (6.96 mol/L) chemical activation. The maximum adsorption capacity (qmax) of
Isotherm BTAC was experimentally observed to be 166.51 mg/g at 25 °C, and adsorbent dose of 1.5 g/L for 250 ppm dye
Kinetics
concentration. The MB dye adsorption onto BTAC reached equilibrium within 20 min of contact time. The ki-
Methylene blue
Thermodynamics
netic data shown equilibrium achieved quickly (20 min) and followed a linear equation of the pseudo-second-
order kinetic model. The adsorption of dye molecules stacking in three layers on the surface of the BTAC, after
each layer formation the rate of adsorption slow down, as evident from the intraparticle diffusion study. The
thermodynamic study shown that adsorption was spontaneous and exothermic.

1. Introduction and other industries like cosmetic, pharmaceutical, rubber, plastic,

food, and paper industry (Rafatullah et al. 2010). Artificial dyes are also
Water soluble dye molecules are considered to be a hazardous or- toxic to various microorganisms which can either cause inhibition or
ganic compound for the aquatic environment. They are used in textile destruction to their catalytic and functional capabilities. The presence

Abbreviations: qmax, the maximum uptake of MB dye corresponding to the sites saturation through Langmuir isotherm model (mg/g); KL, Constant used in Langmuir
model, it corresponds to the energy of adsorption (L/g).; RL, Dimensionless separation factor; KF, Constant used in the Freundlich isotherm model, it corresponds to
adsorption capacity.; N, Constant used Freundlich isotherm model, it corresponds to adsorption intensity; KT, Temkin isotherm constant, it expressed the equilibrium
binding constant (L/mg); B, Temkin constant for the heat of adsorption (~RT/b); B, Heat of adsorption constant; T, Temperature in Kelvin scale (K); R, Universal gas
constant (8.314 J/K/mol); A, Interaction parameter which can be positive or negative values; KFM, Frumkin constant related to adsorption equilibrium.; ΔG, Gibbs
free energy change; KD-R, Dubinin and Radushkevich constant correspond to the adsorption energy.; EA, Mean free energy of adsorption; Ε, Polanyi potential ~ RTln
(1 + 1/Ce); Ɵ, Fractional occupation calculated by the ratio of adsorption capacity at equilibrium and theoretical monolayer saturation capacity.; qm, Maximum
monolayer adsorption capacity determined through D-R isotherm; HA & HB, Harkins–Jura isotherm constant for multilayer adsorption; W & Wb, Constant parameters
for Smith isotherm equation; U, Fractional attainment of equilibrium; Ce, the equilibrium concentration of MB dye (mg/L).; qe, the amount of MB dye uptake at
equilibrium (mg/g).; kn, Net first order reversible rate constant(min−1); k1, Rate of adsorption of the first-order reversible kinetic model (min−1).; k−1, Rate of
desorption of first-order reversible kinetic model (min−1).; Kc, Equilibrium constant; k2, Rate of adsorption for the pseudo-second-order kinetic model (min−1).; h,
Initial sorption rate for pseudo-second order kinetic model (mg/g/min); qt1, Weber–Morris adsorption capacity in the first phase of adsorption (mg/g); Kd1,
Weber–Morris adsorption rate constant in the first phase of adsorption (mg/g/min.1/2); C1, Boundary layer in the first phase of adsorption in the first phase; qt2,
Weber–Morris adsorption capacity in the second phase of adsorption (mg/g); Kd2, Weber–Morris adsorption rate constant in the second phase of adsorption (mg/g/
min.1/2); C2, Boundary layer in the first phase of adsorption in the second phase; qt3, Weber–Morris adsorption capacity in the third phase of adsorption (mg/g); Kd3,
Weber–Morris adsorption rate constant in the third phase of adsorption (mg/g/min.1/2); C3, Boundary layer in the first phase of adsorption in the third phase
⁎
Corresponding author at: Bioengineering Technology Section, Universiti Kuala Lumpur Malaysian Institute of Chemical and Bioengineering Technology (MICET),
Universiti Kuala Lumpur, Lot 1988, Kawasan Perindustrian Bandar Vendor, Taboh Naning, 78000 Alor Gajah, Melaka, Malaysia.
E-mail address: mdanish@unikl.edu.my (M. Danish).

https://doi.org/10.1016/j.biteb.2018.07.007
Received 12 June 2018; Received in revised form 28 July 2018; Accepted 28 July 2018
Available online 11 August 2018
2589-014X/ © 2018 Elsevier Ltd. All rights reserved.
M. Danish et al.
of various dye molecules in aquifer reduces light penetration which
directly affects the photosynthesis process of aquatic flora. The waste-
waters discharged after dyeing processes showed high biological
oxygen demand (BOD), high chemical oxygen demand (COD), visible
pollutants, and large amounts of dissolved solids. Some dyes are mu-
tagenic, carcinogenic and teratogenic (Bhattacharyya and Sharma
2005; Kaur et al. 2015). Water streams contaminated with artificial
dyes can cause dermatitis, allergy, irritation of the skin, which in turn
can cause the mutation in the nucleotides of deoxyribonucleic acid
(DNA), that leads to the growth of cancer cells in humans and animals
(Veliev et al. 2006). The presence of dye makes the water objectionable
for drinking. Therefore, it is in dire need to scavenge dye from waste-
water to prevent the continuous environmental pollution and to protect
the water quality for flora and fauna.
Methylene blue (MB) has a wide range of applications especially as
a coloring agent for hair, paper, cotton, wools, and coating paper.
Chemical studies showed that MB dye molecule is a heterocyclic aro-
matic compound. The chemical properties of the MB dye molecules
have been intensively studied due to its strong binding with solids, and
quite often it serves as a model compound for the separation of colored
bodies and colorless organic compounds from various contaminated
mixtures (Rafatullah et al. 2010). Many advanced techniques and
treatment methods were employed for the separation/mineralization of
dye molecules from wastewater such as photo-catalytic (Houas et al.
2001), Fenton process and electrochemical combined treatments
(Lahkimi et al. 2007), adsorption process (Danish et al. 2013), elec-
trochemical degradation (Panizza et al. 2007), flocculation (Han et al.
2002), chemical coagulation and ozonation (Sarasa et al. 1998), nano-
filtration and ultrafiltration (Fersi and Dhahbi 2008), cloud point ex-
traction (Bezerra et al. 2005), and reverse osmosis (Al-Bastaki 2004;
Nataraj et al. 2009). Adsorption is a surface phenomenon which occurs
at the surface, and the adsorbate is remained stuck at the surface of the
adsorbent without any change in chemical composition or structure. So,
it has the advantage to be recovered the adsorbate species in its original
form through desorption. The adsorption methods can be widely ap-
plied to recover the specific chemical species from wastewater or
aqueous solutions if we use highly selective adsorbents. The low cost,
sustainable, selective, and eco-friendly adsorbents could be proved to
be an effective and advanced technique to recover dyes from waste-
water. Contemporary researchers are showing great interest in devel-
oping new adsorbent materials with excellent properties, diverse com-
positions, and selective functionalities. The biomass waste derived
activated carbons (AC) are the most promising materials which can
serve as excellent adsorbent materials. Although commercial activated
carbon (mostly derived from coal mining dust) is a widely used ad-
sorbent to remove various dye molecules, it is too expensive to be used
in small-scale industries. Literature survey shows that in last decades so
many low-cost alternative adsorbents are proposed that includes co-
conut shells (Dwivedi et al. 2008), Acacia mangium wood (Danish et al.
2011), rice husk (Sahu et al. 2009), pomegranate shell (Ghaedi et al.
2012), bamboo (Hameed et al. 2007), banana waste (Ahmad and
Danish 2018), oil palm waste (Rafatullah et al., 2013) and date stone
(Danish et al. 2014). Methylene blue dye removal through biochar from
oak wood (Babaei et al. 2016), pine wood, pig manure, and cardboard
(Lonappan et al. 2016) were also tried.
Banana is the second most commonly cultivated fruit in Malaysia.
According to the statistical report of the department of agriculture
Malaysia, the banana tree plantation cover around 30,320 ha and pro-
duced 321,810 metric tonnes of fresh banana fruits in the year 2016.
Whereas, the world production of banana in 2016 was 144 mil-
lion metric tonnes (Ahmad and Danish 2018). Banana plant can pro-
duce fruit once in a lifetime, so after fruit harvesting, the whole plant is
discarded as waste. It was estimated that near 100 kg of waste gener-
ated for every tonne of banana fruit production. If this much huge waste
can be transformed into useful material, will be a great help to banana
grower farmers. Keeping these in view, the activated carbon formation
128
Bioresource Technology Reports 3 (2018) 127–137
from banana waste will benefit the farmers in two possible ways: it will
increase the revenue as well as reduce the volume of the waste sig-
nificantly. At the same time, it could support the environment by fixing
the carbon as a solid framework. Otherwise, these waste dumping
disposal in water and humid conditions could lead to methane and
carbon monoxide gas formation or their burning could produce a large
quantity of CO2 gas; all these gases are responsible for global warming.
The current study was designed to assess the scavenging behavior of
banana trunk activated carbon (BTAC) against aqueous methylene blue
(MB) dye. For the first time kinetic, thermodynamic, and isotherm
study of MB dye adsorption onto the novel prepared banana trunk
waste activated carbon (BTAC) was studied. The effect of adsorbent
dosage, initial MB dye concentration, contact time, and solution tem-
perature was evaluated for the scavenging of MB dye through BTAC
adsorbent. The thermodynamic parameters of the scavenging behavior
of BTAC and MB dye were calculated, and the kinetic rate of MB ad-
sorption onto BTAC was established through various models. The me-
chanism of scavenging behavior and isotherms has also been in-
vestigated.
2. Materials and methods
2.1. Preparation of BTAC
The banana trunk was collected from a banana plantation farm at
Tampin, Negeri Sembilan, Malaysia. The banana trunk was cut into
small pieces (dimension, 3 cm × 3 cm × 4 cm) and washed thoroughly
several times with water to remove sand and soil residue from the
surface. In a subsequent step, the washed pieces of the banana trunk
were set for drying at 105 °C for 24 h in a forced draft oven. The
moisture content of the representative sample of the banana trunk was
taken in triplicate. Nearly 10 g of banana trunk pieces were taken in
glass Petri dishes and kept for drying at 105 °C till constant weight was
obtained. After drying, the dried banana trunk pieces were grounded
and sieved into a uniform particle size of 0.5 μm.
For activated carbon preparation, 100 g of dried banana trunk
powder was mixed with 5.09 mol/L of phosphoric acid (H3PO4) (opti-
mized activating agents for methylene blue removal study, Danish et al.
2018) and kept for complete soaking of the activating agent into the
banana trunk powder. The soaking was performed at room tempera-
ture. Then, the mixture was placed in the muffle furnace at 845 °C for
50 min in a loosely covered silica crucible. After the activation process,
the muffle furnace was left for 12 h to bring the temperature down. The
washed BTAC product was dried at 105 °C for 24 h inside a hot air oven.
Finally, the dried BTAC product was kept in tight lid glass bottles for
further analysis and application studies.
2.2. Methylene blue dye stock solution
Methylene blue dye was procured from Scharlau's chemicals,
1.000 ± 0.005 g of dye was dissolved in 1 L standard flask to prepare
1000 ppm stock solution. Later this stock solution was used to prepare a
desired concentration dye solution for further studies.
2.3. Adsorbent dosage optimization experiment
Initially, the experiments were performed to optimize the adsorbent
dosage (g/L) for maximum removal of MB dye through BTAC ad-
sorbent. Randomly selected adsorbent dosage of 0.3, 0.5, 0.7, 1.0, 1.5,
1.7, 2.0 g/L were used for finding the optimum dosage for maximum
removal percentage against 50 ppm MB dye solution. The experiments
required three conical flasks for each selected dosage, to find the de-
viation in the reproducibility of the dye adsorption. The BTAC ad-
sorbent was weighed on butter papers using analytical balance
(Sartorius Quas) that was capable of weighing accurately in milligrams.
Butter paper was preferred during the activated carbon weight
M. Danish et al.
measurement due to its non-sticky surface that minimizes the mass loss
and prevents the powder from being scattered around. For 30 mL of
50 ppm MB dye, the weight of the BTAC adsorbent was accurately
measured using the following relationship (Eq. (1)).
dosage (g /L) × MB dye vol. (mL)
Adsorbent weight =
1000 (1)
The precise weight of BTAC adsorbent was transferred into conical
flasks, containing 30 mL of 100 ppm MB solution. The mixture was
thoroughly mixed and set for 1 h continuous agitation. After that, BTAC
was filtered through the Whatman filter paper No. 42, and residual MB
dye concentration was measured through UV-VIS spectrophotometer
(Perkin Elmer, Lambda 35 model). The UV-VIS spectrophotometer was
calibrated before the actual measurement was conducted. The standard
solution of MB dye of various concentrations such as 0.01 ppm,
0.03 ppm, 0.05 ppm, 0.07 ppm, and 0.10 ppm was prepared carefully.
The calibration curve was prepared between the standard solution
concentration and their corresponding absorbance as shown in
Supplementary Fig. S1. The regression coefficient (R2) of the calibration
curve was calculated to be 0.995 with the intercept at 0.00. This high
correlation coefficient (R2) value gave the highly precise results of re-
sidual MB dye concentration.
2.4. Kinetic measurements
Thirty-nine conical flasks were prepared with a fixed dosage of
1.5 g/L (45 mg of BTAC for 30 mL of 100 ppm MB dye solution) BTAC
adsorbent that was determined through dosage experiment. Each con-
ical flask after mixing the MB dye solution was agitated for a selected
time interval of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, and 30 min. The
filtered residual MB dye solution was measured through the UV-VIS
spectrophotometer as stated in the previous section. Each time interval
was repeated three times to find the deviation in the measured value.
2.5. Thermodynamic measurements
Thermodynamic parameters of MB dye adsorption onto BTAC ad-
sorbent were measured for three dye concentrations viz., 50, 100, and
150 ppm at 30, 40, 50, and 60 °C. For each concentration of MB dye
solution, 1.5 g/L adsorbent dosage was used. The temperature of the
dye and adsorbent mixture inside a conical flask was maintained by
immersing the conical flask inside the water bath shaker for a fixed time
of 1 h. After the fixed time of agitation inside the water bath at a
constant selected temperature, the residual MB dye solution was fil-
tered and kept in a vial at room temperature (25 °C). Later residual
concentration of the MB dye was measured through the UV-VIS spec-
trophotometer as mentioned in section 2.3.
2.6. Adsorption isotherm study
Isotherm study of MB dye adsorption onto BTAC was conducted
with five different concentrations of dye solutions viz., 50, 100, 150,
200, and 250 ppm using a fixed dosage of 1.5 g/L adsorbent. The
maximum deviation in the dilution of stock solution (1000 ppm) to the
selected concentration was ± 10 ppm. These deviations in the dye
concentration were considered during the calculations to get the correct
values of isotherm model constants and adsorption capacity. Isotherm
study was conducted at room temperature only. The amount of MB
adsorbed per unit mass of adsorbents (q) at equilibrium was calculated
using the following equation:
(Ci − Ce ) V
qe =
m (2)
The amount of MB adsorbed per unit mass of adsorbents at the time
t, was calculated through the following equation:
129
Bioresource Technology Reports 3 (2018) 127–137
(Ci − Ct ) V
qt =
m (3)
The percentage MB removal has been calculated by the following
Eq. (4):
(Ci − Ce )
%MB removal = × 100
Ci (4)
where,
Ci, Ce and Ct (mg/L), = Initial, equilibrium, and after time-t con-
centration of MB dye, respectively.
V = Solution volume of MB dye (units in L).
m = Amount of adsorbent (units in g).
3. Results and discussion
3.1. Effect of adsorbent dosage and contact time on MB adsorption
The adsorption percentage of MB onto different dosage of BTAC
adsorbent with 100 ppm of initial dye concentration (as shown in
Supplementary Fig. S2). The adsorbent dosage increased from 0.3 g/L
to 1.5 g/L, the adsorption percentage increased with regular increment
in the dosage and reached 99.98%. Further increase in BTAC dosage up
to 2.0 g/L didn't change the adsorption percentage anymore. So BTAC
dosage of 1.5 g/L was chosen as maximum removal for 100 ppm MB dye
solution for further studies.
At an optimum dosage of BTAC adsorbent, the equilibrium contact
time was established through the plot of percent adsorption vs. time
curve (as shown in Supplementary Fig. S3). The curve showed that MB
dye adsorption was rapid and 99.53% dye was scavenged in the initial
10 min of BTAC and MB dye interaction. At equilibrium, the MB dye
removal percentage was found to be 99.87%.
3.2. Kinetic studies
The adsorption of MB dye vs. time data was tested against various
available kinetic models. The aim of the kinetic studies was to explore
the possible mechanism of sorption of MB dye onto BTAC adsorbent.
The well established kinetic models such as reversible first order reac-
tion, pseudo-first-order, and pseudo-second-order models were tested in
this study. The conformity between predicted model values and ex-
perimental data was expressed by the regression coefficient (R2). The
higher regression coefficient value with the available kinetic experi-
mental data is considered as an applicable model.
A first-order reversible kinetic model was used to explore the pos-
sibility of the applicability of the MB dye adsorption data. The simpli-
fied reversible kinetic model is given below:
ln(1 − U ) = −kn t (5)
where, U represents the fractional attainment of equilibrium; kn is net
rate constant, and t is a time in min.
The plot between ln(1-U) vs. t, should give a straight line that must
pass through the origin for a perfect first order reversible kinetic re-
action between adsorbent and adsorbate. We applied MB dye adsorp-
tion data to calculate U (as shown in the supplementary data file), then
plot ln(1-U) vs. t. The representative of the plot is shown in Fig. 1(a). It
was observed that the line was not a straight line and the regression
coefficient (R2) was found to be 0.856, which suggested that MB dye
adsorption was not followed the first-order reversible kinetic model.
Constants kn, k1, and k−1 were calculated and reported in Table 1.
Pseudo-first order kinetic model was applied to the MB dye ad-
sorption data; the following equation was used for model calculation.
k′
log(qe − qt ) = log qe − ⎛ 1 ⎞ × t
⎜ ⎟
⎝ 2.303 ⎠ (6)
where, qt and qe (mg/g) = adsorption capacity at time, t and
M. Danish et al.
Fig. 1. (a) First order reversible kinetic model plot, (b) Pseudo-first order kinetic model plot, (c) Pseudo-second-order kinetic model, (d)Weber–Morris diffusion
model plot, for MB dye adsorption onto BTAC.
equilibrium, respectively.
k1’ (1/min) = rate constant for pseudo-first-order adsorption.
The representative of the plot is shown in Fig. 1(b). The regression
coefficient, R2 for this model is 0.961 and not close to the ideal corre-
lation coefficient value. Constant k value was calculated and mentioned
in Table 1.
The pseudo-second-order kinetics model (Ho and McKay, 1999) can
be expressed as:
t 1 1
= + t
qt h qe
where;
qe and qt (mg/g) = The adsorption capacities at equilibrium and at
time t, respectively.
k2 (g/(mg·min)) = Rate constant of the pseudo-second-order reac-
tions.
h = Initial sorption rate as qt/t → 0 h = k2 × qe2.
The plot of t/qt vs. t of Eq. (7) is shown in Fig. 1(c) and give a linear
relationship, from which qe, k2, and h can be calculated. The values for
qe, k2, and h were calculated and are summarized in Table 1. The re-
gression coefficient (R2) value for this pseudo-second-order model is
0.999 which is very close to 1.00, the ideal value of the regression
coefficient. Therefore, it can be concluded that the sorption of MB onto
Bioresource Technology Reports 3 (2018) 127–137
BTAC follows the pseudo-second-order kinetic model perfectly.
Intraparticle diffusion of the MB dye molecules was calculated
through Weber–Morris model (the model is represented in Eq. (8)).
qt = kd × t 1/2 + c (8)
where, qt (mg/g) = The adsorption capacities at time t; kd (mg/g/min1/
2
) = diffusion rate constant, t = time, and c (mg/g) = boundary
thickness.
It can be seen from Fig. 1(d), the plot shows three different slopes.
(7) Initial slope was sharp increasing with high diffusion rate constant
value (kd = 14.694 mg/g/min1/2), when the BTAC adsorbent surface
and pores were freely available for the MB dye molecules, so thickness
boundary (35.35 mg/g) was also less. In the second stage, the diffusion
rate decreased to 0.6082 mg/g/min1/2, and boundary thickness in-
creased to 62.69 mg/g. In the third stage, the diffusion rate further
decreased to 0.1358 mg/g/min1/2, and boundary thickness increased to
65.90 mg/g. It is clear from the results that as the adsorption of MB dye
progresses with time the diffusion rate decreased due to pores and
surface spaces were occupied the dye molecules. Consequently, an in-
crease in boundary thickness at the surface of BTAC adsorbent was
observed. The Weber–Morris model parameters with correlation coef-
ficients (R2) are reported in Table 1.
130
M. Danish et al. Bioresource Technology Reports 3 (2018) 127–137

Table 1
Kinetic models parameters for the adsorption of MB onto BTAC.
Kinetic parameters Values

qe (mg/g) (for 100 ppm initial conc of MB dye) 66.57

First-order-reversible reaction kinetics model
kn (min−1) 0.319
k1(min−1) 0.047
k−1(min−1) 0.271
Kc 0.175
R2 0.856

Pseudo-first order reaction kinetics model

qe,cal (mg/g) 31.19
k1(min−1) 0.067
R2 0.961

Pseudo-second order reaction kinetics model

qe,cal (mg/g) 67.57
k2(min−1) 0.056
h (mg/g/min) 256.4
R2 0.999

Weber–Morris model
qt1(mg/g) 101.068
Kd1(mg/g/min.1/2) 14.694
C1 35.354
R12 0.9856
qt2(mg/g) 65.414
Kd2(mg/g/min.1/2) 0.6082
C2 62.694
R22 0.8237
qt3(mg/g) 66.517
Kd3 (mg/g/min.1/2) 0.1358
C3 65.91
R32 0.7019

3.3. Effect of temperature on MB dye sorption

Adsorbate solution temperature is an extremely significant factor
during adsorption processes, so the experiments were conducted to
observe it for MB dye adsorption onto BTAC. The experiments were
designed at selected temperatures such as 303.15 K, 313.15 K,
323.15 K, and 333.15 K, for different initial concentrations (50 ppm,
100 ppm, and 150 ppm) of MB dye. The percentage sorption of MB dye
onto BTAC adsorbent was calculated against various temperature and
initial concentrations to explore the nature of the adsorbate-adsorbent
interaction. With the help of Fig. 2(a), the effect of temperatures on
three different initial concentrations of MB dye was represented. It was
observed that with the rise in temperature from 303.15 K to 333.15 K,
the adsorption percentage was marginally decreased for each higher
initial concentrations of MB dye. At a higher initial concentration of MB
dye and higher temperature among the selected one, the effect of
temperature was observed to be more. This behavior can be explained
based on the kinetic movements of the adsorbate (MB dye) molecules
and adsorbent particles (BTAC). Since at higher concentration of MB
dye molecules, the more molecules adsorb and desorb at a higher
temperature, so net adsorption was observed to be lower. Further, this
thermal interaction was used to calculate the thermodynamic para-
meters.
3.4. Thermodynamic studies
The thermodynamic calculations for MB dye sorption onto BTAC
was conducted using Von't Hoff relation and standard Gibbs free energy
change (ΔG°), standard enthalpy change (ΔH°), and standard entropy
change (ΔS°) relationship (as given in Eqs. (9) and (10)). The ΔH° and
ΔS° were evaluated through the slope and intercept of Fig. 2(b) plots,
respectively. The ΔG° was estimated by using ΔH° and ΔS° (calculated
from the ln (Kc) vs. 1/T plot) at different temperatures in Eq. (10).
Fig. 2. (a) Effect of temperature on MB dye adsorption onto BTAC, (b) Vont
Hoff plot for MB dye adsorption onto BTAC.
ΔS ° ΔH ° 1
ln K c = − ⎛ ⎞
R R ⎝T ⎠ (9)
ΔGo = ΔH o − T ΔS o (10)
where, Kc is the thermodynamic equilibrium constant (calculated
through the ratio of adsorbed concentration to residue MB dye con-
centration, at equilibrium), T is the temperature in Kelvin scale (K), and
R represents the universal molar gas constant (8.314 J/mol/K).
Fig. 2(b) indicated that the rate of sorption decreased marginally
along with the rise in temperature from 303.15 K to 333.15 K. The
linearity of the Vont Hoff plots were observed to be 0.9892, 0.993, and
0.9872 for 50 ppm, 100 ppm, and 150 ppm initial concentration of MB
dye, respectively. The thermodynamic parameters for MB adsorption
onto BTAC is reported in Table 2. The result showed that the value of
ΔG° for MB dye sorption onto BTAC at different temperature and initial
concentrations were varied between −18.313 kJ/mol
and − 19.719 kJ/mol. The ΔG° < 0 indicated that MB dye sorption
onto BTAC was thermodynamically favorable and spontaneous. Since
the ΔG° values fall within the range of 0 and − 20 kJ/mol, that in-
dicated the electronic interaction between adsorption sites in the ad-
sorbent (BTAC) and the adsorbate molecules (MB dye) (Al-Othman
et al. 2013). Meanwhile, ΔG° values ranging from −80 and − 400 kJ/
mol revealed that the sorption involving sharing or transferring of
charge from the surface of the adsorbent to the adsorbate to form a
coordinate bond.
At a fixed temperature, when we compared the ΔG° values of dif-
ferent initial concentrations. It was observed increasing trends, which
indicated the decrease in the spontaneity of sorption. The increase in
ΔG° values with the rise of temperature indicated that the better sorp-
tion of MB dye onto BTAC could be found at lower temperatures. The

131
M. Danish et al. Bioresource Technology Reports 3 (2018) 127–137

Table 2 higher initial concentration (150 ppm). Because, at low initial MB dye
Thermodynamics parameters for MB dye adsorption onto BTAC. concentrations more heat evolved (for 50 ppm ΔH° = −24.571 kJ/mol
Concentration Temperature ΔG° ΔH° ΔS° and for 100 ppm ΔH° = −22.039 kJ/mol) compared to higher initial
(ppm) (°C) (kJ/mol) (kJ/mol) (kJ/mol K−1) MB dye concentration (150 ppm, ΔH° = −15.600 kJ/mol). Negative
standard entropy change (ΔS°) can be explained as the decrease in
50 30 −19.719 −24.571 −0.0157
randomness, and positive ΔS° values indicated the increase in ran-
40 −19.639
50 −19.482
domness in the system. We found negative ΔS° for 50 ppm and
60 −19.324 100 ppm MB dye solution but positive ΔS° values for 150 ppm solution.
100 30 −19.358 −22.039 −0.0088 The reason for the increase in randomness in the system for higher
40 −19.270 concentration was the replacement of some of the small molecules from
50 −19.182
the surface of adsorbent due to a large crowd of adsorbate molecules
60 −19.093
150 30 −18.313 −15.600 0.0089 approaches to the surface. Some authors considered even displacement
40 −18.403 of water molecules from the surface of the adsorbent added more
50 −18.492 translational entropy than it lost due to the settling of adsorbate mo-
60 −18.582
lecules on the surface of adsorbent; this phenomenon also caused an
increase in randomness in the system (Malkoc and Nuhoglu 2007).
overall ΔG° obtained in this study was indicating for physisorption of
MB dye molecules onto the BTAC surface because of ΔG° lies between 3.5. Adsorption isotherm models
−20 kJ/mol to 0.00 kJ/mol in all cases studied here (Mahmoodi 2011).
The standard enthalpy and entropy changes in the selected range of The adsorption isotherm identifies the distribution of concentration
temperature (303.15 K to 333.15 K~30–60 °C) were found to be variation of adsorbate molecules between solid (adsorbent) and liquid
−24.571 kJ/mol and − 0.0157 kJ/ mol/K, respectively for 50 ppm in- phases at a constant temperature. The isotherms successfully represent
itial MB dye concentration. For 100 ppm MB dye solution the value for the dynamic adsorption behavior of adsorbate. At equilibrium, it can be
ΔH° is −22.039 kJ/mol while the value for ΔS° obtain was expressed as the amount of adsorbate molecules adjusted at the surface
−0.0088 kJ/mol/K. Lastly, for 150 ppm MB dye solution, the standard of per unit mass adsorbent. All available adsorption isotherm models
enthalpy and entropy change in the range of 30–60 °C temperature were are composed of certain constant values which assigned to specific
found to be −15.600 kJ/mol and 0.0089 kJ/mol/K. The negative va- surface behavior and used to compare the adsorption properties of the
lues of the ΔH° indicated that the adsorption was exothermic adsorbents against pollutants (Dursun et al. 2005). To identify the
(ΔH° < 0) (Mortimer 2008). It can be inferred from the obtained data, sorption mechanism of the MB dye onto the BTAC, different initial
at a fixed initial concentration the increased in temperature decreased concentrations of MB dye was keep in contact with the BTAC adsorbent
the spontaneity of the MB dye adsorption onto BTAC surface except at (1.5 g/L) and their respective equilibrium concentrations values were

Table 3
MB dye adsorption onto BTAC isotherm model constants and their correlation coefficients.
Isotherms Models constants Units Values

Langmuir isotherm
Ce
=
1
+
Ce qmax mg/g 227.272
qe qmax × KL qmax
KL L/g 11.000
RL 18.15–3.64 × 10−4
R2 0.9635

Freundlich isotherm
1 Kf 377.851
ln(qe ) = ln(Kf ) + × ln(Ce )
N
N 1.765
R2 0.9926

Dubinin-Raduskevich isotherm
ln(qe) = ln (qm) − KD−R × ε2 KD-R mol2/kJ2 2.00 × 10−11
qm mg/g 199.877
EA kJ/mol 5.00
R2 0.9863

Temkin isotherm
qe = B × ln (KT) + B × ln (Ce) KT L/g 116.531
B 46.207
B J/mol 54.546
R2 0.9608

Frumkin isotherm
A −0.905
ln ⎡
⎣ ( ) θ
1−θ
1
⎤
Ce ⎦
= ln(KFM ) + 2 × a × θ
ln(KFM) 4.3344
ΔG kJ/mol −10.924
R2 0.6385

Harkins–Jura isotherm
1 HB 1 HA 1428.571
= −⎡ × log(Ce ) ⎤
qe2 HA ⎣ HA ⎦ HB −0.71429
R2 0.8190

Smith isotherm
qe = Wb − W × ln (1 − Ce) Wb 40.378
W 487.94
R2 0.9565

132
M. Danish et al. Bioresource Technology Reports 3 (2018) 127–137

Fig. 3. (a) Langmuir plot, (b) Freundlich plot, (c) D-R isotherm plot, (d) Temkin isotherm plot, (e) Frumkin isotherm plot, (f) Harkins–Jura isotherm plot, (g) Smith
isotherm plot, for MB dye adsorption on BTAC (h) FESEM image of BTAC.

applied to the linearized form of Langmuir, Freundlich, Dubinin-Ra- as summarized in Table 3.

duskevich, Temkin, Frumkin, Harkins–Jura, and Smith isotherms
models. The adsorption isotherm constants and regression coefficient
(R2) were calculated through respective linearized isotherm equations 3.5.1. Langmuir isotherm model for monolayer adsorption
The Langmuir isotherm is based on the assumption that the

133
M. Danish et al.
adsorbent surface has uniformly distributed homogenous surface ad-
sorption sites available for adsorbate molecules. It also assumes that
during adsorption the energy is uniformly distributed between the ad-
sorbate surface and adsorbent molecules for monolayer adsorption at a
fixed temperature.
From Fig. 3(a), the scattered data points of Ce/qe vs. Ce plot has been
shown. The best fit line with their equation is also represented there.
Five gradual increasing initial concentrations (50, 100, 150, 200, and
250 ppm) of MB dye were considered for this plot. The slope and in-
tercept of the best fit line were employed to determine the Langmuir
model parameters such as qmax and KL. The values of isotherm constants
qmax and KL were found to be 227.27 mg/g and 11.00 L/g, respectively.
The nature of the MB dye adsorption on BTAC was also tested through
dimensionless constant commonly known as equilibrium parameter or
separation factor, RL. The separation factor was calculated by the fol-
lowing relation (Eq. (11)):
1 sorption capacity (qe = 166.50 mg/g).
RL =
1 + KL Co (11)
where C0 is the initial MB dye highest concentration (mg/L), KL is the
Langmuir isotherm model constant corresponds to the adsorption en-
ergy (L/g). The RL value is an essential feature of the Langmuir iso-
therm to explore whether the adsorption is “favorable (0 ˂ RL ˂ 1)”,
“unfavorable (RL ˃ 1)”, “linear (RL = 1)” or “irreversible (RL = 0)”. For
MB dye adsorption on BTAC, the RL values were found to be 0.001815,
0.000908, 0.000606, 0.000454, and 0.000364 while initial concentra-
tions of MB dye were 50, 100, 150, 200, and 250 mg/L at 303.15 K,
respectively. These RL values indicated that adsorption of MB dye on
BTAC was favorable. Table 3 contains all the calculated parameters of
the Langmuir isotherm model. The regression coefficient (R2) of this
model was found to be 0.9635, this regression coefficient shows the
isotherm data deviated from the linearity. Therefore, adsorption of MB
dye onto BTAC did not seem to be a monolayer.
3.5.2. Freundlich model
This isotherm assumes that the energy is not uniformly distributed
at the surface site of the adsorbent and the adsorbate molecules, rather
energy is exponentially varied in adsorbent surface and the adsorbate
molecules. The Freundlich isotherm model was developed by assuming
the non-uniform distribution of adsorption energy at the heterogeneous
surface of the adsorbent. The experimental data was applied to the plot
of ln(Ce) vs. ln(qe), and the extent of linear relationship was established
through the regression coefficient (R2). The linearized Freundlich
model is shown in Table 3. The Freundlich isotherm helps to explore the
possibility of multilayer adsorption characteristics of the MB dye onto
BTAC.
The experimental data plot of ln(Ce) vs. ln(qe) is shown in Fig. 3(b),
the experimental data points are in good agreement with the linearity of
the plot. The regression coefficient (R2) was found to be 0.9926, which
seems to be the best fit for the linearity test of the Freundlich isotherm
model. The sorption of MB dye onto the BTAC was a multilayer. The
Freundlich constant related to adsorption (Kf) for MB dye has very high
value 377.85, and Freundlich constant related to the intensity of ad-
sorption was also high (1.765). This model better explains the ad-
sorption characteristics of the MB dye onto BTAC.
3.5.3. Dubinin-Radushkevich (D-R) adsorption isotherm model
Dubinin-Radushkevich isotherm also considering the concept of
heterogeneity of the adsorbent surface as in Freundlich isotherm and
assume that the sorption sites are not identical (Misra 1969). The lin-
earized equation of isotherm is represented in Table 3. The Polyani
potential (Ɛ) was calculated using the following relation (Eq. (12)).
1⎞
ε = RT ln ⎛1 +
⎜ ⎟
⎝ Ce⎠ (12)
134
Bioresource Technology Reports 3 (2018) 127–137
The Dubinin-Radushkevich isotherm constant (KD-R) can be used to
the mean free energy of adsorption (EA) per molecule of adsorbate
when the adsorbate molecules move from infinity to the surface of the
adsorbent. It can be calculated by the given below equation (Eq. (13)).
1
EA =
2KD − R (13)
The Dubinin-Radushkevich isotherm constants and its related mean
free energy of adsorption for MB dye adsorption onto BTAC are re-
ported in Table 3. The linearized D-R plot is shown in Fig. 3(c), the
correlation coefficient (R2) for the linear plot was found to be 0.9863,
which is in very close agreement with the perfect linear (R2 = 1). After
Freundlich isotherm, this isotherm model was more closely followed by
the MB dye adsorption data. According to D-R isotherm model pre-
dicted maximum adsorption capacity (qm = 199.87 mg/g) of the BTAC
adsorbent was also very close to the experimentally calculated ad-
3.5.4. Temkin adsorption isotherm model
Temkin isotherm is modeled by assuming that the decrease in the
heat of adsorption followed the linear trend rather than a logarithmic
curve. The non-linearized form of Temkin isotherm can be mathema-
tically expressed by the following equation (Eq. (14)).
RT
qe = ln(KT × Ce )
b (14)
RT
B=
b (15)
where, B is constant dealing with the heat involved during adsorption.
The heat of adsorption constant (b) can be calculated through the slope
of qe vs. ln Ce plot as shown in Fig. 3(d). The calculated values of the
Temkin isotherm constants and its related parameters are summarized
in Table 3. The correlation coefficient of the model for MB dye ad-
sorption data was found to be 0.9608, so the calculated values are near
to the actual heat involved in the adsorption.
3.5.5. Frumkin adsorption isotherm model
The Frumkin isotherm assumes the homogeneous surface of the
adsorbent with uniform interaction with adsorbent molecules. This
isotherm used a constant term ‘a’ which stands for the interaction of
adsorbate molecules with the adsorbed layer. The positive value of ‘a’
indicated that during adsorption the energy increased due to the lateral
interaction of the adsorbate molecule with the surface of the adsorbent.
The negative value of ‘a’ pointed that the repulsive force was operated
between the incoming adsorbate molecules and the molecules settled
on the surface of the adsorbent. The linear form of Frumkin isotherm
with its parameter values are shown in Table 3. The fractional occu-
pation (θ) of adsorbate at the surface of adsorbent was calculated
through the ratio of experimental adsorption capacity to the monolayer
adsorption capacity (calculated through D-R isotherm) for each initial
concentration of MB dye. From the experimental data of MB dye ad-
sorption on BTAC, it was observed that Frumkin isotherm model gave
poor linearity with a correlation coefficient (R2) 0.6385 as shown in
Fig. 3(e). The isotherm constant parameter ‘a’ was having negative
values that indicated that there was repulsion between the incoming
MB dye molecules with the molecules settled on the surface. The re-
pulsion between the bounded and incoming adsorbate molecule is not
true because the experimental data verified multilayer adsorption
(Freundlich isotherm) characteristics. Therefore, the other parameters
of the isotherm model could not be explained because experimental
data was not following this model.
3.5.6. Harkins–Jura adsorption isotherm model
This isotherm explains the multilayer adsorption on a hetero-
geneous surface with a range of pore distribution. The linearized
M. Danish et al. Bioresource Technology Reports 3 (2018) 127–137

CH2 H2C OH CN-

OH

O
S-
BTAC adsorbent surface functional groups
COOH
+

CH3
H3C
N S N Cl
CH3
MB dye molecules CH3

Third layer of molecules Second layer of molecules

N
Cl
H3C CH3 H3C
N CH3
H3C N CH3
N S N Cl CH3
MB dye molecules CH3 H3C N
SH CH3
SH
N
H3C
CH3 N N
N
S
H3C First layer of molecules N
H3C
CH2 H2C OH CN-

OH
H3C N
CH3
O Cl
S-

BTAC adsorbent surface functional groups

COO H
+

N CH3

S CH3

H3C N

CH3

Fig. 4. Schematic representation of mechanism of MB dye molecules adsorption on the macromolecular surface of BTAC. Different layers of dye molecules are also
represented here.

Harkins–Jura adsorption isotherm in terms of 1/qe2 and log(Ce) was
used to apply on the adsorption data of MB dye on BTAC adsorbent. The
plot is shown in Fig. 3(f). The HA represents for multilayer adsorption
isotherm constant and explains the existence of heterogeneous pores,
and HB represents the isotherm constant. The relevant isotherm
parameters with their values are reported in Table 3. The correlation
coefficient (R2) of the model was found to be 0.8190, which indicated
that the obtained MB dye adsorption data do not follow this model.

135
M. Danish et al.
3.5.7. Smith adsorption isotherm model
This isotherm model assumes the adsorbent has a heterogeneous
surface, and the adsorbed molecules at the surface of adsorbent divided
into bounded and condense fractions. The bounded fraction of the ad-
sorbate at the inner or outer surface of the adsorbent facilitates the
condensation of the incoming adsorbate molecules (Smith 1947). The
condensed fraction of the adsorbate molecules forms in layers, each
condense fractions have more than one layers. The linearized form of
the Smith isotherm with their constants values are reported in Table 3.
The plot between qe and ln(1-Ce) is shown in Fig. 3(g), the correlation
coefficient value was found to be 0.9565, which again confirms the
heterogeneous surface of BTAC adsorbent and adsorption of MB dye
was a multilayer. The heterogeneous surface of the BTAC adsorbent can
be in field emission scanning electron microscopic (FESEM) image as in
Fig. 3(h). The various size of the diameter of the pores varies between
5.71 μm to 20.22 μm.
3.6. Mechanism and comparison of MB dye adsorption
Possible functional groups in the BTAC and MB dye, and changes in
the surface of BTAC after MB dye adsorbed was identified through FTIR
spectra (as shown in Supplementary Fig. S4). Based on the FTIR spec-
trum information the functional groups on the surface of BTAC was
observed at wavenumbers 3443 cm−1 (-OH groups, a broad peak),
2366 cm−1 (-CN groups, weak peak), 1637 cm−1 (-C=C-COO– groups,
medium peak), 1592 cm−1 (-C=C-O-S groups, medium peaks),
1415 cm−1 (heterocyclic ring skeleton, weak peak). In MB dye the
peaks were observed at wavenumbers 3433 cm−1 (-OH groups) due to
presence of moisture in the MB dye, and at wavenumber 2357 cm−1
(-C=N-C groups, sharp and strong peak),1645 cm−1 (-C=N- group,
weak peak), and 1550 cm−1 (-S-C-C-N-, heterocyclic ring, medium
peak) was due to presence of functional groups in the MB dye mole-
cules. After MB dye adsorption on to the surface of the BTAC, the BTAC-
MB dye complex was also analyzed through the FTIR, and spectrum
shown some peaks of similar functional groups get stronger, like peak at
wavenumber 3443 cm−1 getting strong and broad, in BTAC the weak
peak was observed at 2366 cm−1, but after MB dye adsorption this peak
shifted 2363 cm−1 with medium strength. Similarly, the peaks in the
BTAC surface at wavenumber 1637 cm−1, shifted to 1644 cm−1, with
increased peak strengths. These changes in the functional groups peak
position and strength in the BTAC-MB dye complex gave the evidence of
MB dye adsorption onto the BTAC surface. The interaction sites in the
BTAC and MB dye macromolecule was identified and drawn in Fig. 4.
The negatively charged functional groups such as -CN-, –O-S-, and
–COO– at the surface of BTAC interact with positively charged
site = N+(CH3)2 of the MB dye molecules. The adsorption of MB dye
on BTAC was a multilayer as established through the isotherm and
intraparticle diffusion models. The possible BTAC surface macro-
molecule interaction with dye molecules are presented in Fig. 4. The
first layer of adsorption was quick as indicated by the first diffusion rate
(Kd1 = 14.694 mg/g/min1/2) due to negatively charged functional
groups (-COO-) on the BTAC and positively charged site (=N+(CH3)2)
of MB dye molecules. The second layer of adsorption was due to in-
duced dipole formed due to the approach of incoming dye molecules
but the diffusion rate of stacking of molecules reduced to 0.6082 mg/g/
min1/2, and in the third layer it further reduced and reached
0.1358 mg/g/min1/2. As the layers increased on the surface of BTAC the
induced dipole effect decreased, that was observed through the diffu-
sion rate experiments.
The adsorption of the methylene blue onto various adsorbents were
tried. The biochars were prepared from pine wood, pig manure, and
paper waste for MB dye removal. The maximum adsorption capacity
was reported to be 3.99 mg/g (pine wood biochar), 16.30 mg/g (pig
manure biochar), and 1.66 mg/g (paper waste biochar) (Lonappan et al.
2016). Oak wood was activated to prepare the biochar for MB dye re-
moval from aqueous solution. The maximum adsorption capacity of oak
136
Bioresource Technology Reports 3 (2018) 127–137
wood biochar through Langmuir isotherm was reported to be
97.55 mg/g at 50 °C (Babaei et al. 2016). On comparing adsorption
capacities of these biomass-derived adsorbents, BTAC was found to be
more efficient with maximum adsorption capacity 199.87 mg/g calcu-
lated through Dubinin-Radushkevich (D-R) isotherm model at 25 °C and
adsorbent dose 1.5 g/L.
4. Conclusions
The present study is dedicated to kinetic, thermodynamics, and
isotherm behavior of MB dye adsorption onto BTAC adsorbent. The
following conclusion was drawn from the study:
(1) Percentage MB removal increased with an increase in time and
achieves equilibrium after 20 min of contact time.
(2) The kinetics data of MB dye adsorption on BTAC was found to
follow the pseudo-second-order kinetic model with a correlation
coefficient (R2 > 0.99) close to absolute linearity (R2 = 1.00).
(3) The Weber–Morris intraparticle diffusion model was also applied to
the kinetic data to estimate the diffusion rate constants and
boundary thickness after each layer of adsorption. The results re-
vealed that three layers of adsorbate formed on the surface of the
adsorbent for each subsequent layers the diffusion rate was ob-
served to be decreased, and boundary thickness increased.
(4) The thermodynamic parameters are shown adsorption was spon-
taneous and decrease with increasing temperature (exothermic).
The thermodynamic parameter ΔG°, ΔH°, and ΔS° indicated that the
adsorption process was spontaneous and exothermic.
(5) The isotherm data were tested against the Langmuir, Freundlich,
Dubinin-Radushkevich, Temkin, Frumkin, Harkins–Jura, and Smith
isotherm models to verify the isotherm characteristics. The iso-
therm data followed the Dubinin-Radushkevich model closely, and
the model predicted qmax was 199.87 mg/g; whereas, the maximum
adsorption capacity of BTAC calculated through experimental va-
lues with 250 ppm initial MB dye concentration was 166.51 mg/g.
In view of the experimental findings, this study recommended that
the banana trunk chemically activated carbon (BTAC) can be used ef-
fectively in the scavenging of MB dye from aqueous solution.
Acknowledgment
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors. However,
the authors acknowledge the Universiti Kuala Lumpur Malaysian
Institute of Chemical and Bioengineering Technology (MICET) for
providing research facilities for this research.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.biteb.2018.07.007.
References
Ahmad, T., Danish, M., 2018. Prospects of banana waste utilization in wastewater
treatment: a review. J. Environ. Manag. 206, 330–348. https://doi.org/10.1016/j.
jenvman.2017.10.061.
Al-Bastaki, N., 2004. Removal of methyl orange dye and Na2SO4 salt from synthetic
waste water using reverse osmosis. Chem. Eng. Process. Process Intensif. 43 (12),
1561–1567. https://doi.org/10.1016/j.cep.2004.03.001.
Al-Othman, Z.A., Habila, M.A., Ali, R., Hassouna, M.S.E., 2013. Kinetic and thermo-
dynamic studies for methylene blue adsorption using activated carbon prepared from
agricultural and municipal solid wastes. Asian J. Chem. 25, 8301–8306.
Babaei, A.A., Alavi, S.N., Akbarifar, M., Ahmadi, K., Ramazanpour Esfahani, A.,
Kakavandi, B., 2016. Experimental and modeling study on adsorption of cationic
methylene blue dye onto mesoporous biochars prepared from agrowaste. Desalin.
Water Treat. 57 (56), 27199–27212. https://doi.org/10.1080/19443994.2016.
1163736.
M. Danish et al.
Bezerra, M.d.A., Arruda, M.A.Z., Ferreira, S.L.C., 2005. Cloud point extraction as a pro-
cedure of separation and pre-concentration for metal determination using spectro-
analytical techniques: a review. Appl. Spectrosc. Rev. 40 (4), 269–299. https://doi.
org/10.1080/05704920500230880.
Bhattacharyya, K.G., Sharma, A., 2005. Kinetics and thermodynamics of methylene blue
adsorption on Neem (Azadirachta indica) leaf powder. Dyes Pigments 65 (1), 51–59.
https://doi.org/10.1016/j.dyepig.2004.06.016.
Danish, M., Hashim, R., Ibrahim, M.N.M., Rafatullah, M., Ahmad, T., Sulaiman, O., 2011.
Characterization of Acacia mangium wood based activated carbons prepared in the
presence of basic activating agents. Bioresources 6 (3), 3019–3033.
Danish, M., Hashim, R., Ibrahim, M.N.M., Sulaiman, O., 2013. Characterization of phy-
sically activated Acacia mangium wood-based carbon for the removal of methyl or-
ange dye. Bioresources 8 (3), 4323–4339.
Danish, M., Hashim, R., Ibrahim, M.N.M., Sulaiman, O., 2014. Optimized preparation for
large surface area activated carbon from date (Phoenix dactylifera L.) stone biomass.
Biomass Bioenergy 61 (0), 167–178. https://doi.org/10.1016/j.biombioe.2013.12.
008.
Danish, M., Ahmad, T., Nadhari, W.N.A.W., Ahmad, M., Khanday, W.A., Ziyang, L., Pin,
Z., 2018. Optimization of banana trunk-activated carbon production for methylene
blue-contaminated water treatment. Appl Water Sci 8, 9. https://doi.org/10.1007/
s13201-018-0644-7.
Dursun, G., Çiçek, H., Dursun, A.Y., 2005. Adsorption of phenol from aqueous solution by
using carbonised beet pulp. J. Hazard. Mater. 125 (1), 175–182. https://doi.org/10.
1016/j.jhazmat.2005.05.023.
Dwivedi, C.P., Sahu, J.N., Mohanty, C.R., Mohan, B.R., Meikap, B.C., 2008. Column
performance of granular activated carbon packed bed for Pb(II) removal. J. Hazard.
Mater. 156 (1), 596–603. https://doi.org/10.1016/j.jhazmat.2007.12.097.
Fersi, C., Dhahbi, M., 2008. Treatment of textile plant effluent by ultrafiltration and/or
nanofiltration for water reuse. Desalination 222 (1), 263–271. https://doi.org/10.
1016/j.desal.2007.01.171.
Ghaedi, M., Tavallali, H., Sharifi, M., Kokhdan, S.N., Asghari, A., 2012. Preparation of low
cost activated carbon from Myrtus communis and pomegranate and their efficient
application for removal of Congo red from aqueous solution. Spectrochim. Acta A
Mol. Biomol. Spectrosc. 86, 107–114. https://doi.org/10.1016/j.saa.2011.10.012.
Hameed, B.H., Din, A.T.M., Ahmad, A.L., 2007. Adsorption of methylene blue onto
bamboo-based activated carbon: kinetics and equilibrium studies. J. Hazard. Mater.
141 (3), 819–825. https://doi.org/10.1016/j.jhazmat.2006.07.049.
Han, B., Runnells, T., Zimbron, J., Wickramasinghe, R., 2002. Arsenic removal from
drinking water by flocculation and microfiltration. Desalination 145 (1), 293–298.
https://doi.org/10.1016/S0011-9164(02)00425-3.
Ho, Y.S., McKay, G., 1999. Pseudo-second order model for sorption processes. Process
Biochem. 34 (5), 451–465. https://doi.org/10.1016/s0032-9592(98)00112-5.
Houas, A., Lachheb, H., Ksibi, M., Elaloui, E., Guillard, C., Herrmann, J.-M., 2001.
Photocatalytic degradation pathway of methylene blue in water. Appl. Catal. B
Environ. 31 (2), 145–157. https://doi.org/10.1016/S0926-3373(00)00276-9.
Kaur, S., Rani, S., Mahajan, R.K., 2015. Adsorptive removal of dye crystal violet onto low-
137
Bioresource Technology Reports 3 (2018) 127–137
cost carbon produced from Eichhornia plant: kinetic, equilibrium, and thermo-
dynamic studies. Desalin. Water Treat. 53 (2), 543–556. https://doi.org/10.1080/
19443994.2013.841109.
Lahkimi, A., Oturan, M.A., Oturan, N., Chaouch, M., 2007. Removal of textile dyes from
water by the electro-Fenton process. Environ. Chem. Lett. 5 (1), 35–39. https://doi.
org/10.1007/s10311-006-0058-x.
Lonappan, L., Rouissi, T., Das, R.K., Brar, S.K., Ramirez, A.A., Verma, M., ... Valero, J.R.,
2016. Adsorption of methylene blue on biochar microparticles derived from different
waste materials. Waste Manag. 49, 537–544. https://doi.org/10.1016/j.wasman.
2016.01.015.
Mahmoodi, N.M., 2011. Equilibrium, kinetics, and thermodynamics of dye removal using
alginate in binary systems. J. Chem. Eng. Data 56 (6), 2802–2811. https://doi.org/
10.1021/je101276x.
Malkoc, E., Nuhoglu, Y., 2007. Determination of kinetic and equilibrium parameters of
the batch adsorption of Cr(VI) onto waste acorn of Quercus ithaburensis. Chem. Eng.
Process. Process Intensif. 46 (10), 1020–1029. https://doi.org/10.1016/j.cep.2007.
05.007.
Misra, D.N., 1969. Adsorption on heterogeneous surfaces: a dubinin-radushkevich equa-
tion. Surf. Sci. 18 (2), 367–372. https://doi.org/10.1016/0039-6028(69)90179-4.
Mortimer, R.G., 2008. Physical Chemistry, 3rd edition. Elsevier Academic Press.
Nataraj, S.K., Hosamani, K.M., Aminabhavi, T.M., 2009. Nanofiltration and reverse os-
mosis thin film composite membrane module for the removal of dye and salts from
the simulated mixtures. Desalination 249 (1), 12–17. https://doi.org/10.1016/j.
desal.2009.06.008.
Panizza, M., Barbucci, A., Ricotti, R., Cerisola, G., 2007. Electrochemical degradation of
methylene blue. Sep. Purif. Technol. 54 (3), 382–387. https://doi.org/10.1016/j.
seppur.2006.10.010.
Rafatullah, M., Sulaiman, O., Hashim, R., Ahmad, A., 2010. Adsorption of methylene blue
on low-cost adsorbents: a review. J. Hazard. Mater. 177 (1), 70–80. https://doi.org/
10.1016/j.jhazmat.2009.12.047.
Rafatullah, M., Ahmad, T., Ghazali, A., Sulaiman, O., Danish, M., Hashim, R., 2013. Oil
palm biomass as a precursor of activated carbons: a review. Crit. Rev. Environ. Sci.
Technol. 43 (11), 1117–1161.
Sahu, J.N., Agarwal, S., Meikap, B.C., Biswas, M.N., 2009. Performance of a modified
multi-stage bubble column reactor for lead(II) and biological oxygen demand re-
moval from wastewater using activated rice husk. J. Hazard. Mater. 161 (1),
317–324. https://doi.org/10.1016/j.jhazmat.2008.03.094.
Sarasa, J., Roche, M.P., Ormad, M.P., Gimeno, E., Puig, A., Ovelleiro, J.L., 1998.
Treatment of a wastewater resulting from dyes manufacturing with ozone and che-
mical coagulation. Water Res. 32 (9), 2721–2727. https://doi.org/10.1016/S0043-
1354(98)00030-X.
Smith, S.E., 1947. The sorption of water vapor by high polymers. J. Am. Chem. Soc. 69
(3), 646–651. https://doi.org/10.1021/ja01195a053.
Veliev, E.V., Öztürk, T., Veli, S., Fatullayev, A.G., 2006. Application of diffusion model for
adsorption of azo reactive dye on pumice. Pol. J. Environ. Stud. 15 (02), 347–353.