Journal of Cleaner Production 137 (2016) 1246e1259

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Journal of Cleaner Production

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

Removal of methylene blue and phenol onto prepared activated

carbon from Fox nutshell by chemical activation in batch and
xed-bed column
Arvind Kumar, Hara Mohan Jena*
Department of Chemical Engineering, National Institute of Technology (NIT), Rourkela 769008, Orissa, India

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 21 February 2016
Received in revised form
28 June 2016
Accepted 26 July 2016
Available online 28 July 2016

Fox nutshell was used as a new precursor for the production of a high surface area activated carbon with
zinc chloride activator at 600
C activation temperature and 2.0 impregnation ratio. The Brunauer
eEmmetteTeller (BET) surface area of the prepared activated carbon was 2869 m2/g with total pore,
micropore and mesopore volume of 1.96, 1.68 and 0.28 cm3/g. Methylene blue and phenol were used as
adsorbates for adsorption experiment onto prepared high surface area activated carbon in batch and
column scale. Adsorption kinetics of methylene blue and phenol was studied by using commonly kinetic
models, i.e., the pseudo-rst-order model, the pseudo-second-order model, and the intraparticle diffusion model. The experimental adsorption isotherms of these adsorbates on the prepared activated carbon
were analysed using three isotherm models: the Langmuir, Freundlich and Tempkin. The equilibrium
adsorption (qe) of methylene blue was increased from 249.88 to 968.74 mg/g and for phenol was
increased from 19.84 to 75.37 mg/g when initial concentration was enhanced from 100 mg/L to 500 mg/
L. The negative values of the enthalpy change (DH0 2.93 kJ/mol for MB and 16.92 kJ/mol for phenol)
indicate that the MB and phenol adsorption process onto FNAC was exothermic in nature. In column
experiments, the effects of the bed height of the packing material and ow rate of methylene blue and
phenol onto prepared activated carbon were studied.
2016 Elsevier Ltd. All rights reserved.

Keywords:
Fox nutshell
Activated carbon
Adsorption
Methylene blue
Phenol

1. Introduction
Dyes and Phenols are widely used in industries such as the
textile, paper, pulp mill, leather, dye synthesis, printing, food, and
plastics industries (Altenor et al., 2009; Bazrafshan et al., 2012b).
The wastewaters from such industries are generating considerable
amounts of colored and phenolic pollutants. These pollutants are
toxic, causing allergy, skin irritation, and even carcinogenic, posing
a serious hazard to living organisms (Altenor et al., 2009; Cazetta
et al., 2011; Royer et al., 2009). Therefore, it is necessary to
remove them from wastewater before it is discharged. For this
purpose, many treatment methods, such as chemical oxidation,
solvent extraction, chemical coagulation, photocatalytic degradation, membrane ltration, electrochemical methods, adsorption,
and biological treatments, have been developed for treating dyes as

* Corresponding author.
E-mail addresses: arvindkr202@gmail.com (A. Kumar), hmjena@nitrkl.ac.in
(H.M. Jena).
http://dx.doi.org/10.1016/j.jclepro.2016.07.177
0959-6526/ 2016 Elsevier Ltd. All rights reserved.

well as organic pollutants containing wastewater (Bazrafshan et al.,

2013, 2012a, 2014; Benadjemia et al., 2011; Din et al., 2009). Among
these methods, adsorption is highly effective for the removal of
dyes, as well as other organic and inorganic pollutants. Adsorption
by activated carbon is most favorable method due to bearing high
surface area, well-developed internal pore structure and surface
chemical functional groups located at the outer and inner surfaces
(Din et al., 2009; Nowicki et al., 2016; Royer et al., 2009).
Activated carbon (AC) is a carbonaceous material and the widely
used as industrial adsorbents. AC contains adsorption behavior, has
many important applications such as ltration and purication

s et al., 2002), catalysts (Gomes et al., 2010), hydrogen stor(Valde
age (Lee et al., 2007), supercapacitors (Fang et al., 2005), and so on.
However, the high production cost of AC restricts usages in large
scale (Hayashi et al., 2000). The renewable resources like biomassbased agriculture byproducts such as oil palm shell (Tan et al.,
2008), coconut shells (Cazetta et al., 2011), corn cobs
(Ka

zmierczak et al., 2013; Sych et al., 2012), globe artichoke leaves
(Benadjemia et al., 2011), cotton stalks (Deng et al., 2009), cumin
herb wastes (Bazrafshan et al., 2013), Brazilian pine-fruit shell

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

(Royer et al., 2009), Eucalyptus wood (Tancredi et al., 2004), jute

ber (Senthilkumaar et al., 2005), pistachio nut shells (Lua and
Yang, 2005), tropical fruit skins (Nowicki et al., 2016), coffee
grounds (Reffas et al., 2010), pomelo peel (Peng et al., 2014), pomelo
skin (Foo and Hameed, 2011), waste tea (Gokce and Aktas, 2014),
pistachio nut shells (Nowicki et al., 2015), is one of the useful ways
chosen by researchers to reduce the raw material cost.
Fox nutshell available as a low-cost agriculture waste. Fox
nutshell was used as a precursor material for activated carbon
preparation by chemical activation method with ZnCl2 activating
agent in the previous study (Kumar and Jena, 2015). To the best of
our knowledge, no studies have been reported in the adsorption
studies of methylene blue (MB) and phenol onto the prepared
activated carbon from Fox nutshell. Therefore, the objective of this
study was to remove MB and phenol from aqueous solution in
batch as well as xed-bed column processes.
2. Materials and methods

1247

determined using the following relations:

qe

C0  Ce V
;
ms

R%

(1)

C0  Ce
 100;
C0

(2)

Kinetic studies were also performed according to the method

described in batch equilibrium method. The adsorption capacity qt
(mg/g) at different contact time t (min) was determined using the
following equation:

qt

C0  Ct V
;
ms

(3)

where C0, Ce, and Ct are the initial, equilibrium, and at time t (min)
of adsorbates concentration (mg/L), V the volume of solution (L)
and ms the dry weight of the added adsorbent (g).

2.1. Preparation of adsorbent

2.4. Fixed-bed column adsorption studies
Fox nutshell was collected from the locally available processing
plant in Madhubani, Bihar, India. The sample preparation was
briey discussed in the previous study (Kumar and Jena, 2015). The
dried Fox nutshell (10 g) was added to 150 ml solution of 20 g ZnCl2,
and the resulting reaction mixture was kept for 24 h. The resulting
material was dried in an oven at 110
C for 24 h. The impregnated
material was maintained in a tubular furnace at preset of 5
C/min
increment temperature of 600
C for 60 min of activation time with
150 ml/min ow rate of N2. The produced carbonized material was
soaked in 0.5 N HCl and left for 24 h to remove residual zinc from
the pores of the carbon. The mixture was washed with hot distilled
water and nally with cold distilled water to remove residual
chemical until pH of activated carbon reached neutral. The wet
sample was dried in an oven at 110
C for 24 h. The resulting Fox
nutshell activated carbon (FNAC) was kept in air tight container and
used as an adsorbent. FNAC was characterized by using N2
adsorption-desorption isotherm at 77 K and Field emission scanning electron microscopy (FESEM) techniques.
2.2. Adsorbates and analytical methods
Methylene blue (C16H18N3SCl.3H2O) and phenol (C6H5OH) were
used in the study are of brand Merck, India. Stock solutions of
1000 mg L1 of both adsorbates were prepared by dissolving an
appropriate quantity of MB and phenol in a liter of distilled water.
The working solutions were prepared by diluting the stock solution
with distilled water.
Aliquots of both adsorbates were withdrawn from the suspension at preset time intervals and were centrifuged (2 ml) at
10,000 rpm for 5 min to remove the adsorbent particles before
analytical measurements were made. The concentrations of MB and
phenol before and after adsorption were measured at 664 nm and
270 nm by using UVeVisible spectrophotometer (Jasco, Model V530, Japan).

A Perspex glass cylindrical tube having 2.5 cm internal diameter

and 20 cm height was used to construct the adsorption column. The
real and schematic photograph of xed bed adsorption column is
shown in Fig. 1. The column was packed with the calculated amount
of the FNAC to obtain the desired bed height. The prepared activated carbon (size of 0.5e1.5 mm) was lled up to 4 cm height of
the column and after that the lled carbon was taken out from bed,
and the material weighed using standard weighing scale. Therefore,
4 cm bed height of the column was packed with 6.0 g wt. of activated carbon. The bed was held in place between two plugs of
cotton. The glass beads supported the cotton in the lower and upper
part of the column. The volumetric ow rate of MB and phenol was
adjusted to 5, 10 and 15 mL/min in the experiments. The adsorbates
solutions were fed continuously to the column in an upward ow
mode using the peristaltic pump at room temperature. Efuent
samples were collected from the sample collecting sites of the
column at different time intervals, and the concentration of MB and
phenol was analysed with a UV/visible spectrophotometer.
The loading behavior of MB and phenol in its dynamic adsorption from solution by FNAC could be shown in the form of breakthrough (BT) curves which is usually expressed in terms of
normalized concentration, dened as the ratio of outlet adsorbate
concentration to the inlet adsorbate concentration (Ct/C0) or the
adsorbed solute concentration (Cad), which is the difference between inlet and outlet adsorbate concentration (C0Ct), as a function of time (t) for a given bed height. The breakthrough point was
taken as the position at which Ct/C0 0.05 and the exhaustion
point when Ct/C0 0.95 (Salman et al., 2011). The time taken for
outlet concentration of adsorbate to reach the breakthrough point
is known as breakthrough time. The area under the BT curve which
is obtained by integrating the plot, can be used to estimate the total
adsorbed quantity of adsorbate, qtot (mg) in the column for a given
inlet concentration and ow rate and is given by Eq. (4) (Aksu and
nen, 2004; Salman et al., 2011).
Go

2.3. Batch adsorption and kinetic experiment

The batch adsorption experiments were conducted in a set of
250 mL of conical asks containing 100 mL of MB and phenol (100,
200, 300, 400, 500 mg/L) solution with predetermined amount of
adsorbents (0.04 g of MB and 0.5 g of phenol). The asks were
agitated in an isothermal orbital shaker at optimized 150 rpm and
30
C temperature until the equilibrium is reached. The equilibrium
adsorption capacity, qe (mg/g) and percentage removal, R (%) were

qtot

Q
1000

tt
Z tot

Cad dt;

(4)

t0

where Q (mL/min) is the volumetric ow rate, Cad (mg/L) is the

difference between the initial and nal concentrations of adsorbates at the end of the total ow time till exhaustion ttot (min).
Equilibrium adsorbates uptake in the column or maximum capacity

1248

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

Fig. 1. Real and schematic photograph of a xed bed adsorption column.

3. Results and discussion

(Yorgun et al., 2009). The yield of FNAC is 32.83%. The ultimate

analysis and pore structure characteristics of the prepared activated
carbon FNAC were tabulated in Table 1. The carbon content in FNAC
is 89.77%.
The nitrogen adsorptionedesorption isotherm of the FNAC obtained at 77 K is shown in Fig. 2 (a). The BET surface area of the
FNAC was calculated by the BrunauereEmmetteTeller (BET)
method is 2869 m2/g. The total pore volume, micropore volume,
and mesopore volume of FNAC was 1.96, 1.68, and 0.28 cm3/g. The
DFT pore size distribution of the prepared activated carbon FNAC is
shown in Fig. 2 (b). The most of the pores are formed to have sizes
smaller than 20 , indicating a development of microporosity in
FNAC.
Field Emission Scanning Electron Microscopy (FESEM) images of
the Fox nutshell and FNAC are shown in Fig. 3. There are signicant
differences in the surface morphology of the Fox nutshell and the
prepared activated carbon. The surface of Fox nutshell is moderately smooth and has no pores on the surface, but in the prepared
activated carbon, more pores are developed that conrms the
prepared activated carbon of high surface area.

3.1. Characterization of the prepared activated carbon FNAC

3.2. Effect of agitation speed

The yield of prepared activated carbon is dened as the nal

weight of produced activated carbon, washing, and drying, divided
by the initial weight of the raw material; both on a dry basis

In the batch adsorption study, agitation speed plays a signicant

role in affecting the external boundary lm and the distribution of
the solute in the bulk solution (Weng et al., 2009). Fig. 4 shows the
effect of agitation speed on % removal of MB and phenol onto FNAC.
A series of agitation speed experiments performed by using 0.04 g
FNAC for MB and 0.5 g for phenol solution of 100 mL of the concentration of 100 mg/L each at 30
C and different shaking speeds in
the range of 90e170 rpm. From Fig.4, the results show that the
removal efciency of MB and phenol increases with increase in
agitation speed and maximum removal by FNAC are achieved at
150 rpm, and above 150 rpm, the % removal is almost same. Thus,
the agitation speed was xed at 150 rpm for MB and phenol
adsorption in further experiments. These results indicate that an
effective transport of MB and phenol ions towards the adsorbent
surfaces occurred, due to less resistance to diffusion at higher
agitation speed. Some studies have reported similar behavior

of the column (bed capacity), qbed (mg/g) is dened by Eq. (5) (Aksu
nen, 2004; Salman et al., 2011):
and Go

qbed

qtot
;
ms

(5)

where ms is the dry weight of the adsorbent (g).

The quantity of adsorbates sent to the column (mtot) is given in
Eq. (6) (Girish and Murty, 2015):

mtot

C0 Qttot
;
1000

(6)

The % removal of adsorbates are given by Eq. (7) (Girish and

Murty, 2015):

%rem

qtot
 100;
mtot

(7)

Table 1
Product yields, proximate, ultimate analysis and Pore structure characterization of
prepared activated carbon FNAC.
Ultimate analysis

Prepared activated carbon (wt%)

Pore structure
characteristics

C
H
N
S
Oa

89.77
2.33
0.43
0.06
7.41

SBET (m2/g)
VT (cm3/g)
Vmicro (cm3/g)
Vmeso (cm3/g)
Vmicro/VT (%)
Dp (nm)

By difference.

2869
1.96
1.68
0.28
85.71
2.75

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

1249

Fig. 4. Effect of shaking speed on the % removal of MB and phenol on FNAC

(C0 100 mg/L, temperature 30
C, FNAC quantity 0.04 g for MB and 0.5 g for
phenol).

between adsorbents and adsorbates at higher agitation speed

(Abussaud et al., 2016; Auta and Hameed, 2014; Deng et al., 2009;
Yang et al., 2015).
3.3. Effect of solution pH on MB and phenol uptake

Fig. 2. (a) Nitrogen adsorptionedesorption isotherms and (b) pore size distribution for
prepared activated carbon FNAC.

The adsorption of MB and phenol onto the FNAC was studied for
three hours over a pH range of 3e12 and 3e9. The initial concentration of MB and phenol was 100 mg/L, and the adsorbent dose
was kept at 0.03 g and 0.05 for MB and phenol respectively. The pH
was adjusted by adding a few drops of diluted 0.1N NaOH or 0.1N
HCl. The mixture was agitated in an orbital shaker at an optimized
agitation speed of 150 rpm at 30
C.
MB is a cationic dye with the estimated dimensions of
1.43 nm  0.61 nm  0.4 nm and its adsorption by activated carbon
is very susceptible to solution pH (Gokce and Aktas, 2014). Fig. 5
shows the initial pH increases from 3 to 12 then increases the %
removal of MB. The low adsorption rate of MB on FNAC observed at
pH 3 was due to the positive charge on the surface, causing H ions
to compete effectively with MB cations. When the pH of the solution increases, the positive charge on the interface of the solution
decreases and the negatively charged appeared on the adsorbing
surface, thereby resulting in an increased adsorption of MB due to

Fig. 3. Field Emission Scanning Electron micrographs of samples: (a) of Fox nutshell, and (b) of FNAC.

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A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

Fig. 5. Effect of pH on the % removal of MB and phenol by FNAC with solution pH

(C0 100 mg/L, contact time (t) 3 h, temperature 30
C).

an increase in the electrostatic attraction between positively

charged adsorbate and negatively charged adsorbent (Altenor et al.,
2009; Senthilkumaar et al., 2005). The maximum % removal of MB
was observed at pH 11. Similar results are reported for the
adsorption of methylene blue on jute ber carbon and wheat shells
(Bulut and Aydn, 2006; Senthilkumaar et al., 2005).
Fig. 5 shows the inuence of solution pH on phenol removal by
FNAC in the pH range of 3.0e9.0. The phenol adsorption is
increased with pH from 3.0 to 7.0 and is decreased with increased
pH from 7.0. The maximum adsorption was observed at pH of 7.0.
As pH increased from 3.0 to 7.0 the static repulsion force decreases
and the phenol adsorption increases. At pH 8, the phenol adsorption decreased due to three reasons. First, the negative charges on
the FNAC surface increased with increase of pH and phenol changes
from molecular state to ionic state, which makes the repulsion force
between phenol ions and the activated carbon. Second, the phenol
ions adsorbed by the FNAC also has a repulsion force between
themselves. Third, the negative charges on the FNAC surface are
repulsive. While at acidic pH, the percentage removal was higher
because phenol was undissociated and the dispersion interaction
predominated (Hameed and Rahman, 2008). Similar results are
reported for the adsorption of phenol on cherry stone based activated carbon and rattan sawdust activated carbon (Beker et al.,
2010; Hameed and Rahman, 2008).
3.4. Effects of adsorbent dose on MB and phenol adsorption
To study the effect of FNAC dose (g) on MB and phenol uptake,
experiments were conducted at an initial solution concentration of
100 mg/L at 30
C. Fig. 6(a) shows the effect of adsorbent dose on
the % removal of MB. Activated carbon dosage was ranged from 0.01
to 0.1 g/100 mL and equilibrated for three hours. The % removal of
MB increased with the increase in adsorbent dose up to 0.04 g
signicantly, and after that remained unchanged. Thus, to get the
better MB removal and to not consume a signicant quantity of
FNAC, 0.04 g was chosen as an optimal mass of the adsorbent for
the further experiments. At equilibrium time, the % removal
increased from 79.82 to 99.96%. The rise in colour removal was due
to the increase in the available sorption surface sites on the activated carbon.
Fig. 6(b) shows the effect of adsorbent dose on the % removal of
Phenol. It is found that the removal of phenol increased with the

Fig. 6. Effect of adsorbent dosage (C0 100 mg/L, pH 11 for MB and 7 for phenol,
temperature 30
C, contact time (t) 3 h) on the % removal of (a) MB and (b) phenol.

increase in adsorbent dose up to 0.4 g, then increased slowly with

further increase in adsorbent dose up to 0.5 g and after that
remained unchanged. Thus, 0.5 g was chosen as an optimal mass of
the FNAC for the further experiments to get the better removal of
phenol and to not consume a considerable quantity of adsorbent. At
equilibrium time, the % removal of phenol increased from 59.42 to
99.72%.

3.5. Effects of contact time and initial MB and phenol

concentrations
Figs. 7(a) and (b) show the effects of contact time on the
adsorption of MB and phenol onto FNAC at different initial concentrations (100, 200, 300, 400 and 500 mg/L) at 30
C. Adsorption
studies were carried out for three hours. It can be easily observed
that the adsorption capacity of MB and phenol on FNAC drastically
increased during the initial stage and then at a slow speed. The
growing trend stopped when a state of equilibrium was reached.
From Fig. 7(a), the adsorption equilibrium time is found to increase
with increase the initial concentration of MB. A larger amount of
MB was removed by FNAC in the rst 10 min of contact time due to
available of a large number of vacant sites with active surface

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

1251

3.6. Adsorption kinetic studies

In the present study, the most used kinetic models of pseudorst-order (Budinova et al., 2006) and pseudo-second-order (Ho
and McKay, 1999) were used to t the experimental data. Linear
forms of pseudo-rst-order and pseudo-second-order kinetic
equations are given in Eqs. (8) and (9), respectively.

lnqe  qt lnqe  k1 t;

(8)

 
t
1
1
t;

qt k2 q2e
qe

(9)

where qe (mg/g) and qt (mg/g) are the amounts of pollutant

adsorbed onto FNAC at the equilibrium and at any time t (min), and
k1 (min1) and k2 (g/min/mg) are the rate constant of the pseudorst and pseudo second-order adsorption.
The study of adsorption kinetics describes the solute uptake
rate, and evidently this rate controls the residence time of adsorbate at the solidesolution interface. The adsorption kinetics of
pseudo-rst-order and pseudo-second-order for MB and phenol
onto FNAC is shown in Figs. 8 and 9. As observed, the adsorption
kinetics for both adsorbates presents the same trend with the

Fig. 7. Effects of contact time on the adsorption capacity at different initial concentrations at mass of adsorbent: (a) 0.04 g for 100 mL MB solution, pH: 11 and (b) 0.5 g
for 100 mL phenol solution; pH: 7.

functional groups on the surface. But the time to reach equilibrium

was observed to be 20 min for 100 mg/L, whereas this increased to
60 min for a concentration of 500 mg/L. The adsorption capacity of
FNAC increases with increasing of initial MB concentration. Because
the initial concentration provided an important driving force to
overcome all mass transfer resistance. Similar results have been
reported in the literature for the removal of dyes (Bedin et al., 2016;
an et al., 2007; Dural et al., 2011; Kannan
Cheri et al., 2013; Dog
and Sundaram, 2001). The adsorption equilibrium increased from
249.88 mg/g to 968.74 mg/g when MB initial concentration
enhanced from 100 mg/L to 500 mg/L. The higher mass transfer is
because of increase in the driving force, i.e., the initial concentration of MB. Reverse behavior was observed in the case of % removal
of MB, as the initial concentration increased from 100 mg/L to
500 mg/L then removal % of MB decreased from 99.95% to 77.49%.
The phenol adsorption onto the FNAC was as same trend as MB
adsorption. The adsorption equilibrium of phenol adsorption was
achieved in 60 min for all concentrations studied (see Fig. 7(b)). The
adsorption capacity at equilibrium (qe) increased from 19.84 to
75.37 mg/g while % removal was decreased from 99.19 to 75.37%
with an increase in the initial phenol concentrations from 100 to
500 mg/L.

Fig. 8. (a) Pseudo rst-order model and (b) pseudo second-order model for the
adsorption of MB onto the FNAC.

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A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

Table 2. As observed, the experimental kinetic data are better tted

by the pseudo-second-order model (R2 1 for all MB concentrations and 0.999 for all phenol concentrations). Moreover, all the
calculated normalized standard deviation (Dq) (shown in Table 2)
resulted in relatively lower values for the pseudo-second-order
kinetic model than the pseudo-rst-order kinetic model for both
adsorbates. Also, the qe calculated value that was derived from the
second-order equation is quite similar to those obtained experimentally, which indicates that the second-order model is suitable
for the observed kinetics of both adsorbates. The linear plots of t/qt
vs. t are shown in Figs. 8(b) and 9(b) indicate good agreement with
experimental data with the pseudo-second-order kinetic model for
both MB and phenol at all concentrations.
3.7. Intraparticle diffusion model
Since neither the pseudo-rst-order nor the pseudo-secondorder model can identify the diffusion mechanism. The kinetic results were analysed by the intraparticle diffusion model to elucidate the diffusion mechanism (Hameed and Rahman, 2008). The
intraparticle diffusion model can be described as:

qt ki t 0:5 c;

(10)

where ki is the intraparticle diffusion rate constant (mg g1 min1/

), and c is the intercept. The constants (ki) for both MB and phenol
adsorption were calculated and tabulated in Table 2. If the value of c
is zero, then the rate of adsorption is controlled by intraparticle
diffusion for the entire adsorption period but in the present study, c
is not zero. However, the plot of q against t0.5 usually shows more
than one linear portion. As seen from Fig. 10, the plots are not linear
over the whole time range, that conrms more than one process
affect the MB and phenol adsorption (Hameed and Rahman, 2008;
Senthilkumaar et al., 2005).
2

3.8. Adsorption isotherms

Fig. 9. (a) Pseudo rst-order model and (b) pseudo second-order model for the
adsorption of phenol onto the FNAC.

adsorption process to be faster for MB. A higher adsorption capacity

for MB than phenol is also observed. The derived kinetic parameters of pseudo-rst-order and pseudo-second-order are listed in

At equilibrium state, the adsorption isotherm is very useful to

describe how the adsorbed molecules distribute between the liquid
phase and the solid phase. The Langmuir, Freundlich and Temkin
isotherm models were used for the adsorption isotherm. Fig. 11
shows the non-linear curve (Ce/qe versus Ce) ts of the adsorption isotherms data of MB and phenol onto the FNAC by the three
models mentioned above. The results from the tting done for

Table 2
Kinetic constants obtained for the adsorption of phenol adsorption onto FNAC at 30
C.
C0 (mg/L)

Parameters

MB

1

qe,exp (mg g )
Pseudo rst-order
qe,cal (mg g1)
h0 (mg g1 min1)
K1 (min1)
R2
Dq (%)
Pseudo second-order
qe,cal (mg g1)
k2 (g (mg min)1)
h0 (mg g1 min1)
R2
Dq (%)
Intraparticle diffusion
Ki (mg g1 min1/2)
R2
C

Phenol

100

200

300

400

500

100

200

300

400

500

249.88

483.84

695.55

836.07

968.74

19.84

38.25

55.25

67.06

75.37

10.45
8.74
0.087
0.8915
31.94

85.63
7.93
0.079
0.9231
9.14

101.65
7.74
0.0774
0.9703
30.4

93.82
7.77
0.0773
0.8222
29.59

348.53
7.80
0.078
0.8885
2.06

2.07
4.10
0.041
0.9904
20.11

16.42
11.60
0.058
0.995
9.23

17.55
17.52
0.0584
0.994
9.18

32.37
23.40
0.0585
0.998
6.31

33.63
29.80
0.0596
0.996
6.38

250.00
0.031
1937.50
1
0.0025

487.80
0.0022
518.73
1
0.037

699.30
0.00296
1447.50
1
0.02

840.34
0.00264
1864.30
1
0.017

970.87
0.00094
886.03
1
0.0072

19.82
0.081
31.82
0.999
0.023

38.21
0.0101
14.75
0.999
0.017

55.23
0.0094
29.29
0.999
0.005

67.01
0.0051
22.90
0.999
0.009

75.33
0.0057
34.37
0.999
0.006

0.64
0.4904
243.19

10.91
0.3916
375.72

8.34
0.3718
612.13

9.34
0.3852
742.50

19.84
0.6204
763.88

0.17
0.766
17.98

1.48
0.667
22.85

1.52
0.7465
39.13

2.51
0.7545
40.37

2.41
0.7097
49.86

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

1253

transmigration in the plane of the adsorbent surface (Langmuir,

1918). The linear form of the Langmuir equation is represented as
follows:

Ce
1
Ce

;
kL qm qm
qe

(11)

where qm represents the maximum adsorption capacity of the solid

phase loading and kL is the energy constant related to the heat of
adsorption. Fig. 12 shows a linear relationship of Ce/qe versus Ce
using experimental data obtained for MB and phenol adsorption.
The intercept and the slope of the plot, qm, and kL values are
tabulated in Table 3.
The separation factor (RL) is dimensionless quantity and it is an
essential characteristic of the Langmuir isotherm (Hall et al., 1966)
and is dened as:

RL

1
;
1 kL C0

(12)

where kL is the Langmuir constant and C0 is the highest MB and

phenol concentration (mg/L). The value of RL indicates the type of
the isotherm to be either unfavourable (RL > 1), linear (RL 1),
favorable (0 < RL < 1) or irreversible (RL 0) (Hall et al., 1966). The
values of RL was found to be 0.0116 and 0.0153 for MB and phenol,
and this again conrms that the Langmuir isotherm is favorable for
MB and phenol adsorption on the FNAC under the conditions used
in the present study.
The Freundlich isotherm equation is based on sorption onto a
heterogeneous surface and given as (Freundlich, 1906):
1

qe kF Ce n ;

Fig. 10. Intraparticle diffusion model for the adsorption of (a) MB and (b) phenol onto
the FNAC.

(13)

where kF ((mg/g) (L/mg)1/n) and n are Freundlich constants related

to adsorption capacity and adsorption intensity, respectively. The
value of n > 1 represents a favorable condition. The linear form of
Eq. (14) is

1
ln qe ln kF ln Ce ;
n

(14)

A linear plot of ln qe versus ln Ce conrms the validity of the

Freundlich model and is shown in Fig. 13.
Temkin and Pyzhev (Temkin and Pyzhev, 1940) have suggested
that the heat of adsorption should decrease linearly with the surface coverage because of the existence of adsorbate-adsorbate interactions. The following equation can adjust the corresponding
adsorption isotherm:

qe B lnA B lnCe ;

Fig. 11. Adsorption isotherms of MB and phenol on FNAC.

modelling of MB and phenol adsorption are listed in Table 3.

The Langmuir isotherm is valid for monolayer and homogeneous sites within the adsorbent surface with a uniform distribution of energy level. The model assumes uniform adsorption and no

(15)

where B RT/b is related to the heat of adsorption (L/g), and A is

the dimensionless Tempkin isotherm constant. The constant A and
B values are listed in Table 3.
The R2 value estimates the goodness of the t of the studied
models. The data of Table 3 show that the Langmuir model
(R2 0.9897 for MB and R2 0.9956 for phenol) is the most
adapted for tting adsorption isotherms of MB and phenol onto the
FNAC than the Freundlich model (R2 0.9784 for MB and
R2 0.9867 for phenol). Thus, from Table 3, the comparison of
tested models for the description of equilibrium adsorption isotherms
on
the
FNAC
is
as
follows:
Langmuir
>
Freundlich
>
Tempkin
for
MB
and
Langmuir > Tempkin > Freundlich for phenol.

1254

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

Table 3
Isotherms constants for adsorption of MB and phenol onto FNAC at 30
C.
Adsorbates

MB
Phenol

Freundlich

Langmuir

Tempkin

kF (mg/g (L/mg)1/n)

R2

qm (mg/g)

kL (L/mg)

R2

A (L/g)

R2

402.02
20.42

5.79
3.5

0.971
0.987

980.39
78.74

0.171
0.129

0.9863
0.996

28.85
212.24

188.67
4.26

0.8661
0.988

Fig. 12. Langmuir isotherms for the adsorption of MB and phenol onto the FNAC.

Dispersive interaction is related with the pe p electron coupling on

the surface of the activated carbon. The dispersive interaction easily
occurs between the p electrons exist within the molecular structure of MB and delocalized p electrons on the basal planes of the
activated carbon. The pore size distribution of AC is another
parameter that affects the MB adsorption onto AC. The molecular
dimension of the MB is larger than the micropores means that a
molecular sieving effect reduces the adsorption capacity of the AC
(Gokce and Aktas, 2014; Pereira et al., 2003).
Three adsorption routes are widely accepted and investigated in
the phenol adsorption studies: the electron donoreacceptor
interaction, dispersive interaction of pe p electron coupling and
competing for adsorption of solvent molecules (Da browski et al.,
2005). It was reported that two different ways of electron
donoreacceptor interaction occurred during phenol adsorption.
One involves the interaction of the aromatic ring of phenol (electron acceptor) with carbonyl groups (electron donor) of AC
(Mattson et al., 1969). Another one involves the interaction between aromatic ring (electron acceptor) of phenol and basic sites of
AC (electron donor) (Da browski et al., 2005). The strength of
donoreacceptor interaction during phenol adsorption depends
mainly on the dipole moment of the oxygen groups on basal plane.
Carbonyl groups on the activated carbon surface are known as
strong donors because of their high dipole moments (Gokce and
Aktas, 2014). The solvent also affects to phenol adsorption onto
activated carbon. It occurs when some of the most active sites
adsorbing phenols are blocked by water adsorption (Da browski
et al., 2005). In other words, some pores may be inaccessible to
phenolewater aggregates (Hameed and Rahman, 2008). Carboxyl
and hydroxyl groups inhibit the adsorption of phenol and increase
the afnity of carbon towards the water, and therefore, solvent
molecules can block some pores (Da browski et al., 2005). The inuence of electrostatic interactions, which strongly depend on pH
of the solution, has been already discussed in the pH study.

3.10. Thermodynamic studies

Fig. 13. Freundlich isotherms for the adsorption of MB and Phenol onto the FNAC.

3.9. MB and phenol adsorption mechanism

Three consecutive mass transport steps are associated with the
adsorption of a solute from solution by the porous adsorbent. First,
the adsorbate migrates through the solution, i.e., lm diffusion; in
the second step, the solute movement from particle surface into the
interior site by pore diffusion and nally the adsorbate is adsorbed
on the active sites of the interior of the adsorbent particle (Gokce
and Aktas, 2014).
Two simultaneous adsorption routes have been proposed for the
active site adsorption of MB molecules. One involves the electrostatic interaction of MB cations with negatively charged carbon
surface functional groups and other is the dispersive interaction of
MB molecules with a surface layer of AC (Pereira et al., 2003).

The temperature effect on the MB and phenol adsorption process was investigated with the thermodynamic parameters like a
change in Gibbs free energy (DG0), change in enthalpy (DH0) and
change in entropy (DS0). Its original concept assumes that energy
cannot be gained or lost, where entropy change is the driving force.
The values of DH, DG, and DS were calculated according to the
following equations:

KC

qeW=V
Ce

(16)

DG RTlnKC ;
lnKC

DS
R

DH
RT

(17)
;

(18)

Where R (8.314 J/mol K) is the universal gas constant, T (K) is the

absolute solution temperature, and KC (L/g) is the Langmuir
isotherm constant. The values of DH and DS were determined from

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

1255

adsorption shows the decreased randomness at the solid-solute

adsorption systems (Gao et al., 2013; Ma et al., 2013). The negative values of the enthalpy change (DH0 2.93 kJ/mol for MB
and 16.92 kJ/mol for phenol) indicate that the MB and phenol
adsorption process onto the FNAC is exothermic in nature.
3.11. Comparison to some other carbonaceous materials
A comparison of the textural properties and maximum
adsorption capacities of the FNAC with other reported values for
some commercial and agricultural-based ACs are listed in Table 5.
Table 6 shows the comparative study of MB and phenol removal by
different techniques. From Table 5, the FNAC seems to be an alternative precursor for the commercial AC preparation, in which its
sorption capacity of MB is higher than 7 many commercial and
others agricultural waste-based carbonaceous sorbents. FNAC
could be employed as an efcient carbonaceous adsorbent to
compare with the commercial ones for the removal MB and phenol
from wastewater.
3.12. Cost estimation of prepared activated carbon

Fig. 14. Thermodynamic studies of MB and phenol adsorption onto the FNAC.

the slope and intercept of the van't Hoff plot of lnKC versus 1/T
(Figs. 14(a) and (b)). The calculated thermodynamic parameter
values are tabulated in Table 4. Generally, a value of DG0 in between
0 and -20 kJ/mol indicates physical adsorption i.e., electrostatic
interaction between adsorption sites and the adsorbing ion while a
more negative DG0 value ranging from 80 to 400 kJ/mol indicates that the adsorption involves charge sharing or transferring
from the adsorbent surface to the adsorbing ion to form a coordinate bond (chemisorption) (AlOthman et al., 2014; Singh, 2000).
The MB and phenol uptake increased with increasing temperature
up to 40
C. From Table 4, the negative Gibbs free energy (DG0) of
the experimental value indicates a typical physical process. The
positive value of DS shows an increased randomness or disorder of
the adsorbed species during MB adsorption process by FNAC
(AlOthman et al., 2014). The negative value of DS of phenol

Table 4
Thermodynamic parameters for the adsorption of MB and phenol onto FNAC.
Adsorbents

T(K)

DG (kJ/mol)

DH (kJ/mol)

DS (J/mol K)

MB

298
303
308
313
318
298
303
308
313
318

7.80
8.002
7.98
8.06
8.18
0.23
0.29
0.92
0.97
0.11

2.93

16.46

16.92

57.35

Phenol

The production of activated carbons from agricultural waste, Fox

nutshell may help in two ways. First, the agricultural waste is
converted into value-added materials as activated carbons, which
are generated in huge amounts annually. Second, activated carbon
prepared is of very high surface area and pore volume can be used
for the removal of water pollutant such as MB and phenol. The
prepared FNAC has high surface area (2869 m2/g) than commercial
activated carbon (Filtrasorb 400 of 1216 m2/g surface area). The
estimated cost of production of FNAC by chemical activation with
ZnCl2 activator of analytical grade and commercial grade on lab
scale production are 82.87 US$/kg and about 8.31 US$/kg (shown in
Table 7). Thus the cost of FNAC on commercial scale production will
be near about the cost of commercial activated carbon, but FNAC
will have very high surface area. FNAC would be an alternative for
the commercially available activated carbon in the removal of
pollutants from wastewater.
3.13. Column studies
3.13.1. Effect of activated carbon bed height
Figs. 15(a) and (b) show the Breakthrough (BT) curves obtained
for MB and phenol adsorption onto FNAC at bed heights of 2, 3 and
4 cm, and a constant ow rate of 5 mL/min and both adsorbates
initial concentration of 100 mg/L. The gures show that both the BT
and exhaustion times increased as bed height increased for adsorbates. The increase in the breakthrough time could be ascribed
to the longer distance it takes the mass transfer zone to move from
the entrance of the bed to the exit when the bed height is increased.
Furthermore, higher uptake of MB and phenol was observed at
higher bed height, which could be attributed to rising in the specic
surface area of FNAC, which provided more xation binding sites
for both adsorbates to adsorb. The increase in FNAC mass in a
higher bed depth also gave rise to an increase in the volume of the
MB and phenol solution treated per unit mass of FNAC at exhaustion point. Similar results were reported by other researchers
(Girish and Murty, 2015; Mohammed et al., 2016; Tan et al., 2008;
Yu et al., 2015). Table 8 shows the calculated parameters like BT,
exhaustion times and % removal of FNAC in xed-bed column at
three-bed heights.
3.13.2. Effect of the solution ows rate
The effect of ow rate on the adsorption of MB and phenol onto
FNAC was investigated by varying the ow rate at 5, 10 and 15 mL/

1256

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

Table 5
A comparison of textural and adsorption capacity of some ACs reported in literature.
ACs
Methylene blue
Coconut shell AC
NAC60
Activated carbon produced from New Zealand coal
Filtrasorb 400
Calgon (F-400) AC
Grapefruit AC (GAC)
VetP0.5
Grape industrial processing waste AC
Tomato processing solid waste AC
Activated carbon produced from Venezuelan bituminous coal
vet-H20
Commercial AC
Coffee grounds AC
Filtrasorb 400
Rattan sawdust AC
Norit
Buriti shells AC
Posidonia oceanica (L.) dead leaves AC
Picacarb
Oil palm shell AC
Cocoa shell AC
Cotton stalk
Pine Cone AC
FNAC
Phenol
Filtrasorb100 (commercial)
CS850A
PAC6 (commercial from PICA)
Rattan sawdust based activated carbon
Vet-H20
Rice husk char
VetP0.5
WTAC
CAC1 (commercial, from Norit)
CAC2 (commercial, from Norit)
Commercial activated carbon
Activated carbon-commercial grade (ACC)
Activated carbon-laboratory grade (ACL)
Tectona grandis AC
Activated coal
FNAC

SBET (m2/g)

Vt (cm3/g)

Qm (mg g1)

Reference

2825
524
857.14
1216.4
997
1198
1170
1455
1093
863.50
1185
1440
925
e
e
e
843
1483
e
596.20
85
e
939
2869

1.498
0.2855
8.211
4.695
e
0.65
0.76
2.318
1.569
4.67
0.69
0.713
0.718
e
e
e
0.490
1.022
e
0.34
0.058
e
e
1.96

916
683.6
588
476
470
456.28
423
417
400
380
375
370
367
299
294.12
276
275
270.03
246
243.90
213
193.50
60.97
968.74

(Cazetta et al., 2011)

(Gokce and Aktas, 2014)
(El Qada et al., 2008)
(El Qada et al., 2008)
(Rodrguez et al., 2009)
(Nowicki et al., 2016)
(Altenor et al., 2009)
l et al., 2015)
(Sayg
l and Gzel, 2015)
(Sayg
(El Qada et al., 2008)
(Altenor et al., 2009)
(Reffas et al., 2010)
(Reffas et al., 2010)
(Raposo et al., 2009)
(Hameed et al., 2007)
(Raposo et al., 2009)
(Pezoti et al., 2014)
(Dural et al., 2011)
(Raposo et al., 2009)
(Tan et al., 2008)
(Ahmad et al., 2012)
(Deng et al., 2009)

(Ozhan
et al., 2014)
Present study

937
1026.0
1226
e
1185
230.09
1170
1417
1350
620
e
336.6
492
585
e
2869

0.494
0.5768
0.53
e
0.69
e
0.76
1.1866
0.713
0.637
e
e
e
0.442
e
1.96

206
205.8
154
149.25
145
142.8
122
108.4
104
73
49.72
30.2187
24.6458
2.82
1.481
75.37

(Hu and Srinivasan, 1999)

(Din et al., 2009)
(Figaro et al., 2006)
(Hameed and Rahman, 2008)
(Altenor et al., 2009)
(Ahmaruzzaman and Sharma, 2005)
(Altenor et al., 2009)
(Gokce and Aktas, 2014)
(Fierro et al., 2008)
(Fierro et al., 2008)

(Ozkaya,
2006)
(Srivastava et al., 2006)
(Srivastava et al., 2006)
(Mohanty et al., 2005)
(Vazquez et al., 2007)
Present study

Table 6
A comparison of % removal of MB and phenol by adsorption and other techniques.
Adsorbates

Methods

Method description

% Removal

Reference

Methylene blue

Chemical oxidation
Decolorization
Electrochemical degradation
Electrochemical oxidation
Ozonation
Adsorption
Physico-chemical
Degradation
Degradation and mineralization
Biodegradation
Adsorption

Fenton-like reaction
Fe2.22Ti0.78O4
Pt/MnO2 electrode
e
e
FNAC
Coagulants (Al2(SO4)3, Fe2(SO4)3, FeSO4, FeCl3)
Iron phthalocyanine-graphene donor-acceptor hybrids
BiPO4 photocatalysis assisted with H2O2
Immobilized by entrapment in calcium-alginate gel beads
FNAC

98
98
90
80
95.3
99.95
94
77.1
70
>98
99.19

(Dutta et al., 2001)

(Yang et al., 2009)
(Alaoui et al., 2015)
(Asghar et al., 2015)
(Wu and Upreti, 2015)
Present study

(Ozbelge
et al., 2002)
(Wang et al., 2016)
(Liu et al., 2013)
(Gonzalez et al., 2001)
Present study

phenolic compounds
Phenol
Phenol
Phenol
Phenol

Table 7
The estimated cost of 1 kg of prepared granular activated carbon from Fox nutshell (US$/kg).
Requirements

Cost of FNAC when analytical grade chemicals used (US$/kg)

Cost of FNAC when commercial grade chemicals will use (US$/kg)

Raw materials
Zinc chloride
Power consumption
NaOH N2 gas HCl
Total

0.89
79.88
0.74
1.36
82.87

0.44 (in bulk amount)

5.95
0.74
1.18
8.31

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

1257

Fig. 16. Breakthrough curves for a) MB and b) phenol adsorption on prepared activated
carbon (FNAC) at different ow rates (initial adsorbates concentration 100 mg/L, bed
height 4 cm).

Fig. 15. Breakthrough curves for a) MB and b) phenol adsorption on prepared activated
carbon (FNAC) at different bed heights (initial adsorbates concentration 100 mg/L,
ow rate 5 mL/min).

residence time of the adsorbates solute in the column to allow for

diffusion of the solute into the pores of the adsorbent (Girish and
Murty, 2015; Mohammed et al., 2016; Tan et al., 2008).

min with a constant FNAC bed depth of 4 cm and 100 mg/L initial
concentration of both adsorbates. The effects of ow rate on the BT
curves are shown in Figs. 16(a) and (b). These BT curves show that
the column performed better at a lower ow rate, which resulted in
longer BT, exhaustion times and percent removal (Table 8). At a
lower ow rate for both MB and phenol, the BT time is longer than
that at a higher ow rate because a longer time is required to reach
its effective bed load. As the ow rate increased, the BT curve
became steeper since a shorter time was required to attain the
effective bed load and hence the effective adsorption capacity of the
FNAC column reduced. This is attributed to the insufcient

4. Conclusions
The prepared activated carbon from Fox nutshell has large BET
surface area and more pore volume. FESEM conrmed the pores are
developed on the surface of prepared activated carbon. The
maximum % removal was observed at pH 11 for MB and 7 for
phenol. The maximum removal % of MB and phenol was 99.95 and

Table 8
Column data parameters obtained at different bed heights and ow rates.
Adsorbates initial concentration (100 mg/L) Bed height (cm) Flow rate (mL/min) Breakthrough time (min) Exhaustion time (min) Bed capacity, qeq (mg/g) % Removal
MB

Phenol

4
3
2
4
4
4
3
2
4
4

5
5
5
10
15
5
5
5
10
15

430
160
30
150
25
410
220
130
80
30

2310
1520
980
1440
880
1980
1440
1060
1320
850

126.16
71.38
37.74
71.11
35.85
76.26
35.34
18.62
51.84
28.00

61.54
52.87
39.72
28.45
14.94
42.37
38.40
25.45
27.19
20.68

1258

A. Kumar, H.M. Jena / Journal of Cleaner Production 137 (2016) 1246e1259

99.19%. The experimental kinetic data was better tted by the

pseudo-second-order model (R2 1 for all MB concentrations and
0.999 for all phenol concentrations). The equilibrium adsorption
isotherms
on
the
FNAC
has
followed
the
order:
Langmuir
>
Freundlich
>
Tempkin
for
MB
and
Langmuir > Tempkin > Freundlich for phenol. The adsorption capacity of MB and phenol increased with increasing bed depth but
decreased with increasing ow rate. The highest bed capacity of
126.16 and 76.26 mg/g was obtained using 100 mg/L initial MB and
phenol concentration at 4 cm bed height, and 5 mL/min ow rate.
Fox nutshell proved to be an effective adsorbent for removing MB
and phenol from aqueous solutions.
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