Preparation, characterization and evaluation of adsorptive properties of orange

peel based activated carbon via microwave induced K

2
CO
3
activation
K.Y. Foo, B.H. Hameed

School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
a r t i c l e i n f o
Article history:
Received 8 August 2011
Received in revised form 30 September
2011
Accepted 1 October 2011
Available online 8 October 2011
Keywords:
Activated carbon
Adsorption
Methylene blue
Microwave
Orange peel
a b s t r a c t
This work explores the feasibility of orange peel, a citrus processing biomass as an alternative precursor
for preparation of activated carbon (OPAC) via microwave assisted K
2
CO
3
activation. The operational
parameters, chemical impregnation ratio, microwave power and irradiation time on the carbon yield
and adsorption capability were investigated. The virgin characteristics of OPAC were examined by pore
structural analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, nitrogen
adsorption isotherm, elemental analysis, surface acidity/basicity and zeta potential measurement. The
optimum conditions resulted in OPAC with a monolayer adsorption capacity of 382.75 mg/g for methy-
lene blue and carbon yield of 80.99%. The BET surface area, Langmuir surface area and total pore volume
were identied to be 1104.45 m
2
/g, 1661.04 m
2
/g and 0.615 m
3
/g, respectively. Equilibrium data were
simulated using the Langmuir, Freundlich, DubininRadushkevich, RedlichPeterson, and Toth isotherms,
and kinetic data were tted to the pseudo-rst-order, pseudo-second-order and Elovich kinetic models.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Orange, specically known as Citrus sinensis, is one of the most
favored subtropical fruits in the world. The fruit is globose, subglo-
bose and oblate, with a width from 6.5 to 9.5 cm. The outer epicarp
is orange when ripe, while the inner mesocarp is white, spongy and
non-aromatic (Morton, 1987). Orange fruit is primarily eaten fresh
and available as food complements in desserts, salads, gelatins,
fruit cocktail, jam or juice combinations in the citrus processing
industries (Armando et al., 2001). According to the Food and Agri-
culture Organization (FAO), the annual production of orange fruit
in 2010 is projected at 64 million MT, translating to approximately
32 million MT of peels as the byproducts (Spreen, 2010).
Traditionally, orange peels (OPs) were processed to obtain the
volatile and nonvolatile fractions of essential oils and avoring in
the carbonated drinks, ice creams, cakes, air-fresheners, perfumes
and cosmetic products (Li et al., 2008). Besides, OPs have been re-
ported to have germicidal, antioxidant and anti-carcinogenic prop-
erties as a remedy against breast and colon cancer, stomach upset,
skin inammation, muscle pain, and ringworm infections (Spreen,
2000). However, the application of these extracted constituents is
limited due the overall demands for these value-added products
are relatively insignicant. Therefore, it is necessary to nd a rapid
and easy route towards upgrading of the citrus processing biomass.
In this sense, the present work is aimed at evaluating the viabil-
ity of microwave irradiation for preparation of activated carbon
from OP via K
2
CO
3
activation. The signicant inuences of micro-
wave power, radiation time and chemical impregnation ratio on
the carbon yield and adsorption capacity were investigated sys-
tematically. Structural, functional and surface chemistry of the pre-
pared adsorbent was performed. Moreover, the adsorption
equilibrium, isotherms, kinetics and thermodynamics were
outlined.
2. Methods
2.1. Adsorbate
Methylene blue (MB), a monovalent cationic pollutant (Supple-
mentary Fig. 1) difcult to be degraded in natural environment was
selected as the model adsorbate in the present study. A stock solu-
tion of 500 mg/L was prepared by dissolving an appropriate quan-
tity of MB in double distilled water and then diluted to the desired
concentrations.
2.2. Preparation of activated carbon
Orange peel (OP), a by-product collected from the local restau-
rant, was the precursor used in the present study. The raw precur-
sor was washed exhaustively with deionized water to remove
adhering dirt particles from the surface. Dried OP was cut, ground
and screened to a particle size of 12 mm. The carbonization
0960-8524/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2011.10.005

Corresponding author. Tel.: +60 45996422; fax: +60 45941013.

E-mail address: chbassim@eng.usm.my (B.H. Hameed).
Bioresource Technology 104 (2012) 679686
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j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech
process was carried out by loading 500 g of dried precursor into a
tubular furnace, and heated up to a carbonization temperature of
700 C under puried N
2
ow (150 cm
3
/min). The char produced
was mixed with K
2
CO
3
pellets with different impregnation ratio
(IR), dened as:
IR
w
K
2
CO
3
w
char
1
where w
K
2
CO
3
and w
char
is the dry weight of K
2
CO
3
pellets (g) and
char (g), respectively.
A modied microwave oven with a frequency of 2.45 GHz was
applied for the activation step. Nitrogen gas at a pre-set ow rate
(300 cm
3
/min) was used to purge air in the reactor before the start
of microwave heating and it continued to ow during the activa-
tion stage. The oven has a power controller to select different
power levels and a timer for various exposure times at a set micro-
wave power level. The resultant activated carbon (OPAC) was
washed repeatedly with 0.1 M hydrochloric acid and distilled
water until pH 67 was reached in the residual liquid. The yield
is dened as the weight of activated carbon per weight of char uti-
lized for activation.
2.3. Equilibrium adsorption studies
The batch adsorption experiments were carried out by agitating
0.20 g of OPAC with 200 mL MB solution of desired concentrations
in a set of 250 mL Erlenmeyer asks using a water bath shaker (agi-
tation speed of 120 rpm). The dye concentration in the supernatant
was determined using a double beam UVVis spectrophotometer
(UV-1601 Shimadzu, Japan) at 668 nm. Each experiment was
duplicated under identical conditions. MB uptake at equilibrium,
q
e
(mg/g), was calculated by:
q
e

C
0
C
e
V
W
2
where C
0
and C
e
(mg/L) are the liquid-phase concentrations of dye
at initial and equilibrium, respectively. V (L) is the volume of the
solution, and W (g) is the mass of adsorbent used. The effect of
pH on dye removal was examined by varying the pH from 2 to
12, with initial dye concentration of 500 mg/L, OPAC dosage of
0.20 g/200 mL and adsorption temperature of 30 C. The initial pH
of the dye solution was adjusted by addition of 0.10 M solution of
HCl or NaOH. The equilibrium data were simulated using the Fre-
undlich, Langmuir, DubininRadushkevich, RedlichPeterson and
Toth isotherm models.
2.3.1. Freundlich isotherm
Freundlich isotherm (Freundlich, 1906) is the earliest known
relationship describing the non-ideal and reversible adsorption.
The model can be applied to multilayer adsorption, with non-uni-
form distribution of adsorption heat and afnities over the hetero-
geneous surface. Freundlich isotherm is given by:
q
e
K
F
C
1=n
e
3
where K
F
(mg/g) (L/mg)
1/n
and 1/n are the Freundlich adsorption
constant and a measure of adsorption intensity.
2.3.2. Langmuir isotherm
Langmuir isotherm (Langmuir, 1916) assumes monolayer
adsorption, with adsorption can only occur at a nite number of
localized sites that are identical and equivalent. The mathematical
expression of Langmuir isotherm is dened as:
q
e

Q
0
K
L
C
e
1 K
L
C
e
4
where Q
0
(mg/g) and K
L
(L/g) are Langmuir constants related to
adsorption capacity and free energy of adsorption.
2.3.3. DubininRadushkevich isotherm
DubininRadushkevich isotherm (Dubinin and Radushkevich,
1947) is an empirical model initially conceived for the adsorption
of subcritical vapors onto microporous solids which follows a pore
lling mechanism. It is generally applied to express the adsorption
mechanism with a Gaussian energy distribution over the heteroge-
neous surface. The model was proposed as:
q
e
q
s
expk
ad
e
2
5
with the mean free energy, E (J/mol) per molecule of adsorbate can
be calculated by the relationship:
E
1

2B
DR
p

6
where B
DR
is the isotherm constant. Meanwhile, the Polanyi poten-
tial, e can be correlated as:
e RT ln 1
1
C
e

7
2.3.4. RedlichPeterson isotherm
RedlichPeterson isotherm (Redlich and Peterson, 1959) is a hy-
brid isotherm featuring both Langmuir and Freundlich isotherms,
which incorporates three parameters into an empirical equation
derived as:
q
e

K
R
C
e
1 a
R
C
g
e
8
where K
R
(L/g) and a
R
(1/mg)
g
are RedlichPeterson isotherm con-
stants, and g is the isotherm exponent. The model has a linear
dependence on concentration in the numerator and an exponential
function in the denominator to represent adsorption equilibrium
over a wide concentration range. In the limit, it approaches Freund-
lich isotherm model at high concentration and in accordance with
the low concentration limit of the ideal Langmuir condition.
2.3.5. Toth isotherm
Toth isotherm model (Toth, 1971) is another empirical equation
developed to improve Langmuir isotherm ttings and useful in
describing the heterogeneous adsorption systems, which satises
both low and high-end boundary of concentrations:
q
e

K
T
C
e
a
T
C
e

1=t
9
where K
T
(mg/g), a
T
(L/mg) and t are the Toth isothermconstants. Its
correlation presupposes an asymmetrical quasi-Gaussian energy
distribution; with most binding sites have adsorption energy lower
than the peak (maximum) or mean value.
2.4. Adsorption kinetic
The procedure of adsorption kinetic was identical to adsorption
equilibrium where the aqueous samples were withdrawn at differ-
ent time intervals and the concentrations of MB were similarly
measured. The amount of adsorption at time t, q
t
(mg/g), was cal-
culated by:
q
t

C
0
C
t
V
W
10
where C
t
(mg/L) is the liquid-phase concentration of dye at time, t.
When adsorption is preceded by diffusion through a boundary, the
kinetics in most systems follow pseudo-rst-order equation. The
680 K.Y. Foo, B.H. Hameed/ Bioresource Technology 104 (2012) 679686
rst-order expression of Lagergren (Langergren and Svenska, 1898)
based on solid capacity is dened as:
ln
q
e
q
e
q
t

k
1
2:303
t 11
where k
1
(1/h) is the adsorption rate constant. Contrary to pseudo-
rst-order equation, pseudo second-order equation (Ho, 1995) pre-
dicts the behavior over the whole range of adsorption and repre-
sented by:
1
q
e
q
t

1
q
e
k
2
t 12
where k
2
(g/mg h) is the adsorption rate constant of pseudo second-
order equation. Elovich (Aharoni and Tompkins, 1970) kinetic equa-
tion is one of the most useful models describing chemisorption pro-
cesses, given by:
q
t

1
b
lnab
1
b
lnt 13
where a (mg/g h) is the initial sorption rate and b (g/mg) is related
to the extent of surface coverage and activation energy for chemi-
sorption. The value of (1/b) is indicative of the available number
of sites for adsorption while (1/b) ln(ab) is the adsorption quantity
when lnt = 0.
2.5. Characterization of OPAC
The surface morphologies of the resultant samples were imaged
using a scanning electron microscope (Zeiss Supra 35VP). Chemical
characterization of functional groups was detected by Fourier
transform infrared spectrometer (FTIR-100, Shimadzu) in the scan-
ning range of 4000400 cm
1
. The pore structure of OPAC was
characterized by nitrogen adsorption at 77 K with an accelerated
surface area and porosimetry system (Micromeritics ASAP 2020).
2.6. Surface acidity/basicity and zeta potential measurement (pH
pzc
)
The surface acidity was estimated by mixing 0.20 g of OPAC
with 25 mL of 0.05 M NaOH solution in a closed ask, and agitated
for 48 h at room temperature. The suspension was decanted, and
the remaining NaOH was titrated with 0.05 M HCl. The surface ba-
sicity was measured by titration with 0.05 M NaOH after incuba-
tion 0.20 g of OPAC with 0.05 M HCl.
The determination of pH
pzc
was conducted by adjusting pH of
50 mL 0.01 M NaCl solution to a value between 2 and 12. OPAC
of 0.15 g was added and the nal pH was measured after 48 h un-
der agitation. The pH
pzc
is the point where pH
initial
pH
nal
= 0.
3. Results and discussion
3.1. Preparation of OPAC
3.1.1. Effect of chemical impregnation ratio
Effect of chemical impregnation ratio (IR) on the carbon yield
and adsorption equilibrium of MB was evaluated at the microwave
input power of 360 W and irradiation time of 5 min (Fig. 1a). It can
be clearly observed that carbon yield increased from 72.45% to
85.14% with increasing IR from 0.25 to 1.25. Beyond the value, fur-
ther increase in IR showed a gradually decrease of carbon yield.
Similarly, augmenting IR from 0.25 to 1.25 illustrated an enhance-
ment of adsorption uptake from 56.52 to 171.15 mg/g, and then
steadily decreased. The best adsorption capacity and carbon yield
of OPAC was obtained at the K
2
CO
3
/char ratio of 1.25.
The development of porosity was associated to the reduction
of K
2
CO
3
under inert condition to form K, K
2
O, CO and CO
2
. The
potassium compound formed during the activation step would dif-
fuse into the internal structure of char matrix, widens the existing
pores and creates new porosities, in according to the reactions
(McKee, 1983):
K
2
CO
3
2C !2K 3CO 14
K
2
CO
3
!K
2
O CO
2
15
K
2
O 2C !2K CO 16
Therefore, by increasing the ratio of K
2
CO
3
/char, the activation pro-
cess would be strengthened, and correspondingly, the adsorption
uptake was further enhanced.
When IR was lower than 1.25, the carbons on the active sites re-
acted partially lowering the adsorption uptake and carbon yield.
0
40
80
120
160
200
70
75
80
85
90
0.25 0.5 0.75 1 1.25 1.5 1.75 2
Adsorption capacity
Yield
Y
i
e
l
d

(
%
)
A
d
s
o
r
p
t
i
o
n

u
p
t
a
k
e

c
a
p
a
c
i
t
y

(
m
g
/
g
)
0
50
100
150
200
250
300
60
70
80
90
100
90 180 360 600 800
Adsorption capacity
Yield
Y
i
e
l
d

(
%
)
A
d
s
o
r
p
t
i
o
n

u
p
t
a
k
e

c
a
p
a
c
i
t
y

(
m
g
/
g
)
Impregnation ratio
Power level (W)
180
200
220
240
260
280
300
72
74
76
78
80
82
84
4 5 6 7 8
Adsorption capacity
Yield
Y
i
e
l
d

(
%
)
A
d
s
o
r
p
t
i
o
n

u
p
t
a
k
e

c
a
p
a
c
i
t
y

(
m
g
/
g
)
a
b
c
Radiation time (min)
Fig. 1. Effects of (a) chemical impregnation ratio (preparation conditions: micro-
wave power = 360 W; radiation time = 5 min), (b) microwave power (preparation
conditions: chemical impregnation ratio = 1.25; radiation time = 5 min) and (c)
radiation time (preparation conditions: chemical impregnation ratio = 1.25; micro-
wave power = 600 W) on the carbon yield and adsorption capacity.
K.Y. Foo, B.H. Hameed/ Bioresource Technology 104 (2012) 679686 681
Beyond the optimum value, the excess of K
2
CO
3
and metallic
potassium left in the carbon surface caused blocking of the pores
leading to a dramatic decrease of accessible area. Additionally,
the pores would be widened and burnt off.
3.1.2. Effect of microwave power
Effect of microwave power on the adsorption uptake capacity
and carbon yield were investigated at the IR of 1.25 and irradiation
time of 5 min (Fig. 1b). As suggested by the result, under low
microwave power levels of 90 and 180 W, the adsorption uptake
and carbon yield remained almost unchanged, indicating no
continual activation between the char and activating agent. At
higher microwave power of 360 and 600 W, the adsorption uptake
was drastically increased, possibly ascribed to the combined effect
of internal and volumetric heating responsible for the expansion of
carbon structure. At high radiation power of 800 W, over gasica-
tion might occur with detrimental impact of reducing surface area
and porosity, thus the adsorption uptake and yield were progres-
sively decreased. Meanwhile, the loss rate of carbon increased
proportional to the power levels, possibly due to the erce reaction
at high microwave power level which intensied a greater weight
loss of the carbon sample.
3.1.3. Effect of radiation time
Effect of microwave radiation time was conducted at the IR of
1.25 and microwave input power of 600 W. From Fig. 1c, prolong-
ing microwave radiation time from 4 to 6 min exhibited an
enhancement of adsorption uptake from 193.81 to 297.16 mg/g.
Obviously, prolonging time exposure promotes an acceleration of
energy, which in turn increases the reaction rates, thus developed
the porosity and rudimentary of the pore structure. However, as
the radiation time attains its optimum value, the absorption and
reection of energy tends to balance; and OPAC achieve its maxi-
mum adsorption capacity.
A slight drop (26.84 mg/g) was observed at 7 min. The phenom-
enon implied that temperature has risen dramatically as activation
proceeded, leading to the opening of the micropores and mesop-
ores, thus enlarging the average diameter. Besides, further heat
treatment might produce local hotspots, leading to the ablation
and shrinkage of the carbon internal channels reducing accessibil-
ity of the carbon active sites. Meanwhile, higher pyrolytic temper-
ature could promote CK
2
CO
3
, CK
2
O and CCO
2
reactions
facilitating breaking of the COC and CC bonds thus decreasing
the carbon yield (Adinata et al., 2007). Therefore, the optimal com-
bination for improvement of carbon yield and adsorption perfor-
mance was inferred at the IR of 1.25, microwave power of 600 W
and irradiation time of 6 min.
3.2. Characterization of OPAC
Nitrogen adsorption isotherm provides qualitative information
on the adsorption mechanism and porosity of the carbonaceous
adsorbents (Yang et al., 2010). The isotherm (Fig. 2a) features an
intermediate between type I and II of the International Union of
Pure and Applied Chemistry (IUPAC) classication, associated with
a combination of microporousmesoporous structures. The BET
surface area was determined using the BrunauerEmmettTeller
(BET) equation. The total pore volume was estimated as the liquid
volume of nitrogen at a relative pressure of 0.98, while the micro-
pore volume, micropore surface area and external surface area
were predicted using the t-plot method. The surface physical
parameters obtained from the N
2
adsorption isotherms were sum-
marized in Table 1. From the data, it is evident that the BET surface
area, Langmuir surface area and total pore volume of OPAC were
greatly improved (compared to char), implying pore development
during the microwave irradiation.
The pore size distribution of OPAC was ascertained using the
Density Functional Theory (DFT) model by minimizing the grand
potential as a function of uid density prole, as depicted in
Fig. 2b. The result detected the sharpest peak at pore diameter be-
tween 2 and 5 nm, with an average pore size of 22.27 , showing a
vast majority of the pores fall within the range of mesoporous
structures.
The elemental analysis of char and OPAC was listed in Table 2.
Microwave treatment led to an increase in carbon content but
caused a drastic decrease in oxygen content, resulting in an in-
crease in the C/O ratio from 1.49 to 2.93. The content of nitrogen
and hydrogen was slightly decreased, but the sulfur content in
the carbonized char was thermally stable.
The examination of the textural structures of char and OPAC
were evaluated from the scanning electron micrographs, as illus-
trated in Supplementary Fig. 2. It can be clearly seen that the pores
formed during the carbonization stage were narrowed, constricted
310
335
360
385
410
0 0.2 0.4 0.6 0.8 1
Relative Pressure (P/Po)
0.000
0.001
0.002
0.003
0.004
0.005
0.006
15 25 35 45
Pore width ()
Q
u
a
n
t
i
t
y

A
d
s
o
r
b
e
d

(
c
m

/
g

S
T
P
)
I
n
c
r
e
m
e
n
t
a
l

p
o
r
e

v
o
l
u
m
e

(
c
m
3
/
g
.

)
a
b
Fig. 2. Nitrogen adsorptiondesorption curve (a) and pore size distribution (b) of
OPAC.
Table 1
Porosity structure of the OP derived char and OPAC.
Properties Char OPAC
BET surface area (m
2
/g) 6.88 1104.45
Micropore surface area (m
2
/g) 3.32 420.09
External surface area (m
2
/g) 3.56 684.36
Langmuir surface area (m
2
/g) 9.81 1661.04
Total pore volume (cm
3
/g) 0.016 0.615
Micropore volume (cm
3
/g) 0.008 0.247
Mesopore volume (cm
3
/g) 0.008 0.368
Average pore size () 24.84 22.27
682 K.Y. Foo, B.H. Hameed/ Bioresource Technology 104 (2012) 679686
and dispersed by deposited tarry substances. However, OPAC dem-
onstrated a well organized and uniform pore structures, indicating
good possibility for the dyes to be adsorbed.
Representative FTIR spectra of char and OPAC were presented in
Supplementary Fig. 3. The bands located at 3436, 3237, 2361, 2343,
16491497, 1425, 1276, 1053 and 806 cm
1
corresponds to the
presence of NH, OH (hydroxyl), CC (alkynes), COOH, in-plane
OH (hydroxyl), CH
2
(alkyl), COC (ester, ether and phenol), CO
(anhydrides) and CH derivatives. For OPAC, the elimination of
peaks at 3436, 1497 and 806 cm
1
were indicative of the decompo-
sition of functional groups and release of volatiles matters by
microwave irradiation.
The surface acidity and basicity is an important criterion
describing the surface chemistry of the carbon adsorbents (El-
Sheikh et al., 2011). The pH
pzc
value of OPAC, the point which the
net charge of adsorbent is zero was measured using the acid/base
titration method as illustrated in Supplementary Fig. 4. From the
gure, the pH
ZPC
was found to be 6.33. Analysis of the data from
Table 2 shows that OPAC exhibited an acidic character. It has been
proposed that the acidic nature of OPAC was derived primarily
from the oxygen-containing groups (mainly carboxylic, anhy-
drides, lactones and phenols). However, the surface basicity is re-
lated to the presence of oxygen-free Lewis sites and carbonyls,
pyrone and chromene type structures at the edge of the carbon
layers.
3.3. Adsorption equilibrium studies
The curve adsorption uptake capacity, q
t
as a function of time, t
at concentrations 50, 100, 200, 300, 400, and 500 mg/L was dis-
played in Fig. 3a. Adsorption uptake capacity and dye removal ef-
ciency increase with prolonging the contact time. The adsorption
process increases sharply at the initial stage and gradually reduces
as equilibrium approaches. This phenomenon is attributed to the
reduction of immediate solute adsorption due to the lack of avail-
able open sites for dye adsorption (saturation), which in turn sup-
ported lm diffusion. The time required to attain this state of
equilibrium is termed as equilibrium time (Li et al., 2011).
Initial concentration provides an essential driving force for alle-
viating the mass transfer resistance between the aqueous phase
and the solid medium. In the present study, the adsorption equilib-
rium, q
e
increased from 50.46 to 389.53 mg/g with an increase in
initial concentration from 50 to 500 mg/L. The time prole of dye
uptake is a single, smooth and continuous curve leading to satura-
tion, suggesting possible monolayer coverage of dye onto the sur-
face of OPAC.
Solution pH exerts a profound inuence on the adsorptive up-
take of adsorbate molecule by regulating the surface charge and
ionization/dissociation of the adsorbate molecules. The adsorption
behavior of MB over a broad pH range of 212 was shown in
Fig. 3b. Increasing solution pH illustrates a signicant enhance-
ment from 319.41 to 438.92, mainly ascribed to the protonation
of MB in the acidic medium, and presence of excess H
+
ions
competing with dye cations for the adsorption sites. At higher solu-
tion pH, the number of negatively charged sites increased which
favors the adsorption of MB cations (Fernandez et al., 2010). Effect
of pH can be described on the basis of zero point of charge (pH
ZPC
).
The experimental determination of pH
ZPC
of OPAC was identied to
be 6.33. When solution pH < pH
ZPC
, activated carbon adsorbent will
react as a positive surface and as a negative surface when solution
pH > pH
ZPC
. Therefore, for pH values above 6.33, the formation of
electric double layer changes its polarity, consequently the surface
charge density and electrostatic attraction force increases.
3.4. Adsorption isotherm
Adsorption isotherm is an essential data source for practical de-
sign and fundamental understanding of the carbonaceous adsor-
bents. The parameters obtained from different isotherm models
are important for optimization of the adsorption mechanism path-
ways and expression of the surface properties of adsorbents (Foo
and Hameed, 2010). Due to the inherent bias resulting from linear-
ization, alternative isotherm parameter sets were determined by
non-linear regression.
Thus, in this study the nonlinear Freundlich, Langmuir, Dubi-
ninRadushkevich, RedlichPeterson, and Toth isotherm models
were established. This provides a mathematically rigorous method
for determining isotherm parameters using the original form of
isotherm equation. The detailed parameters for different forms of
isotherm equations were listed in Table 3. The correlation coef-
cients reported in Table 3 showed strong positive evidence on
the adsorption of MB onto OPAC follows Langmuir isothermmodel,
which suggests that the adsorption takes place on homogeneous
Table 2
Elemental analysis and acidity/basicity of the OPAC.
Element Char (wt.%) OPAC (wt.%)
Carbon 57.16 72.66
Oxygen 38.37 24.83
Hydrogen 1.42 0.76
Nitrogen 2.83 1.54
Sulfur 0.22 0.21
Acidity (mmol/g) 2.425
Basicity (mmol/g) 1.025
Total content of surface oxides (mmol/g) 3.450
0
100
200
300
400
0 5 10 15 20 25 30
500 mg/L
400 mg/L
300 mg/L
200 mg/L
100 mg/L
50 mg/L
300
340
380
420
460
0 2 4 6 8 10 12 14
pH
q
e
(
m
g
/
g
)
q
t
(
m
g
/
g
)
time (h)
a
b
Fig. 3. Effect of initial concentrations and time (a) and effect of pH (b) on the
adsorption of MB onto OPAC at 30 C.
K.Y. Foo, B.H. Hameed/ Bioresource Technology 104 (2012) 679686 683
sites that are identical and energetically equivalent. The results
also demonstrate no interaction and transmigration of dyes in
the plane of the neighboring surface. The suitability of Langmuir
isotherm to t the data was justied by the exponent value of Red-
lichPeterson and Toth isotherm models, g and t which approxi-
mate to unity, resulted to the original Langmuir equation.
The essential feature of Langmuir isotherm can be expressed in
terms of separation factor, R
L
, a dimensionless constant dened as:
R
L

1
1 K
L
C
0
17
which R
L
indicates isotherm to be either unfavorable (R
L
> 1), linear
(R
L
= 1), favorable (0 < R
L
< 1) or irreversible (R
L
= 0). From Supple-
mentary Fig. 5, it was clearly revealed that adsorption process
was favorable at the concentrations range being studied. Increasing
concentration from 50 to 500 mg/L demonstrated a gradually de-
crease of R
L
, indicating higher initial dye concentration may en-
hance the sorption process.
Table 4 lists the comparison of maximummonolayer adsorption
capacity of various activated carbons derived from different pre-
cursors. It can be concluded that the activated carbon prepared
in this work showed relatively large adsorption capacity of
382.75 mg/g as compared to the literature. Thus, it is noteworthy
that considerable changes in the surface properties were achieved
within a short time, which should be attributed to the distinct
mechanism of microwave heating (Foo and Hameed, 2009).
3.5. Adsorption kinetics
Adsorption kinetic describes the controlling mechanism of
adsorption processes which in turn governs the mass transfer
and equilibrium time (Mestre et al., 2011). The experimental data
of MB adsorption onto OPAC at different time intervals were exam-
ined using pseudo-rst-order, pseudo second-order and Elovich ki-
netic models, using the plots ln(q
e
q
t
) against t, t/q
t
versus t and
q
t
versus lnt, respectively. The corresponding results were tabu-
lated in Table 5. The suitability of the kinetic model to describe
the adsorption process was further validated by the normalized
standard deviation, Dq (%) dened as:
Dq 100

P
q
exp
q
cal
=q
exp

2
n 1
s
18
where n is the number of data points, q
exp
(mg/g) and q
cal
(mg/g) are
the experimental and calculated adsorption capacity, respectively.
Pseudo-second-order kinetic model yielded the best t, with
highest correlation coefcients and lowest normalized standard
deviation, Dq values which ranged between 0.07% and 5.43% for
MB initial concentration ranging from 50 to 500 mg/L. This sug-
gested that the overall rate of the adsorption process was con-
trolled by chemisorption which involved valency forces through
electrons sharing between the adsorbent and adsorbate.
3.6. Thermodynamic modeling
Adsorption thermodynamics provide an insight into the mech-
anism and adsorption behavior of an isolated system. Its original
concept assumes that energy cannot be gained or lost, which en-
tropy change is the driving force. The values of enthalpy change
(DH), Gibbs free energy change, (DG) and entropy change, (DS)
were computed according to the following equations:
lnK
L

DS
R

DH
RT
19
Table 3
Isotherm parameters for the adsorption of MB onto OPAC.
Isotherms Constants
Langmuir Q
0
(mg/g) K
L
(L/mg) R
2
382.75 0.98 0.998
Freundlich n K
F
(mg/g) (L/mg)
1/n
R
2
5.16 172.66 0.855
DubininRadushkevich q
s
(mg/g) E (J/mol) R
2
348.47 1984.97 0.923
RedlichPeterson a
R
(1/mg)
g
K
R
(L/g) g R
2
1.30 437.13 0.965 0.996
Toth a
T
(L/mg) K
T
(mg/g) t R
2
0.76 328.50 1.04 0.997
Table 4
Comparison adsorption capacities of various activated carbons for MB.
Precursor Activation method Activating agent Activation time (min) Adsorption capacity (mg/g) Reference
Orange peel Microwave heating K
2
CO
3
6 379.63 Present study
Coffee press cake Microwave heating 6 0.14 Franca et al. (2010)
Bamboo Microwave heating H
3
PO
4
10 286.10 Liu et al. (2010)
Cotton stalk Microwave heating KOH 10 294.12 Deng et al. (2010)
Spent catalysts of vinyl synthesis Microwave heating Steam 40 285.00 Zhang et al. (2009)
Pine wood powder Microwave heating ZnCl
2
10 200.00 Wang et al. (2009)
Piassava bers Conventional heating ZnCl
2
180 276.40 Avelar et al. (2010)
Rice straw Conventional heating (NH
4
)
2
HPO
4
120 129.50 Gao et al. (2011)
Coffee press cake Conventional heating N
2
60 14.90 Nunes et al. (2009)
Durian peel Conventional heating CO
2
60 284.00 Nuithitikul et al. (2010)
Apricot stone Conventional heating H
2
SO
4
1440 221.23 Demirbas et al. (2008)
Norit SA3 (Commercial grade powdered AC) 91.00 Yener et al. (2008)
Nuchar WWH (Commercial grade granular AC) 21.50 Yener et al. (2008)
684 K.Y. Foo, B.H. Hameed/ Bioresource Technology 104 (2012) 679686
DG RT lnK
L
20
where R (8.314 J/mol K) is the universal gas constant, T (K) is the
absolute solution temperature and K
L
(L/mg) is the Langmuir iso-
therm constant. The values of DH
s
and DS
s
were determined from
the slope and intercept of the vant Hoff plot of lnK
L
versus 1/T.
Negative DG (0.755 kJ/mol at 313 K and 1.387 kJ/mol at
323 K) dictates spontaneous nature and feasibility of the adsorp-
tion process with high preference of MB onto OPAC. Positive DS
(72.434 J/mol K) reveals the afnity of OPAC and increasing ran-
domness at the solid-solution interface during the adsorption pro-
cess, while positive DH (21.977 kJ/mol) indicates endothermic
nature of the adsorption process. This endothermic process was
due to the increase in temperature that enhanced the diffusion rate
of adsorbate molecules across the external boundary layer and in
the internal pores of adsorbent particle.
4. Conclusion
The results showed that orange peel is a potential raw precursor
for preparation of high quality activated carbon. Integration of
microwave heating has promoted porosity development in a short
heating period. The optimum condition for preparation of OPAC
has been identied at IR of 1.25, heating power of 600 W and irra-
diation time of 6 min. The adsorption behavior could be favorably
described by Langmuir isotherm model, while the adsorption ki-
netic was well tted to the pseudo-second-order model. Positive
DH value indicated endothermic nature of the adsorptive interac-
tion while negative DG veried the feasibility of the adsorption
process.
Acknowledgements
The authors acknowledge the nancial support provided by
Universiti Sains Malaysia under the Research University (RU)
Scheme (Project No. 1001/PJKIMIA/814072) and RU-PRGS grant
scheme (Project 465 No. 8043030).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.biortech.2011.10.005.
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Table 5
Kinetic models parameters for the adsorption of MB onto OPAC at different initial MB concentrations.
C
0
(mg/
L)
q
e,exp
(mg/
g)
Pseudo-rst-order Pseudo-second-order Elovich
k
1
(1/
h)
q
e,calc
(mg/
g)
R
2
Dq
(%)
k
2
(g/
mg)
q
e,calc
(mg/
g)
R
2
Dq
(%)
a b q
e,calc
(mg/
g)
R
2
Dq (%)
50 50.46 2.229 14.35 0.820 71.57 0.626 50.52 0.999 0.12 1.74 10
10
0.471 54.66 0.816 7.68
100 100.15 1.415 53.40 0.889 46.68 0.080 101.60 0.999 0.32 3.69 10
4
0.091 120.45 0.971 15.91
200 200.92 1.484 101.51 0.865 49.48 0.044 204.52 1.000 0.07 6.53 10
4
0.044 245.39 0.896 16.72
300 291.66 1.038 158.11 0.814 45.79 0.028 281.03 0.998 5.43 7.49 10
4
0.032 335.62 0.964 11.46
400 371.86 1.082 255.90 0.937 31.18 0.010 369.67 0.999 0.59 4.80 10
3
0.015 469.85 0.985 20.85
500 389.53 1.041 261.75 0.918 32.80 0.010 382.09 0.999 1.91 5.40 10
3
0.015 488.05 0.978 20.19
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