International Biodeterioration & Biodegradation 102 (2015) 245e255

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International Biodeterioration & Biodegradation

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

Adsorption of benzene and toluene onto KOH activated coconut shell

based carbon treated with NH3
Jibril Mohammed a, b, c, Noor Shawal Nasri a, *, Muhammad Abbas Ahmad Zaini b, e,
Usman Dadum Hamza a, b, c, Farid Nasir Ani d
a

UTM-MPRC Institute for Oil and Gas, Energy Research Alliance, Research University, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru,
Johor, Malaysia
Chemical Engineering Department, Faculty of Chemical Engineering, Research University, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru,
Johor, Malaysia
c
Chemical Engineering Department, Abubakar Tafawa Balewa University, P.M.B 0248 Bauchi, Nigeria
d
Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia
e
Centre of Lipids Engineering & Applied Research (CLEAR), Ibnu Sina ISIR, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 10 December 2014
Received in revised form
11 February 2015
Accepted 11 February 2015
Available online 25 March 2015

Volatile organic compounds (VOCs) have been reported to be responsible for many acute and chronic
health effects and environmental degradations. In this study, coconut shell based porous carbon was
produced through chemical activation with potassium hydroxide (PHAC) and chemically treated with
ammonia (PHAC-AM) to improve the adsorption of benzene and toluene. The porous carbons were
characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM)
and nitrogen adsorption tests. Removal efciencies and adsorption capacities of the activated carbon
samples for benzene and toluene were carried out through batch studies. Langmuir, Freundlich and
Temkin adsorption isotherms were tested for the adsorption process and the experimental data were
best tted by Langmuir model. Pseudo-second-order kinetic model best described the adsorption kinetics for the two VOCs on PHAC and PHAC-AM. The removal of benzene and toluene by PHAC are; 82.5
and 85.6%, while that of PHAC-AM are; 91 and 92.3% respectively with approximately 10% increase in the
uptake after the ammonia treatment. After ve cycles of adsorbents regeneration test, approximately 50%
of benzene and toluene was still able to be removed. The results of this study revealed that ammonia
treated activate carbon (PHAC-AM) is a sustainable adsorbent for treatment of VOCs in polluted waters.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Adsorption
Volatile organic compounds
Ammonia treatment
Characterization
Sustainable porous carbons
Environmental degradation

Introduction
The toxicity of volatile organic compounds (VOCs) such as
benzene and toluene even at very low concentrations makes their
removal from wastewater or contaminated ground water an
important issue in the industries (Abdullahi and Chian, 2011; Li
et al., 2011). Large amounts of volatile organic compounds (VOCs)
are discharged into the atmosphere and aqueous environment by
process industries such as pharmaceutical, renery and paint
through gaseous efuents and produced waste water, some other

* Corresponding author. Sustainability Waste-to-Wealth Unit, UTM-MPRC Oil and

Gas Institute, Energy Research Alliance, Universiti Teknologi Malaysia, 81310 UTM
Johor Bahru, Johor, Malaysia. Tel.: 60 137728200; fax: 60 75545667.
E-mail address: noorshaw@petroleum.utm.my (N.S. Nasri).
http://dx.doi.org/10.1016/j.ibiod.2015.02.012
0964-8305/ 2015 Elsevier Ltd. All rights reserved.

sources of VOCs are gasoline from lling stations, smoking tobacco

products, solvents for manufacturing industries, transportation and
auto exhausts. Many of these VOCs are hazardous to human health
and the environment as they are ammable, toxic, carcinogenic,
and/or mutagenic agents (Bansode et al., 2003; Peng et al., 2003;
Lillo-Rodenas et al., 2006; Wibowo et al., 2007; Zaini et al., 2009;
Su et al., 2010; Li et al., 2011; Abdullahi et al., 2013). Many are also
compounds of fuels, solvents, hydraulic uids and dry cleaning
agents commonly used in urban settings such as bleach (Abdullahi
et al., 2014; Kim et al., 2014). Abdullahi and Chian (2011) studied
VOCs in drinking water in peninsular Malaysia and detected 54
different VOC species in the samples analysed from 11 states which
was attributed to improper disposal practice. VOCs have been reported to be responsible for many acute and chronic health effects
and environmental degradations such as global warming (Tan et al.,
2008a; Su et al., 2010; Li et al., 2011). Air stripping, absorption,

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J. Mohammed et al. / International Biodeterioration & Biodegradation 102 (2015) 245e255

reverse osmosis, biological, thermal and catalytic oxidation, sonochemical and other advanced oxidation processes like Fenton,
photo-Fenton, wet oxidation, ozonation, photo catalysis, electrochemical, membrane-based separation and non-thermal plasma
are among the treatment methods for VOCs (Abdullahi et al., 2014),
but they have limitations towards efciency and cost.
Adsorption of VOCs by activated carbon (AC) has proven to be
sustainable, environmentally friendly, economical and efcient
which makes it the most commonly used technique (Wibowo et al.,
2007; Auta and Hameed, 2013; Nasri et al., 2014a; Ruan et al., 2014).
However, the preparation conditions, porosity characteristics, surface chemistry and modication are responsible for the performance and specic applications of activated carbons (Li et al., 2011;
Nasri et al., 2014b). Modication of AC by treatment with acids or
alkalis is a popular and cost effective technique. Li et al. (2011) reported that ammonia treatment enhances the basic properties of
the AC and is translated into the increase in the removal efciency
of hydrophobic VOC (o-xylene) by 26.5%. Economic, efcient and
sustainable means of treating VOCs remains a challenge and there
is need for further attention in this direction. In view of this, sustainable activated carbon was prepared by chemical activation with
potassium hydroxide under microwave technology (PHAC) and
further modied with ammonia (PHAC-AM) for adsorption of
benzene and toluene.
The spent activated carbon (PHAC-AM) was regenerated to
avoid the common practice of discarding in a landll and making
the process economically competitive against other purication
methods. This also has a dual advantage of reducing waste generation and formation of green-house gases (GHGs) (Sahu et al.,
2010). Microwave (MW) technique was employed for the thermal
regeneration as there are limited studies (Xin-hui et al., 2011; Foo
and Hameed, 2012a) in this area and due to its numerous advantages such as uniform temperature prole (heating), time and energy saving over the conventional heating technique (Furnace)
(Xin-hui et al., 2011; Kim and Ahn, 2014), MW also helps to enhance
the basic properties in the activated carbon which is required for
the removal of hydrophobic volatile organic compounds. The efciency of regeneration in ve successive adsorptioneregeneration
cycles was evaluated. Therefore, this research focuses on the effect
of ammonia treated coconut shell porous activated carbon (PHACAM) on the removal of benzene and toluene through batch studies.
Comprehensive analysis was carried out on the batch studies
through the establishment of equilibrium isotherms and kinetic
models for the correlation and validation of the experimental data.
Materials and methods
Materials
Potassium hydroxide pellets (99%), ammonia (25%), benzene
(99.7%) and toluene (99.9%) were supplied by Merck KGaA, Darmstadt, Germany. Nitrogen and carbon dioxide (CO2) gas were supplied by Mega Mount Industrial Gases Sdn. Bhd., Johor Bahru,
Malaysia. Coconut shells were taken from Johor state, Malaysia. The
shells were adequately cleaned in distilled water and dried at
105  C for 48 h. After that, they were crushed and separated using
sieves and shakers to the size range of 0.5e1.18 mm. The proximate
and ultimate analysis of the precursor used in this study and those
reported by other researchers are presented in Table 1.
Proximate and ultimate analysis
The proximate analysis provides information on the moisture
content, volatile content (e.g. cellulose, hemicellulose and lignin
and all other gases given off during pyrolysis), the xed carbon and

Table 1
Proximate and ultimate analyses showing percentage composition of precursor (CS)
used in this study compared with other studies.
Proximate (%)

This study

Yang et al., 2010

Daud and Ali, 2004

Moisture
Volatiles
Ash
Fixed carbon

5.62
71.4
1.11
23.3

10.5
70.1
0.66
18.8

8.21
73.1
0.1
18.6

Ultimate (%)

This study

Demiral et al., 2011

Daud and Ali, 2004

Carbon
Hydrogen
Nitrogen
Sulphur
Oxygen

48.7
6.34
1.52
0.038
43.4

53.4
7.5
1.7
0.0
37.4

48.6
6.51
0.14
0.08
44.6

the ash (the inorganic residue remaining after pyrolysis of the

sample) of a biomass material or precursor. On the other hand, the
ultimate analysis provides information on the composition of the
biomass material in wt% of carbon, hydrogen, nitrogen, oxygen and
sulfur (CHNOS). The carbon content considered in ultimate analysis
comprises of that existing in the organic biomass substance and any
inherent carbon present as mineral carbonate. However, proximate
analysis is the most often used analysis for characterizing activated
carbon precursors with respect to their application (Ayhan, 2009;
Bouchelta et al., 2012).
The proximate and elemental analysis of the samples were
carried out for elemental composition using an Elemental Analyzer
(LECO CHNS-932), the analysis was done in the central laboratory of
University Malaysia Pahang. The percentage of oxygen content in
the ultimate analysis was calculated by difference of the total percentages of the other components (i.e. Carbon, Hydrogen, Nitrogen
and Sulphur). The results obtained from the proximate and ultimate analyses are presented in Table 1. The precursor contains low
composition of ash, which is an advantage for the synthesis of
porous carbons with high yield and can be translated into highly
carbonaceous activated carbons (Daud and Ali, 2004; Yang et al.,
2010). This also implies an added advantage in terms of cost
effectiveness. In addition, the xed carbon composition (23.3%)
from the proximate analysis is higher than the reported results
from Daud and Ali (2004) and Yang et al. (2010) with xed carbon
compositions of 18.6 and 18.8%, respectively. From the ultimate
analysis, the carbon content of the precursor (CS) from this study
(48.7%) is slightly higher than the reported result from Daud and Ali
(2004) but lower than the reported result from Demiral et al. (2011)
with 48.6 and 53.4%, respectively. High composition of carbon in
coconut shell as presented from the elemental analysis (Table 1)
indicates that it is a good precursor for porous carbon synthesis.
Sample preparation methods
Two-step activation procedure was adopted from our previous
study (Nasri et al., 2014a). In two-step activation, the precursor is
rst carbonized and the resulting char is then activated, this can
help to produce carbon with high specic surface area. Initial pyrolysis of the precursor was carried out in a furnace, under a ow of
nitrogen (150 cm3/min) from ambient temperature to pyrolysis
temperatures (600 and 700  C) at 10  C/min heating rate for 1
through 4 h. The effect of the varying temperature and residence
time on yield of char was also studied, with pyrolysis at 700  C for
2 h offering the highest yield of 32%.
The resulting char was impregnated with potassium hydroxide
at an impregnation ratio of 1.5:1 g/g (mass ratio) of chemical reagent to char (Mohammed et al., 2014). The mixture was mixed
properly and dried in the oven for 24 h at 105  C before being

J. Mohammed et al. / International Biodeterioration & Biodegradation 102 (2015) 245e255

loaded into the glass reactor inside the microwave (MW). The
material was activated by heat treatment under a CO2 ow of
150 cm3/min at power level of 500 W and irradiation time of 4 min
(Mohammed et al., 2014). Then, the resultant AC was cooled and
removed from the MW. The resultant activated samples were
washed with distilled water until the pH of the rinse was close to
six and then dried at 105  C for 24 h (Sun and Webley, 2010). The
sample was designated as PHAC (potassium hydroxide activated
carbon) and was stored in desiccators prior to be used.
Ammonia treatment
In order to improve the hydrophobic properties of the activated
carbon. The potassium hydroxide synthesized activated carbon
(PHACM) was modied by ammonia treatment to obtain (PHACMAM). The ammonia solution for the preparation of PHACM-AM was
made from 6.6 M NH3$H2O (AM) as reported by Li et al. (2011).
Then, it was soaked in the solution at 70  C for 2 h and was then
placed on a rotation vibrator at 35  C for 24 h. The modied activated carbon was separated from the solution and washed
repeatedly with distilled water. It was then dried in an oven at
105  C for 4 h and transferred to a desiccator before use. The
treatment with ammonia caused the introduction of a signicant
number of nitrogen surface groups onto the carbon surface by
displacing the oxygen functional groups (Li et al., 2011).

247

where Co and Ce (mg/L) are the concentrations of benzene and

toluene at initial stage and at equilibrium. V (L) is the volume of
solution, and W (g) is the weight of adsorbent.
Kinetics and equilibrium studies
Kinetics and equilibrium adsorption studies were conducted by
agitating 0.1 g of PHAC with varying initial concentrations
(50e250 mg/L) of VOC solution in Teon covered 30 mL sample
bottles at 30  C in a shaker at 115 rpm. The VOC concentration was
determined at preset intervals using UVeVis spectrometer (Perkin
Elmer Lambda 25) at 254 and 206 nm for benzene and toluene
respectively to reach equilibrium. VOC uptake at equilibrium, Qt
(mg/g), was determined by Eq. (3):

Qt

Co  Ct V
W

(3)

where Co and Ct (mg/L) are the initial concentration and concentration at a particular time t, of benzene and toluene; V (L) is the
volume of the solution; and W (g) is the weight of the activated
carbons.
Regeneration studies

Pore structural analysis was characterized with Micromeritics

ASAP 2020 for full isotherm analysis. Scanning electron microscopy
(SEM) analysis with Karl Zeiss (EVO50 XVPSEM, Germany) was
carried out on PHAC and PHAC-AM to study the development of
porosity and surface morphology. The surface organic structures of
the raw material and AC were chemically and structurally studied
by Fourier Transform Infra-red Spectroscopy (FT-IR) spectra recorded at 4 cm1 of resolution and 16 scans min1 between 4000 and
370 cm1 using a Perkin Elmer Spectrum one series model
instrumental Analysis with the KBr disc method.

The spent activated carbons were submerged in 500 mg/L of

benzene and toluene solution for 24 h to make sure that the active
sites were completely saturated. A 2.5 GHz domestic MW was
modied and a glass reactor was xed into the chamber inside it.
The adsorbents were then introduced into the glass reactor and the
MW power was set to 600 W (Foo and Hameed, 2012a). Nitrogen
gas at a preset ow rate (300 cm3/min) was used to create an inert
atmosphere in the reactor before the start of microwave heating
and it continued to ow during the regeneration stage. The heating
duration chosen for the regeneration of PHACM-AM was 3 min. The
yield is dened as the weight of regenerated activated carbon per
weight of benzene and toluene loaded activated carbon utilized for
regeneration of the previous cycles. The adsorptioneregeneration
process was repeated for ve cycles (Foo and Hameed, 2012b).

Removal efciency of benzene and toluene

Results and discussion

The removal efciency and adsorption capacity of benzene and

toluene on the synthesized activated carbon (PHAC) and its
ammonia treated (PHAC-AM) forms were studied. The removal
efciency was calculated from the equation:

Characterization results

Characterization of samples

% Removal

Co  Ce
 100
Co

(1)

where Co (mg/L) is the initial concentration of the VOCs and Ce (mg/

L) is the nal concentration of benzene and toluene at equilibrium.
Adsorption studies
Batch adsorption studies were conducted by agitating 0.1 g of
the activated carbons (PHAC and PHAC-AM) with varying initial
concentrations (50e250 mg/L) of VOCs solution in Teon covered
30 mL bottles at 30  C in a shaker at 115 rpm. The VOCs concentration was determined using UVeVis spectrometer (Perkin Elmer
Lambda 25) at 254 and 206 nm for benzene and toluene, respectively. VOC uptake at equilibrium, Qe (mg/g), was determined by:

Qe

Co  Ce V
W

(2)

The nitrogen adsorption isotherms result show BET surface area

and pore volume of PHACM and PHACM-AM to be 478 m2/g and
0.61 cm3/g, and 361.8 m2/g and 0.16 cm3/g respectively. The lower
BET surface area and pore volume recorded in PHACM-AM could be
as a result of the ammonia treatment. After the ammonia treatment
process, some of the pores have been broken and enlarged which
could be responsible for the lower surface area and pore volume in
PHACM-AM. Similar result was reported by Li et al. (2011), where
ammonia treated commercial activated carbon was used to adsorb
o-xylene. The SEM further shows the effect of ammonia treatment
in the surface morphology of the adsorbents with PHACM-AM
having wider pores (Fig. 1a). The micrographs for PHACM-AM after benzene and toluene adsorption (REG-A and REG-T) are somewhat covered with the adsorbed VOCs (Fig. 1c and d), unlike the
micrograph structure of the adsorbents before adsorption which
had highly porous surface as presented in (Fig. 1a and b).
FTIR spectrum analysis allows the identication of different
functional groups on the surface of the precursor (CS), PHAC and
PHAC-AM. The spectra for CSC, PHAC and PHAC-AM are shown in
Fig. 2. In Fig. 2, all samples exhibit similar spectra, suggesting they
have similar structure and functional groups. However, the

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J. Mohammed et al. / International Biodeterioration & Biodegradation 102 (2015) 245e255

Fig. 1. SEM images of (a) PHAC, (b) PHACM-AM, (c) REG-B and (d) REG-T.

Fig. 2. FTIR spectra of (A) PHAC-AM (B) PHAC and (C) CSC.

intensity of the spectra varies slightly from the char to the activated
carbons. The spectrum shows the presence of some typical bands of
lignocellulosic materials of coconut shell belonging to functional
groups such as hydroxyl, alkenes, aromatics and carbonyls. The
wide band at 3500 cm1 to 3100 cm1 is ascribable to (OeH) vibrations in the hydroxyl groups (Prauchner and Rodrguez-Reinoso,
2012). However, this peak is more pronounced in the potassium
acetate activated carbon (PHAC-AM) which suggests the presence
of more phenolic groups after chemical treatment with ammonia.
The band at 2900 cm1 to 2600 cm1 is an indication of aldehydes
which is more prominence in PHAC-AM as well. The vibrations
between 1700 cm1 and 1550 cm1 could be assigned to alkenes
conjugation (C]C), i.e., the characteristics of cellulose and hemicelluloses (Sun and Webley, 2010). The band at 1200 and 1100 cm1
could be a result of CeO stretching vibrations in tertiary, secondary
and primary alcohol that is more evident in the char (CSC) (Nabais
et al., 2011). The bands centred in 1050 through 600 and 550 cm1
can be attributed to alkenes and aromatics out of plane bend with
acyclic CeOeC groups conjugated with carbonecarbon double
bounds (C]CeOeC) in olenic or aromatic structures. While the

J. Mohammed et al. / International Biodeterioration & Biodegradation 102 (2015) 245e255

Yield %

Wf
 100
Wi

249

(4)

where, Wf and Wi are the nal weight of char (g) and the precursor
weight (g), respectively. Two hours activation time and 700  C
yielded 32% of char, and was observed to be the best condition with
the highest yield. The trend indicates that the yield increases with
increasing time and temperature from 1 to 2 h and 600e700  C,
after which there was a downward trend indicating the yield
reduction. This implies that any further heating above 2 h and
700  C is not cost effective due to low yield and high energy
consumption.

Fig. 3. Effect of activation time and temperature on yield.

vibrations in the range 900e700 cm1 can be attributed to CeH

deformation due to out-of-plane vibrations and can be assigned to
the aromatic structures. The FTIR result shows that the activated
carbons produced (PHAC and PHAC-AM) are rich in basic surface
functional group which in turn helps in the adsorption process of
hydrophobic contaminants.
Effect of activation time and temperature on yield
Fig. 3 displays the effect of pyrolysis conditions on the yield of
char by varying, time and temperatures between 1e4 h and 600
and 700  C respectively during the carbonization process, to
establish the best operating condition. The percent yield was
determined from the relation:

Effect of contact time on removal efciency of PHAC and PHAC-AM

Contact time is a crucial sorption parameter that gives useful
piece of information on the optimum adsorption time. From Fig. 4a
and b, an initial rapid increase in the percentage removal of benzene and toluene was observed which reached a steady state after
300 min giving the maximum VOCs removal efciency for PHAC
and PHAC-AM. The removal rate was higher in the beginning due to
larger available adsorbent surface area, and after 300 min most of
the available sites have been occupied leading to a linear curve. At
this state, the rate of benzene and toluene uptake was controlled by
the rate of transport of VOCs from the exterior to the interior sites of
the adsorbent particles which is nearly constant throughout the
period of time. The removal of benzene and toluene by PHAC are;
82.5 and 85.6%, while that of PHAC-AM are; 91 and 92.3% respectively with approximately 10% increase in the uptake of benzene
and toluene after the ammonia treatment. The higher removal efciency recorded by PHAC-AM could be as a result of the ammonia

Fig. 4. Removal efciency of PHAC and PHAC-AM for (a) benzene and (b) toluene.

250

J. Mohammed et al. / International Biodeterioration & Biodegradation 102 (2015) 245e255

treatment. Similar result was reported by Li et al. (2011), that the

removal of o-xylene increased by 26.5% after the ammonia
treatment.
Effect of initial concentration on VOC adsorption
Initial concentrations of benzene and toluene from 50 to
250 mg/L were varied to study the effect of concentration on the
adsorption process. Adsorption uptake increased with increase in
initial concentration and faster equilibrium was achieved at lower
concentrations as presented in (Fig. 5aed). This was attributed to
availability of sufcient vacant active sites at lower concentrations
which had limited adsorbate molecules to occupy on both PHAC
and PHAC-AM. The unsaturated vacant sites present in the
adsorption process at low concentrations transformed into lower

adsorption uptake of pollutant from solution. Similar scenario

observed has been reported elsewhere (Tan et al., 2008b; Auta and
Hameed, 2013).
Similarly, VOC concentration at equilibrium is measured at the
point where the amount of VOC adsorbed on PHAC is in a state of
dynamic equilibrium with the amount of VOC desorbing from it and
it reveals the maximum adsorption capacity of the adsorbent. The
results shows that equilibrium position was achieved more rapidly
at lower initial VOC concentrations than at higher initial concentrations of VOCs for both adsorbents. This could be due to the fact
that at lower concentrations, there is less number of VOC molecules
competing for the vacant sites on PHAC and PHAC-AM, as a result,
they will be adsorbed rapidly. While at higher concentrations, there
are more molecules of VOC competing for the xed PHAC and PHACAM dosage vacant sites available (Auta and Hameed, 2014). The

Fig. 5. Effect of initial concentration on adsorption of (a) benzene on PHAC, (b) toluene on PHAC, (c) benzene on PHAC-AM and (d) toluene on PHAC-AM.

J. Mohammed et al. / International Biodeterioration & Biodegradation 102 (2015) 245e255

adsorption process is characterized by the movement of adsorbate

to the adsorbent external surface through a boundary layer, diffusion into the pores of the adsorbent and onto interior pores of the
adsorbent (Tan et al., 2008b). Fig. 5aed shows that the amount of
benzene and toluene adsorbed increased from 14.4 to 55.4 mg/g and
14.91e58.1 mg/g, respectively for PHAC, and 14.4e63 mg/g and
14.91e64 mg/g, respectively for PHAC-AM with an increase in the
initial VOCs concentrations from 50 to 250 mg/L. Therefore, it can
be said that adsorption of benzene and toluene on PHAC and PHACAM increased as the initial concentration increases.

251

Adsorption equilibrium isotherm

Adsorption isotherm is important in describing the interaction
of solutes and adsorbent and how to optimize the use of the adsorbents. Langmuir, Freundlich and Tempkin isotherm models were
studied with their evaluated parameters presented in Table 3. The
Langmuir isotherm assumes monolayer adsorption and is given as:

Qe

Qm bCe
1 bCe

Fig. 6. Langmuir, Freundlich and Temkin adsorption isotherms for (a) benzene on PHAC (b) toluene on PHAC (c) benzene on PHAC-AM and (d) toluene on PHAC-AM.

(5)

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J. Mohammed et al. / International Biodeterioration & Biodegradation 102 (2015) 245e255

Ce (mg/L) is the adsorbate equilibrium concentration, Qe (mg/g)

is the quantity of adsorbate adsorbed per unit mass of adsorbent,
Qm and b are Langmuir constants which translate to the adsorption
capacity and the rate of adsorption respectively (Zaini et al., 2009;
Cadogan et al., 2014; Nasri et al., 2014b). A plot of Qe against Ce gave
curves (Fig. 6aed) with correlation coefcient R2 of 0.99 indicated
that the adsorption data of benzene and toluene on the PHAC and
PHAC-AM were well tted to the Langmuir isotherm.
Freundlich isotherm, on the other hand, assumes heterogeneous
surface. The non-linear form of the Freundlich model is dened by:

Table 2
Langmuir, Freundlich and Temkin isotherm models constants, correlation coefcients of benzene and toluene adsorption on PHAC and PHAC-AM.
Isotherms

Langmuir

(6)

where Qe (mg/g) is VOC equilibrium adsorption, Ce (mg/L) is

adsorbate equilibrium concentration, Kf and n are Freundlich constants. The value of n relates to the favourability of adsorption
process and Kf represents the adsorption capacity. The slope of 1/n
between 0 and 1 is a measure of the adsorption intensity or surface
heterogeneity, becoming more heterogeneous as its value gets
closer to zero (Tan et al., 2008b; Cadogan et al., 2014; Nasri et al.,
2014b) The plot of Qe vs. Ce (Fig. 6aed) gave a less tted curve
and lower R2 value than that of Langmuir.
Lastly, the Temkin model equation is dened as:

Qe

RT
ln ACe
b

(7)

where R represent gas constant (8.314 J/molK), T represents absolute temperature (K), A represents the maximum binding energy, b
represents the heat of adsorption, Qe (mg/g) is the experimental
adsorption capacity, and Ce (mg/L) is VOCs equilibrium concentration. The plot of Qe against Ce gave good curves for both benzene
and toluene (Fig. 6aed). However, Langmuir isotherm had the best
tting with maximum adsorption capacity of 212.77 and
238.10 mg/g for PHAC, and 344.83 and 357.14 mg/g for PHAC-AM,
for benzene and toluene, respectively.
The models were further validated by root-mean-square deviation (RMSD) as enumerated in Table 2.

2 1=2
X
qexp  qp
RMSD 1=n

1
1 bCo

PHAC
PHAC-AM

Temkin

PHAC
PHAC-AM

R2

RMSD

Qm (mg/g)

KL (l/mg)

Benzene
Toluene
Benzene
Toluene

212.77
238.10
344.83
357.14
Kf (mg/g)

0.0014
0.0013
0.0009
0.0009
1/n

0.9978
0.9976
0.9976
0.9984
R2

1.76
2.15
3.60
3.02
RMSD

Benzene
Toluene
Benzene
Toluene

0.49
0.48
0.38
0.40
A (l/g)

0.8661
0.8766
0.9264
0.9222
b

0.9942
0.9927
0.9981
0.9985
R2

1.95
2.33
3.03
2.42
RMSD

Benzene
Toluene
Benzene
Toluene

0.0309
0.0306
0.0285
0.0288

9.45
8.92
8.37
8.15

0.9603
0.9466
0.9549
0.9593

3.05
3.40
3.68
3.58

It shows that PHACM and PHACM-AM activated carbon produced from this research performed better than the commercial
activated carbon (F-400) and that chemically treated with nitric acid
(F-400Cox) (Wibowo et al., 2007), and the carbon nanotubes (CNTs)
as reported by Su et al. (2010) (Table 3). This could be as a result of
hydrophobic properties introduced by the microwave treatment in
PHACM and the ammonia treatment in the case of PHACM-AM. The
commercial activated carbon (GAC) had adsorption capacity of
201.52 and 223.64 mg/g for benzene and toluene, respectively; this
is similar to the adsorption capacity obtained for PHACM with
212.77 and 238.10 mg/g for benzene and toluene, respectively. It was
observed that PHACM-AM also compared favourably well with the
results reported by Su et al. (2010) for oxidized carbon nanotubes
(CNT(NaOCl)). PHACM-AM had 344.83 and 357.14 mg/g compared
to 247.87 and 279.81 mg/g obtained on CNT(NaOCl) for adsorption
of benzene and toluene, respectively. This could be as a result of the
basic properties and well developed surface morphology of PHACMAM as evident in the characterization results.

(8)
Adsorption kinetics on VOC adsorption on AC

where n is the number of data points, qexp (mg/g) and qp (mg/g) are
the experimental and calculated adsorption capacities respectively.
The lower the RMSD value the better the estimated model performs
(Auta and Hameed, 2013; Cadogan et al., 2014; Nasri et al., 2014b),
with Langmuir model having the lowest RMSD values.
From Table 2, it is evident that PHACM-AM had higher benzene
and toluene adsorption capacity (Qm) compared to PHACM, this
could be as a result of the ammonia treatment and the welldeveloped surface morphology from the SEM result.
The favourability of Langmuir isotherm can be expressed in
terms of a dimensionless constant separation factor (RL) dened by:

RL

PHAC
PHAC-AM

Freundlich
1

Qe Kf Cen

Constants

(9)

where b represents Langmuir constant and Co (mg/L) is the highest

VOC concentration. RL value shows whether the isotherm is unfavourable (RL > 1), linear (RL 1), favourable (0 < RL < 1) or irreversible
(RL 0). The values of RL in this study were found to be 0.73 and 0.75
for adsorption of benzene and toluene on PHAC, respectively, and
0.82 for adsorption of both benzene and toluene on PHAC-AM. This
indicates that Langmuir isotherm model was favourable. The
maximum adsorption capacity of benzene and toluene obtained in
this work were compared with the literature (Table 3).

The kinetic models employed in this study are the pseudo-rstorder and pseudo-second-order equations which were used to
determine the model that best described the adsorption of benzene
and toluene on PHAC and PHAC-AM. Pseudo-rst-order model is
given as:

lnqe  qt ln qe  k1 t

(10)

where qe and qt are the quantity of benzene and toluene adsorbed

(mg/g) at equilibrium and at time t (min), and k1 is the adsorption
rate constant (1/min). Values of k1 were obtained from the slopes of
the linear plots of ln (qe e qt) vs. t. The deviations of the calculated
qe values from the experimental qe values were quite high (Table 4),
signifying that this model was not appropriate.
Pseudo-second-order equilibrium adsorption is given by:

t
1
1

t
qt k2 q2e qe

(11)

where k2 (g/mg min) is the second-order adsorption rate constant,

qe and k2 can then be determined from the slope and the intercept
of plot t/qt vs. t. The linear plot (gure not shown) demonstrates a
good correlation between the experimental and the calculated qe

J. Mohammed et al. / International Biodeterioration & Biodegradation 102 (2015) 245e255

253

Table 3
Comparison of maximum adsorption capacity (Qm) of benzene and toluene on different porous carbons.
Samples

Condition

Commercial activated carbon (F-400)

Commercial activated carbon chemically
treated with nitric acid (F-400Cox)
Commercial activated carbon thermally
treated (F-400Tox)
Carbon nanotubes (CNTs)
Oxidized carbon nanotubes CNT(NaOCl)
Commercial activated carbon (GAC)
Durian shell activated carbon (DSAC)
PHACM
PHACM-AM

Surface area (m2/g)

Adsorption capacity (mg/g)

Benzene

Toluene

References

30  C, PH 7
30  C, PH 7

877.82
938.36

151.82
90.82

166.27
98.34

Wibowo et al. (2007)

Wibowo et al. (2007)

30  C, PH 7

863.66

201.52

223.64

Wibowo et al. (2007)

310.75
88.56
1292.10
1404
478
361.8

34.46
247.87
217.32

71.27
279.81
221.13
57.14
238.10
357.14

Su et al. (2010)
Su et al. (2010)
Su et al. (2010)
Tham et al. (2011)
This work
This work

25  C
25  C
25  C
30  C
30  C

values (Table 4) indicating the applicability of the second-order

model to describe the adsorption process.
Pseudo-second-order models predict the behaviour over the
whole range of adsorption with physisorption and chemisorption
being the rate controlling step (Foo and Hameed, 2012a,b). The
results obtained in this study (Table 4), shows that the deviation
between the experimental results and calculated values for
adsorption of benzene and toluene on PHACM and PHACM-AM are
relatively lower in the pseudo-second-order model, indicating that
the values obtained from the pseudo-second-order model are more
correlated to the experimental values. This is also evident in the
higher values of the adsorption rate constant (k2) when compared
to the (k1) values in pseudo-rst-order model. The applicability of
the pseudo-second-order model is more evident at higher initial
concentrations of benzene and toluene as the correlation is more
pronounced at 250 mg/L with k2 and k1 values of 0.0231 and 0.013,
and 0.0108 and 0.0132, obtained respectively for benzene and
toluene adsorption on PHACM, while the k2 and k1 values of
PHACM-AM are 0.0266 and 0.0113, and 0.0363 and 0.0132 for
benzene and toluene adsorption, respectively. This suggests that
chemisorption is most likely the rate controlling step.
Regeneration studies
The reusability test as described in Section 2.6 was repeated ve
times and the results showing the removal efciency and yield

212.77
344.83

against ve cycles are summarized in Fig. 7aeb. The desorption

efciency and yield of PHAC-AM was approximately 50% and 80%
for benzene and toluene respectively, after the fth cycle.
From Fig. 7aeb, it is evident that the trend of removal efciency
of benzene and toluene, and the yield of PHACM-AM are interesting, even after several repetitive regeneration cycles. The
removal efciency decreased from approximately 90 and 80% to
50% for benzene and toluene respectively, after ve successive cycles, while the yield of PHAC-AM reduced by approximately 20% for
both benzene and toluene loaded PHACM-AM as compared to its
original value of 100%. This may be as a result of the collapse of
porosity due to the thermal heating, pore blockage as a consequence of the incomplete desorption of adsorbate molecules
retained in the carbon network and internal reorganizations of the
carbon structure due to the large amount of gases evolved during
the regeneration stage (Foo and Hameed, 2012b). Similar results
were reported by some researchers. Foo and Hameed (2012a,b),
achieved high methylene blue uptake with corresponding high
yield of 74e81% after ve successive cycles. However, there is a
need to explore this promising method further as few literature
(Zhang et al., 2009; Dehdashti et al., 2011; Xin-hui et al., 2011; Foo
and Hameed, 2012a) are available in this research direction.
Furthermore, most of the reported studies are based on the commercial activated carbon and none of the literature considered
regeneration of activated carbon saturated with benzene and
toluene.

Table 4
Parameters of pseudo-rst-order and pseudo-second-order reaction models for Benzene and Toluene adsorption on PHAC and PHAC-AM.
Adsorbent

PHAC

VOC sample

Benzene

Toluene

PHAC-AM

Benzene

Toluene

Initial conc.

qe, exp

Pseudo-rst-order kinetic model

Pseudo-second-order kinetic model

2

qe, cal

K1

qe, cal

K2

R2

250
200
150
100
50
250
200
150
100
50

55.4
51.3
37
26.1
14.4
58.1
54.45
38.5
27.3
14.91

65.41
55.66
36.67
27.73
13.87
85.63
83.53
52.14
33.19
20.02

0.013
0.0133
0.012
0.0112
0.0076
0.0132
0.0134
0.0127
0.0115
0.0076

0.9776
0.996
0.9997
0.9582
0.9073
0.9464
0.9429
0.9609
0.9624
0.7778

60.98
56.82
39.68
27.93
14.10
71.42
69.44
46.08
30.96
17.64

0.0231
0.0246
0.0295
0.0241
0.0234
0.0108
0.0092
0.0126
0.0159
0.0056

0.9647
0.9651
0.9625
0.9304
0.8964
0.7692
0.708
0.8219
0.8822
0.4667

250
200
150
100
50
250
200
150
100
50

63
51.3
40.75
26.1
14.4
64
54.45
41.5
27.3
14.91

72.13
55.66
36.28
27.73
13.87
67.55
83.53
39.90
33.19
20.02

0.0113
0.0133
0.0116
0.0112
0.0076
0.0132
0.0134
0.0127
0.0115
0.0076

0.8154
0.996
0.987
0.9582
0.9073
0.9176
0.9429
0.9902
0.9624
0.7778

63.69
56.82
41.84
27.93
14.10
65.36
69.44
45.25
30.96
17.64

0.0266
0.0246
0.0438
0.0241
0.0234
0.0363
0.0092
0.0280
0.0159
0.0057

0.9625
0.9651
0.9811
0.9304
0.8964
0.9706
0.708
0.9509
0.8822
0.4667

254

J. Mohammed et al. / International Biodeterioration & Biodegradation 102 (2015) 245e255

Fig. 7. Desorption efciency and yield of PHAC-AM after ve successive cycles for (a) benzene and (b) toluene.

The microwave treatment is a promising approach for regeneration studies, with interesting results in terms of the removal
efciency at an acceptable level and life span of activated carbon.

Conclusion
The effect of ammonia treatment on PHAC was evident from the
higher removal efciency and adsorption of benzene and toluene
on PHAC-AM in the batch studies conducted. Higher removal of
toluene was recorded in the batch adsorption studies because;
toluene is less volatile than benzene and tends to adhere more to
the surface of the adsorbent. Hydrophobicity of PHAC also
increased by approximately 10% as a result of ammonia treatment
which in turn enhanced the afnity of the activated carbon towards
volatile organic compounds. The experimental result best correlated with the Langmuir isotherm model indicating that the
adsorption process was largely on the monolayer surface, and the
pseudo-second order kinetic model best described the adsorption
kinetics. The sustainability and renewability of the adsorbent was
established as approximately 50% adsorption efciency was
retained after ve successive regeneration cycles.

Acknowledgement
This study was supported by the University Research Grant
(Q.J130000.2509.06H79) and International Doctoral Fund awarded
by the Universiti Teknologi Malaysia, Johor Bahru.

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