Chemical Engineering Journal 168 (2011) 77–85

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Chemical Engineering Journal

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Methylene blue adsorption on activated carbon prepared from Posidonia oceanica

(L.) dead leaves: Kinetics and equilibrium studies
Mehmet Ulas Dural a , Levent Cavas a,b , Sergios K. Papageorgiou c , Fotis K. Katsaros c,∗
a
Dokuz Eylül University, Graduate School of Natural and Applied Sciences, Department of Chemistry, Tinaztepe Campus, 35160 İzmir, Turkey
b
Dokuz Eylül University, Faculty of Arts and Sciences, Department of Chemistry, Biochemistry Division, Tinaztepe Campus, 35160 İzmir, Turkey
c
NCSR Demokritos, Institute of Physical Chemistry, Terma Patriarchou Gregoriou & Neapoleos, Agia Paraskevi, 15310 Athens, Greece

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

Article history: Posidonia oceanica (L.) is an endemic species in the Mediterranean Sea, which, like terrestrial plants,
Received 13 October 2010 loses it leaves seasonally. The dead leaves are accumulated on the beaches in huge quantities as waste
Received in revised form material, causing great environmental and economical problems. The dead biomass offers an abundant,
13 December 2010
renewable and low cost precursor for the production of activated carbon (AC). In that respect ACs were
Accepted 13 December 2010
prepared by chemical activation of P. oceanica (L.) dead leaves. The preparation process consisted of
zinc chloride impregnation at ratios up to 45%, followed by carbonization in nitrogen atmosphere at
Keywords:
temperatures up to 873 K. The prepared P. oceanica (L.) activated carbons (POAC) were studied by SEM and
Activated carbon
Posidonia oceanica (L.)
Nitrogen porosimetry and the pore structural characteristics were determined. Concerning the POAC45
Chemical activation sample, a specific surface area of 1483 m2 /g and a total pore volume of about 1 cm3 /g were achieved,
Methylene blue adsorption while both microporosity and mesoporosity were obtained. The adsorption potential of POAC for the
Kinetics removal of methylene blue (MB) from aqueous solutions was also investigated under varying conditions
of initial concentration, carbon dosage, pH, temperature and the optimum experimental conditions were
determined. The samples revealed relatively fast kinetics reaching equilibrium in around 60 min, which
follow the second order rate equation, while adsorption was unaffected by the pH of the solution. The
Langmuir model provided the best fit to the experimental data and sorption capacity increased with
increasing temperature. The results showed that proposed precursor lead to AC with increased sorption
capacity for MB reaching a value of 285.7 mg/g at 318 K. In conclusion, P. oceanica (L.) dead leaves can be
used as a raw material for preparation of high quality activated carbon.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction A major drawback in the use of ACs, in commercial scale, is the

In the last few decades, adsorption has been proved to be a
well-established and cheap pollutant removal process among other
purification techniques. From the multitude of available adsorbents
activated carbons (ACs) are one of the most popular for both liquid
and gas purification [1] due to their unique properties, including
porous structure, high specific surface areas and large sorption
capacities. The textural and surface properties of ACs are influenced
by both the precursor material and the method used for their prepa-
ration [2–4]. On the other hand their adsorption capacity is strongly
dependent on its specific surface area, pore size distribution and
existing surface functional groups, with the latter influencing their
behaviour during interaction with polar, non-polar, anionic and
cationic adsorbates [5].
∗ Corresponding author. Tel.: +30 2106503671; fax: +30 2106511766.
E-mail address: fkats@chem.demokritos.gr (F.K. Katsaros).
cost of their production. In the last years, research has been focus-
ing on the utilisation of new precursors, cheap and abundant with
great valorisation potential, such as agricultural residues and waste
biomass [6,7]. A variety of starting materials have been already used
for the preparation of AC, such as sunflower oil cake, bean pods, cot-
ton stalks, nut-shells, bituminous coal, coffee ground, fir sawdust
etc. [8–18].
A very promising candidate that can be used as precursor, for
the large-scale production of AC, is the sea plant P. oceanica (L.).
The total primary production of P. oceanica in the Mediterranean
basin alone has been estimated in the range of 5 × 106 –5 × 107 ton
per year [19]. The plant loses its leaves, especially in autumn
forming wedge structures along sandy coasts. The accumulated
dead biomass causes both aesthetic and economic problems
especially during the summer tourist season and is usually col-
lected and burned. There are several studies in the literature,
reporting the applicability of P. oceanica (L.) raw biomass in numer-
ous adsorption processes, such as the removal of textile dyes
[20], methylene blue [21], methyl violet [22], anionic and non

1385-8947/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2010.12.038
78 M.U. Dural et al. / Chemical Engineering Journal 168 (2011) 77–85
Table 1
Textural characteristics of the produced activated carbons derived by Posidonia oceanica (L.) dead leaves.
Sample (%) Yield (%) BET surface area (m2 /g)
0 36 38.9
15 48 858.7
30 44 1273.9
45 40 1483.3
ionic surfactants [23], phenol [24] and metal complexed dyes
[25].
In a recent study, P. oceanica (L.) fiber balls [26] have been used
for the preparation of raw char and physically activated carbons.
The resulting material exhibited a maximum specific surface area
of 615 m2 /g. However as physical adsorption on activated carbon is
directly related to its surface area, in order to produce a high added
value product for sorption applications, higher surface area mate-
rials should be achieved. An alternative activation route that could
give improved pore structure with tunable structural characteris-
tics [27] involves the impregnation of the precursor by a chemical
agent, usually H2 SO4 , H3 PO4 , ZnCl2 , or alkali metal hydroxides and
then the heat-treatment at moderate temperatures (673–873 K)
in a one-step process [28]. From the available activating agents,
Zinc chloride is preferably used for the activation of lignocellulosic
materials [29,30] as it causes the decomposition of the cellulosic
structure.
Such a chemical activation promotes cross-linking reactions,
leading to the formation of a rigid structure, which reduce the
volatile loss upon heat treatment. The subsequent pyrolysis step
causes partial gasification of the amorphous material and results in
the formation of the final carbon structure [31]. During this step,
aromatisation of the carbon skeleton and creation of the pore struc-
ture are also observed [32].
Chemical activation is a lower temperature process, resulting
in lower energy cost and shorter time than those used in physical
activation with a higher carbon yield [33,34].
In the present study, a different route for the preparation of acti-
vated carbon from P. oceanica (L.) dead leaves was followed based
on chemical activation with zinc chloride. The resulting materials
exhibited high surface areas and increased pore volumes. The influ-
ence of ZnCl2 impregnation ratio on the structural properties was
investigated. Furthermore, the sorption properties of the prepared
ACs were evaluated for the removal of methylene blue (MB) from
aqueous solutions under varying conditions of initial concentration,
carbon dosage, pH and temperature.
2. Material and methods
2.1. Preparation of activated carbons
P. oceanica (L.) dead leaves were collected from the coast of
Urla/IZMIR in February 2010, put into plastic bags and immediately
transported to the laboratory. The dead leaves were washed with
tap water to remove salt, impurities and epiphytes, subsequently
was washed with distilled water, dried at 343 ± 2 K for 16 h and
ground by means of a crusher machine. The resulting ground P.
oceanica (L.) biomass (GPO) with a mean particle size of 500 ␮m
was activated with different concentration of ZnCl2 .
20 g of GPO was added into 200 ml of ZnCl2 solution of desired
concentration (0, 15, 30, 45%, w/v) and stirred for 2 h. Higher per-
centages of ZnCl2 during activation resulted in the formation of
tar. Therefore although ZnCl2 ratios up to 55% were used, 45% was
found to be the highest activation concentration ratio that would
lead to a desired product. The excess of ZnCl2 solution was then
decanted and the zinc treated GPO (ZTGPO) was subsequently dried
Pore volume (cc/g) NLDFT MB adsorption capacity at 298 K (mg/g)
Vmicro Vmeso Vtotal
0.011 0.025 0.041 6.72
0.322 0.063 0.415 99.8
0.479 0.197 0.723 178.6
0.494 0.456 1.022 217.4
in a stove for 24 h at 343 ± 2 K. ZTGPO was then placed in porcelain
capsule and kept in a muffle furnace. The temperature was raised
by 20 ◦ C/min from room temperature to 873 K where it was kept for
2 h. The experiments were carried out under nitrogen atmosphere
at a flow rate of 10 ml/min. The resultant chemically activated car-
bon (POAC) was washed with 0.5N HCl solution at 368 K for 30 min
to remove excess ZnCl2 and subsequently washed with warm water
at 333 K until the effluent contained no zinc ions. The resulting
material was dried in an air oven at 343 K for 16 h.
2.2. Preparation of methylene blue solution
The methylene blue (MB) (C16 H18 ClN3 S, MW 319.87 g/mol) was
supplied by Fluka (97% purity). Double distilled water was used
for the preparation of all the solutions and regents (pH: 6.5). A
1000 mg/L stock solution was prepared and 250, 500, 750 mg/L
solutions were prepared with the necessary dilution from stock
solution. The concentrations of the MB solutions were obtained
from standard calibration curve.
2.3. Characterization of activated carbon
The surface characteristics of P. oceanica (L.) activated carbon
(POAC) samples were examined by scanning electron microscopy
(SEM). A Jeol JSM 7401F Field Emission Scanning Electron Micro-
scope equipped with Gentle Beam mode was used to characterize
the morphology of the activated carbon. The specific surface area
and pore structure parameters of POAC were determined from
the adsorption–desorption isotherm of nitrogen at 77 K using an
automated volumetric system (AUTOSORB-1-Krypton version –
Quantachrome Instruments). Prior to their measurement, the sam-
ples were outgassed at 473 K for 48 h.
2.4. Adsorption kinetics – isotherms
Sorption kinetics experiments were carried out at 298 K using
three different initial methylene blue concentrations, namely 250,
500, and 750 mg/L. All the kinetics measurements were performed
at pH 6.5 (The pH of deionised water), with a maximum contact time
of 360 min. The samples were removed at preset time intervals and
centrifuged at 5000 rpm for 4 min.
For the evaluation of POAC as an adsorbent for MB removal from
aqueous solutions, batch experiments were carried out in polyethy-
lene vessels. The adsorption capacity of activated carbon treated
with 45% ZnCl2 (POAC45) was found to be the highest (Table 1),
so only POAC45 sorption results are presented. Specifically, 0.05 g
of POAC45 were added into 10 ml of the desired MB solutions. The
mixtures were agitated at 130 rpm in a mechanical shaker (GFL
1092) for 6 h. Dye concentration in the supernatant was determined
by means of a Shimadzu UV–vis 1601 spectrophotometer. All the
measurements were made at 665 nm, a wavelength correspond-
ing to the maximum absorbance. The isotherm experiments were
performed at three different temperatures (298, 308 and 318 K).
The solid to liquid ratio was found to be optimum between 5 and
10 g/L (data not presented), therefore in all experiments 10 g/L was
selected because it provided a greater concentration difference
 M.U. Dural et al. / Chemical Engineering Journal 168 (2011) 77–85
Fig. 1. Scanning electron micrographs of POACs obtained under different preparation conditions: (a) 0% activation, (b) 15% activation, (c) 30% activation, (d) 45% activation.
between the initial and final solution thus decreasing the relative
errors.
The amount of dye adsorbed onto POAC45 was calculated by
using the following equation:
C0 − Cf
q= V (1)
M analysis of the activated carbon
where q represents the adsorbed dye amount (mg/g), C0 the initial
dye concentration (mg/L), Cf the final dye concentration (mg/L), V
the volume of dye solution (L) and M the mass of adsorbent (g). All
experiments were performed in triplicates.
3. Results and discussion
3.1. Characterization of activated carbon
3.1.1. SEM analysis of the activated carbon
Scanning electron microscopy (SEM) was used in order to
obtain information about the surface morphology of the POAC.
Fig. 1(a–d) shows the SEM photographs of the POAC with differ-
ent impregnation ratios. The untreated sample (0%) has a relatively
smooth surface without large defects. On the other hand the chem-
ically activated carbons (15%, 30%, 45%) exhibit larger cavities and
rougher surfaces compared to the initial sample. These surface
characteristics are more pronounced as the impregnation ratio
increases. Thus, while the 15% sample has some large cavities in the
range of 10–20 nm, the 45% sample shows additional small pores
and extremely rough surface. The large pores created by the chem-
ical treatment promote the activation in the internal surface of the
carbon particles. Therefore, ZnCl2 was proved to be an effective
activating agent for the production of high-surface area activated
carbon.
White spots observed in the samples, may be due to the presence
of salt residues at 0%-AC. As this POAC was not treated with ZnCl2 it
79
can be concluded that traces of salts are still present in the precursor
indicating that after collection, P. oceanica (L.) biomass should be
washed more thoroughly.
3.1.2. Specific surface area and pore structural characterization
The N2 adsorption isotherms at 77 K of both untreated sam-
ple and chemically activated carbons are shown in Fig. 2a. The
adsorption isotherms of the activated carbons are type I isotherms,
indicating the presence of large fractions of micropores and in some
cases mesopores, while the untreated sample can be considered as
non-porous. Isotherm data were analyzed for BET area, total pore
volume, micropore volume and average pore width. Specific sur-
face areas were calculated according to the BET method. Total pore
volumes were directly derived from the adsorbed quantity at high
relative pressures (p/p0 ∼ 0.95, while p0 is the saturation pressure of
Nitrogen at 77.36 K and equals to 101.38 KPa). The results obtained
from nitrogen isotherms are presented in Table 1. Adsorption data
were analyzed by NLDFT equilibrium model for slit pores and the
pore size distributions (PSD) were calculated [35]. The pore size
distribution (PSD), i.e. the distribution of pore volume with respect
to pore size, is represented by the derivative of dV/dr as a func-
tion of r, where V is the pore volume and r the pore radius. In the
case of carbons, in which the pores are considered to be mostly slit
shaped, pore width (w), can replace pore radius (r), and the PSD can
be presented similarly by the derivative of dV/dw as a function of
w (Fig. 2b).
The activation of P. oceanica (L.) dead leaves without ZnCl2
impregnation resulted in a non-porous sample with relatively low
carbon yield. The carbon produced from the untreated sample has
very low surface area and pore volume: 38.9 m2 /g and 0.041 cm3 /g
respectively. On the contrary, the impregnation process leads to
samples with increased surface area from 858.7 m2 /g (15%) and
80 M.U. Dural et al. / Chemical Engineering Journal 168 (2011) 77–85

a 800 160
0% Ads 0% Des
700 15% Ads 15% des 140
30% Ads 30% Des
600 120
45% Ads 45% Des
/g

500
STP

100
VAds cc

q (mg/g)
400
80
300
60
200
40
100
750 mg/L
0 20 500 mg/L
0.0 0.2 0.4 0.6 0.8 1.0 250 mg/L
0
p/p0 0 50 100 150 200 250 300 350 400
Time (min)
b 0.60
Fig. 3. The adsorption of MB onto POAC45 (temperature = 298 K, pH 6.5, agitation
0.50 rate = 130 rpm) (Lines represent the non linear fit of pseudo second order kinetic
model).

0% Act
dV/dw (cc/g/nm)

0.40
15% Act
30% Act
0.30
45% Act
0.20
0.10
0.00
0 2 4 6
w (nm)
Fig. 2. (a) Nitrogen adsorption isotherms at 77 K on POACs. (b) Pore size distribution
(NLDFT) of activated carbons derived by Posidonia oceanica (L.) dead leaves.
1273.9 m2 /g (30%) up to 1483.3 m2 /g for the sample with 45%
impregnation ratio.
In all samples there is no evidence of ultra micropores, the
average micropore size was in the 0.7–1.5 nm range. Concern-
ing the pore volume of the carbon samples, activation up to 15%
leads mainly to the formation of micropores (increase from 0.001
to 0.322 cm3 /g), while the mesoporosity remains unaffected. This
implies that the treatment initially creates new pores rather than
increasing the size of the already existing ones. This may be
attributed to the removal of amorphous material, which increases
the micropore volume, without significantly altering the pore sizes.
Higher degree of activation (up to 30%) increases both the micro-
pore and the mesopore volume. This fact indicates that additional
treatment after the development of new micropores, affects also
the pre-existing porosity by increasing its pore size. Thus, there is
a shift in the PSD of 30%AC to higher micropore sizes (the average
is increased from 0.75 to 1.0 nm). In addition the PSD is broader
and a shoulder appears at about 1.5 nm. Finally treatment up to
45% leads only to the formation of mesopores of about 3–4 nm. In
this case, the PSD shows a significant increase in mesopore volume,
while the microporosity region remains almost identical. Interest-
ingly these results indicate that the resulting AC pore size can be
tuned (micropores and mesopores) by using different impregnation
ratios.
Concerning the mechanism of the preparation process, the ini-
tial step involves the mixing and chemical attack of the biomass
by the activating agent. During the subsequent step of thermal
treatment, dehydration and cross-linking reactions are taking place
leading to the formation of aromatic rings in the char product. The
volatile organic material is also removed in this step [36]. The heat-
ing rate, the residence time and the final temperature are the crucial
parameters that determine the structural properties of the result-
ing activated carbon. Furthermore the final washing process (with
hot acid water and water) has a great influence on the final porous
structure of the carbon [37].
In general P. oceanica (L.) dead leave biomass can effectively be
used as a precursor for the chemical preparation of high quality
activated carbon. The obtained results reveal that the produced
8 10
ACs have better properties in terms of surface area, pore volume
and average pore size than the corresponding samples prepared by
physical activation [26]. In addition, by applying different impreg-
nation ratios, one can tune the pore size of the final carbon product
(micropores and mesopores). Materials produced in this study have
also superior structural characteristics compared to the properties
of activated carbons derived by other low cost materials. Table 2
summarises the structural properties of the carbon produced by P.
oceanica (L.) and offers a comparison with other activated carbons
reported in the literature.
3.2. Adsorption kinetics
3.2.1. Pseudo-first and pseudo-second order kinetics models
Adsorption kinetics is one of the most important parameters
for the evaluation of adsorption efficiency. Two main kinetic mod-
els namely the pseudo-first order [38] and pseudo-second order
[39] were used in this study to characterize adsorption kinetics.
Non-linear fitting methods were applied using the Origin 7.0©
software. In the kinetics experiments the adsorption reached equi-
librium after 60 min as no significant increase in MB adsorption was
observed after that time (Fig. 3).
The pseudo-first order kinetics is given by the equation:
q = qe (1 − e−k1 t ) (2)
where qe represents the amount of dye adsorbed at equilibrium
(mg/g), q is the amount of dye adsorbed (mg/g) at a certain time, t
is time (min) and k1 is the pseudo first order rate constant (1/min).
The pseudo-second order kinetics is given by the equation
k2 q2e t
q (3)
1 + k2 qe t
where qe represents the amount of dye adsorbed at equilibrium
(mg/g), q is the amount of dye adsorbed (mg/g) at a certain time,
 M.U. Dural et al. / Chemical Engineering Journal 168 (2011) 77–85 81

Table 2
Comparison of textural characteristics of some activated carbons.

Activated carbon type SBET (m2 g−1 ) Vmicro (cm3 g−1 ) Vmeso (cm3 g−1 ) Vtotal (cm3 g−1 ) Reference

Sunflower oil cake 240 0.111 0.005 0.116 Karagöz et al. [8]
Bean pods 258 0.080 0.013 0.206 Budinova et al. [9]
Cotton stalk 594 0.280 0.030 0.381 Girgis et al. [10]
Cotton stalk 794 0.083 N/A 0.630 Deng et al. [11]
Macadamia nut-shell 844 0.391 0.094 0.485 Aworn et al. [12]
Bituminous coal 857 0.390 N/A 0.450 El Qada et al. 2006 [13]
Commercial AC 924 0.426 0.041 0.466 Aworn et al. [12]
Coffee ground 925 0.046 0.666 0.718 Reffas et al. [14]
Coal 970 0.481 0.180 N/A Gong et al. [15]
Coffee ground 1021 0.350 0.950 1.300 Rufford et al. [16]
Chinese firsawdust 1079 0.502 0.050 0.558 Juan and Ke-Qiang [17]
Commercial AC 1118 0.415 0.203 0.618 Wang et al. [18]
Posidonia oceanica (L.)
Physical activation 615 0.021 0.118 0.160 Ncibi et al. [26]
Posidonia oceanica (L.) 1483 0.494 0.456 1.022 This study

t is time (min) and k2 is the pseudo-second order rate constant rate-limiting step [47]. The values of kID1 and kID2 indicate that
(g/mg min). the intraparticle diffusional resistance in micro and mesopores is
The derived kinetic models parameters for MB adsorption onto higher than that in the larger pores. Moreover, sorption is concen-
POAC45 are shown in Table 3. As can be seen by the values for tration dependent as increase in sorbate concentration increases
R2 , the pseudo-second order kinetic model fits the experimental the rates of pore diffusion up to one order of magnitude (Table 4).
results more accurately than the pseudo-first order kinetic model
(Table 3). Thus, it can be concluded that MB adsorption on 45%AC 3.2.3. Boyd plot
follows the pseudo-second order rate equation. This fact suggests In order to investigate the contribution of film resistance to
that the rate of sorption for POAC45 is dependent on the availability the kinetics of MB sorption, the Boyd film-diffusion model was
of the sorption sites rather than the concentration of the sorbate in employed. The model assumes that the main resistance to diffu-
the bulk solution [40,41]. sion is in the boundary layer surrounding the adsorbent particle is
expressed by the equation [48]:
3.2.2. Intraparticle diffusion model  6 
∞ 
1
  
The adsorption mechanism may proceed in several steps the F(t) = 1 − exp −n2 Bt (5)
slowest of which will be the rate determining step. In general, pore 2 n2
n=1
and intraparticle diffusion are often rate limiting in a batch reac-
tor system. However, the pseudo first and pseudo second order where F(t) is the fractional attainment of equilibrium, at different
models cannot give information or evaluate the contribution of times, t, and Bt is a function of F(t):
intraparticle diffusion to the sorption mechanism. For this reason q
an intraparticle diffusion model has been introduced by Weber and F(t) = (6)
qe
Morris [42] and is given by the equation:
√ where q and qe are the dye uptake (mg/g) at time t and at equilib-
qt = kID t (4) rium, respectively.
By applying the Fourier transform and then integration,
where kID represents the rate constant (mg g−1 min−1/2 ). According Reichenberg [49] managed to obtain the following approxima-
to the above mentioned model, the plot of qt , against t1/2 should give tions:for F(t) > 0.85,
a straight line when diffusion plays a role in the sorption rate and
should cross the origin if intraparticle diffusion is the rate deter- Bt = 0.4977 − ln (1 − F(t)) (7)
mining step [43,44]. Multi-linearity can be observed when different
while for F(t) < 0.85,
mechanisms with different rate constants are involved in sorption
and in that case multiple linear regressions must be applied one for  
2
each linear region [45]. √ 2 F(t)
Bt = − − (8)
In this work, the plots obtained (Fig. 4) are comprised of three 3
linear regions. The first part of the curve (0–5 min) can be attributed
to mass transfer effects taking place with boundary layer diffusion, Eqs. (5)–(8) can be used in predicting the mechanistic steps
while the final linear parts indicate intraparticle diffusion (slope involved in the adsorption process, i.e. whether the rate of removal
kID1 and kID2 ) [46]. kID1 relates to the diffusion through the larger of the dye is controlled by particle diffusion or film-diffusion mech-
pores while kID2 represents the micro and mesopore diffusion. The anism. A linear plot of Bt against time, passing through the origin
intercept however, did not cross the origin in any of the test condi- implies that pore-diffusion controls the rate of mass transfer. How-
tions, thereby suggesting that intraparticle diffusion was not the ever, if the plot is nonlinear or linear but does not pass through

Table 3
Pseudo-first and -second order adsorption kinetic parameters at different initial dye concentrations for the adsorption of MB onto POAC45 at 298 K.

Dye concentration (mg/L) Temperature (K) qe(exp) (mg/g) Pseudo-first order Pseudo-second order
2
qe (cal) (mg/g) k1 (1/min) R qe(cal) (mg/g) k2 (g/mg min) R2

250 298 49.98 49.74 0.5909 0.737 50.09 0.0656 0.975

500 298 99.94 98.79 0.2715 0.899 101.40 0.0062 0.981
750 298 149.85 146.44 0.1389 0.842 153.55 0.0016 0.954
82 M.U. Dural et al. / Chemical Engineering Journal 168 (2011) 77–85

9
250 mg/L
8
500 mg/L
250 mg/L 500 mg/L 750 mg/L
160 7 750 mg/L
140 6
120 5
q (mg/g)

100

Bt
4
80
3
60
2
40
1
20
0
0
0 10 20 30 40 50 60 70
0 2 4 6 8 -1
1/2 t(min)

Fig. 4. Intraparticle diffusion and Boyd plot at different initial concentrations onto POAC45 (temperature = 298 K, pH 6.5, agitation rate = 130 rpm).

Table 4
Intra-particle diffusion and Boyd plot parameters at different initial MB concentrations (POAC45).

Cinitial (mg/L) Intraparticle diffusion model Boyd plot

kID1 (mg/g min0.5 ) (0–30 min) R2 kID2 (mg/g min0.5 ) (30–60 min) R2 Intercept R2

250 0.9980 0.997 0.0871 0.9198 3.39 0.953

500 8.2948 0.976 0.9506 0.9804 1.18 0.960
750 14.717 0.972 5.5718 0.9347 -0.26 0.985

the origin film-diffusion or chemical reaction dominate the adsorp-

tion rate [48,49]. The latter seems to be the case in MB adsorption 250
on POAC45 (Fig. 4). However it seems that pore diffusion becomes
more important at higher MB solution concentrations, as the inter-
200
cept approaches 0 with increasing initial concentration (Table 4).
q (mg/g)

3.3. Adsorption isotherms 150

In order to obtain information about the properties and mech-

100
anism of the sorption process, the experimental results of MB
adsorption on 45%AC were represented by adsorption isotherms
and fitted with three model equations (Langmuir, Freundlich and 50
Dubinin-Raduschkevic). Langmuir fit
Freundlich fit
The Langmuir isotherm model [50] is based on the assumption
0
that the adsorption process takes place on a homogeneous sur-
0 1 2 3 4 5 6 7 8 9 10 11
face, assuming monolayer adsorption onto a surface with a finite
Ce(mg/L)
number of identical sites, so a monolayer of adsorbate is formed at
saturation on the adsorbent surface. Fig. 5. MB adsorption isotherm onto POAC45 and fitting of the Langmuir and Fre-
The Langmuir isotherm model is given by the expression: undlich model equations (temperature = 298 K, pH 6.5).

qm bCe
q=
1 + bCe
where qm is the maximum adsorption capacity (mg/g), Ce is the
equilibrium concentration of dye at the equilibrium time (mg/L)
and b the Langmuir constant (L/mg).
On the other hand, Freundlich [51] presented a fairly satisfactory
empirical model to describe non-ideal adsorption on heteroge-
neous surfaces as well as multiplayer adsorption expressed by the
(9)
layer adsorption. As for the Freundlich equation the poor fit to the
experimental data as well as its empirical nature does not allow for
reliable assumptions.
The Dubinin–Radushkevich equation [52,53] was used in
order to gain insight on whether MB sorption on the activated
carbon is due to physical or chemical interactions. The Dubinin-
Raduchkevich isotherm is expressed by the equation;
equation:  1

2
1/n ln qe = ln qm − B RT ln(1 + ) (11)
q = Kf Ce (10) Ce
where Ce , represents the equilibrium concentration of dye at the where qm represents the maximum amount of dye sorbed onto ACs
equilibrium time (mg/L), n, the Freundlich constant related to (mg/g), B is a constant related to the sorption energy (mol2 /J2 ), Ce is
adsorption intensity (dimensionless), Kf , the Freundlich constant the equilibrium concentration of the sorbate (mg/L), R is the ideal
represents the relative adsorption capacity (mg/g). gas constant (8.314 J/mol K), T is the temperature (Kelvin) and ( is
In this work, the Langmuir model provided the best fit for the the Polanyi potential given by the equation:
experimental results (Fig. 5). The calculated Langmuir isotherm
parameters were given in Table 5. Maximum adsorption capacity of 1
ε = RT ln(1 + ) (12)
POAC45 was found 285.7 mg/g at 318 K indicating physical mono- Ce
 M.U. Dural et al. / Chemical Engineering Journal 168 (2011) 77–85 83

Table 5
Langmuir, Freundlich and Dubinin–Radushkevich isotherm constants for the adsorption of methylene blue by POAC45 (solution pH 6.5).

Langmuir constants Freundlich constants Dubinin–Radushkevich constants

2 2
Temperature (K) qm (mg/g) b (L/mg) R Kf (mg/g) n R R2 B (mol2 /J2 ) E (kJ/mol) R2

298 217.39 1.70 0.990 112.12 2.74 0.918 177.76 6 × 10−8 2.89 0.975
308 270.27 1.68 1.000 164.21 1.82 0.974 193.97 5 × 10−8 3.16 0.977
318 285.71 3.18 0.996 225.63 1.99 0.934 217.39 3 × 10−8 4.08 1.000

110 maximum MB adsorption capacity of activated carbons prepared

from numerous low cost precursors as reported in the literature,
commercial activated carbon and POAC45 reported in this work
[10,15,43,59–64]. The high MB adsorption capacity of the POAC45,
that was produced and studied in this work shows that P. oceanica
(L.) dead leaves can be used as a precursor for the preparation of
high quality activated carbon. Specifically, chemical activation with
q (mg/g)

100 45% impregnation ratio can produce a material with very high MB
removal efficiency, over a wide range of pH.

3.4. Thermodynamic parameters

The thermodynamic parameters such as change in standard free

90
2 4 6 8 10
pH
Fig. 6. Effect of pH on MB adsorption onto POAC45 (initial dye concentra-
tion = 500 mg/L, temperature = 298 K, agitation rate = 130 rpm).
The calculated parameters are shown in Table 5. Energy related
to adsorption can be found from the equation [54]:
B−1/2
E= √
2
Energy values ranging between 1 and 8 kJ/mol indicate that the
sorption is due to physical interactions between adsorbent and
adsorbate [55,56]. The values obtained for MB adsorption onto
POAC45 were found to be 2.89, 3.16 and 4.08 kJ/mol at 298, 308, and
318 K, respectively. It can be concluded that weak physical inter-
actions are the driving force of MB adsorption onto POAC45, an
assumption supported as well by the lack of dependence of sorption
to the solution pH (Fig. 6).
The removal of MB, as a pollutant, from waste waters of tex-
tile, paper, printing and other industries has been addressed by
the researchers. Recently, Gupta et al. [57] and Rafatullaha et al.
[58] have reviewed the use of low-cost adsorbents derived from
agricultural wastes, industrial solid wastes, biomass, clays minerals
and zeolites for the removal of dyes from solution. Table 6 lists the
energy (G◦ ), enthalpy (H◦ ), and entropy (S◦ ) were determined
using the following equations:
12
−H 1 S
ln Kd = + (van’t Hoff equation) (14)
R T R
q
Kd = x (15)
Ce
G = H − TS (16)
In Eq. (15) the density of the solution ( = 1000 g/L) was used
to render Kd dimensionless in order for its logarithmic value to be
used for the correct calculation of the thermodynamic parameters
(13) [65]. As seen in Table 7, positive values of H for all dye concen-
trations and negative G values for all temperatures indicate that
MB adsorption on POAC45 is endothermic and spontaneous.
The endothermic nature of the adsorption is somehow con-
tradictory to physical adsorption. Generally speaking, it would
be expected that the physical adsorption processes (either from
gas or liquid phase) would be exothermic, thus adsorption quan-
tity should decrease with increasing temperature [66,67]. Barton
[68] measuring the enthalpy of adsorption of methylene blue from
aqueous solutions onto activated carbon by means of immersion
calorimetry found that the actual dye adsorption phenomenon
was exothermic. The process however involves the wetting of
the sorbent, the endothermic dissociation of the methylene blue
dimer, and exothermic exchange reaction between the dye and
the adsorbed solvent molecules. Thus the endothermicity of the
adsorption process is explained by the necessity of an endother-

Table 6
Methylene blue adsorption capacity of various ACs.

Activated carbon type qm (mg/g) T (K) pH References

Hazelnut shell-based 8.8 – – Aygun et al. [60]

Oil palm wood-based 90.9 303 – Ahmad et al. [61]
Bamboo dust-based 143.2 303 7.2 Kannan and Sundaram [43]
Ground shell-based 164.9 303 7.2 Kannan and Sundaram [43]
Cotton stalk-based 180.0 – – Girgis et al. [10]
Jute fiber-based 225.6 301 4.0 Senthilkumaar [62]
Oil palm fiber-based 277.78 303 6.5 Tan et al. [63]
Coal-based 234.0 – – Gong et al. [15]
Coal-based (KOH washed) 252–271 – – Gong et al. [15]
Oil palm shell-based 243.9 303 6.5 Tan et al. [59]
HCl-treated oil palm shell-based 303.03 303 6.5 Tan et al. [59]
Olive seeds carbon 190–263 – – Stavropoulos et al. [64]
FiltrasorbF300 240.0 – – Stavropoulos et al. [64]
Posidonia oceanica (L.) dead leaves 270.3 308 3–10 Present study
84 M.U. Dural et al. / Chemical Engineering Journal 168 (2011) 77–85
Table 7
Thermodynamic parameters of MB adsorption onto POAC45 (T = 298, 308, 318 K).
Dye concentration (mg/L) H (kJ/mol)
250 38.96
500 40.04
750 65.32
14
13.5
13
lnKd
12.5
250 mg/L
12
500 mg/L
750 mg/L
11.5
11
0.0031 0.00315 0.0032 0.00325 0.0033 0.00335
1/T
Fig. 7. Plots of ln Kd versus 1/T for the adsorption of methylene blue by POAC45 at
different dye concentrations (solution pH 6.5).
mic dissociation of dye dimers, micelles or aggregates prior to the
exothermic adsorption of the dye monomer [68,69]. The involve-
ment of a process such as the dissociation of the MB dimmer, may
explain as well the Boyd plot findings, suggesting that the dominat-
ing adsorption rate of MB onto POAC45 is affected by both chemical
reaction and film resistance.
In agreement with the results presented in this work MB adsorp-
tion has been reported to be endothermic in the literature [70,71].
However as discussed, the values for H calculated in this and sim-
ilar studies using the van’t Hoff equation do not represent the actual
enthalpy of adsorption of the dye onto activated carbon but rather
the sum of enthalpies of the different phenomena involved in the
process (Fig. 7).
4. Conclusion
In this study, P. oceanica (L.) dead leave biomass was used as pre-
cursor material for the preparation of activated carbon by chemical
activation with zinc chloride. The yield as well as the produced car-
bons structural properties are influenced by ZnCl2 impregnation
ratio with best yield of produced activated carbon observed in 15%
ZnCl2 . However impregnation ratio of 45% ZnCl2 was found to be the
optimum treatment for the preparation of activated carbons from P.
oceanica (L.) dead leaves. POAC45 had better structural properties
and higher specific surface area reaching a value of 1483.3 m2 /g,
combining both microporous and mesoporous structure.
The adsorption potential of produced AC for the removal of
methylene blue (MB) from aqueous solutions was also investi-
gated under varying conditions of initial concentration, carbon
dosage, pH, temperature and the optimum experimental conditions
were determined. The POAC45 sample exhibits increased methy-
lene blue adsorption capacity that reached 285.7 mg/g at 318 K,
higher than other low cost adsorbents and commercial activated
carbons, while the pH of the MB solutions did not affect the adsorp-
tion capacity. The MB adsorption onto POAC45 reaches equilibrium
in a little over than 60 min follows the pseudo-second order kinet-
ics. It is influenced by both intraparticle diffusion with different
S (kJ/mol) G (kJ/mol)
298 K 308 K 318 K
0.234 −30.90 −30.37 −28.14
0.236 −33.24 −32.74 −31.28
0.313 −35.59 −35.10 −34.41
rates for different pore sizes and film transfer resistance, especially
in higher initial concentrations.
The Langmuir isotherm equation fits better the experimental
results, indicating monolayer adsorption. In addition, the adsorp-
tion energy, calculated by the Dubinin-Raduchkevich equation,
reaches a value of 4.08 kJ/mol, implying that the adsorption is
dominated by the physical interactions between MB and POAC45.
However the adsorption increases with increasing temperature.
This can be explained by the endothermic nature of the MB dimer
dissociation necessary in order to overcome steric hinderances dur-
ing sorption in small pores. Overall P. oceanica (L.) dead leaves can
be effectively used as a precursor for the preparation of high sorp-
0.0034
tion efficiency activated carbon by chemical activation with zinc
chloride.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.cej.2010.12.038.
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