Journal of Environmental Chemical Engineering 5 (2017) 50615066

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

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

Research paper

Valorization of coee grounds into activated carbon using physicchemical MARK

activation by KOH/CO2

H. Laksacia, , A. Khelia, B. Belhamdia, M. Trarib
a
Laboratory of Physical and Chemical Study of Materials and Applications in the Environment, Faculty of Chemistry (USTHB), BP, 32-16111, Algeria
b
Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry (USTHB), BP 32, 16111 Algiers, Algeria

A R T I C L E I N F O A B S T R A C T

Keywords: Coee grounds were employed for the synthesis of activated carbons (ACs) by combined activation with CO2 and
Porosity KOH. The inuence of CO2 on the morphological properties and the sorption capacities of adsorbents prepared
Physic-chemical activation for phenol (phOH) and methylene blue (MB) was studied. The powders were investigated by infrared spectro-
Adsorption scopy, N2 isotherms and scanning electron microscopy. The activation by KOH under CO2 ow slightly improves
Isotherm
the porous structure (pore volume and specic surface area). The Langmuir isotherm provides a good correlation
Valorization
for both phenol and methylene blue and the adsorption kinetics obey a pseudo-second-order kinetic.
Activation

1. Introduction
Over the last years, adsorption was extensively applied for the
elimination of several pollutants from water. However, many of them
are not easy to eliminate. Recently, combined biological/adsorption
processes on activated carbons (ACs) are becoming attractive because
of their higher performances [1]. ACs are well known for their devel-
oped porosity, great specic surface areas as well as strong adsorption
capacity and thermo stability. They are used in many elds, like se-
paration and purication in both gases and aqueous solutions. They
serve also as catalyst supports to treat wastewaters and as adsorbents
for solvent recovery or discoloration [2,3]. Although ACs were the rst
recognized absorbent and are still widely used in industry, the devel-
opment of appropriate methods for their synthesis and the under-
standing of their porous structure is still of current interest. Un-
fortunately, the cost of ACs remains relatively high and limits their
extensive use [4]. In this study, we use coee ground as biomass in
order to produce inexpensive adsorbent. Indeed, during longtime, the
petroleum residues, woods and natural coal were the principal pre-
cursors for the elaboration of biosorbents [5]. Over the last decades,
this has prompted an increasing interest in the utilization of both
agricultural and industrial waste materials for the ACs preparation. Any
low cost biomass, with a high carbon percentage and low inorganic
content, can be employed as raw material for the ACs preparation [6].
In this regard, various carbonaceous compounds namely olive and dates
stones [7,8], vetiver roots [9], black stone cherries [10] and many
others are employed for the ACs synthesis.
The synthesis of ACs occurs by two successive steps: the carboni-
zation of raw carbonaceous precursors under inert gas ow followed in
a second step by their activation. The carbonization comes from pre-
cursor decomposition, leading to a large carbon mass with a rudimen-
tary porous structure; the activation can be realized physically and/or
chemically. In physical activation process, the precursors are activated
under H2O steam or CO2 ow in a temperature range (8001100 C)
[11,12] while in the chemical activation, the precursors are xed with
basic reagents (KOH, NaOH etc) [13] or acidic reagents (ZnCl2,
H3PO4, HCl, H2SO4 etc) [14]. The simultaneous carbonization and
activation are realized during chemical process: the precursor is mixed
with both the oxidant and dehydrating agents [15,16].
The manner the porosity is developed allows us to control the
porous nature of ACs and can predict their adsorption ability for both
organic and inorganic pollutants. ACs with various pore structures can
be elaborated from the same precursor by changing the operating
parameters and activation agents [16]. The modication of surface
structure of adsorbents in order to enhance their adsorption capacity
toward special adsorbates has gained great interest in the recent years
[1719].
The adsorption onto ACs is strongly dependent on the surface
physical and chemical properties. Because of its large dimensions,
methylene blue (MB) is a cationic dye actively used to probe the me-
soporosity of ACs by adsorption experiments[20]. Many works deal
with the properties of various adsorbents and MB is a model molecule
because of its medium size (diameter 20 ) for the adsorption on
mesoporous materials [21]. Conversely, phenol (phOH) comes from

Corresponding author.
E-mail address: laksaci.hamza@gmail.com (H. Laksaci).

http://dx.doi.org/10.1016/j.jece.2017.09.036
Received 13 July 2017; Received in revised form 16 September 2017; Accepted 19 September 2017
Available online 20 September 2017
2213-3437/ 2017 Elsevier Ltd. All rights reserved.
H. Laksaci et al. Journal of Environmental Chemical Engineering 5 (2017) 50615066

various industries and remains toxic for the aquatic environment. In- Table 1
deed, it is a small size molecule that can penetrate inside the pores with Chemical surface groups (meqg1).
diameter greater than 10 . In addition, phOH is a model adsorbate for
Sample ACK ACKCO2
the characterization of the sorption capacities of phenolic compounds,
well known for their high toxicity [22] Carboxylic groups 0.0704 0.0876
Only few papers on the combined activation of ACs are available in Lactonic groups 0.3872 0.4512
the open literature [23,24]. So, the aim of this study, was to develop a Phenolic groups 0.4664 0.736
Total acidic groups 0.924 1.275
technique for preparation of ACs using coee grounds by combination Basic groups 1.24245 1.3311
of chemical (KOH) at low impregnation ratio and physical (CO2) acti-
vation processes. The eect of CO2 as activation agent on the specic
surface area, total volume, micropore volume and eciency of elabo- each solution was titrated with HCl or NaOH. The amount of acidic
rated activated carbons was studied. The carbonized coconut shell was groups was determined on the assumption that NaOH neutralizes car-
impregnated with ZnCl2 under inert gas ow, followed by activation boxyls, phenols and lactons groups; Na2CO3 neutralizes carboxyls and
with CO2 [25]. It has been found that CO2 enlarged ne pores while the lactons groups while NaHCO3 neutralizes only carboxyls. The basic
mesopores content of AC from coconut and palm seed were 71% and groups content were obtained from the amount of HCl that reacted with
94% respectively. This study deals with the association of KOH/CO2 in carbon. The surface relief of ACs was visualized by scanning electron
the goal to improve the microstructure of prepared ACs. The analysis of microscopy (SEM) thanks to a JEOL, JSM-6360LV microscope.
kinetics data was performed by pseudo-rst and pseudo-second order
models while the equilibrium isotherms were evaluated by the Lang- 2.3. Kinetics and equilibrium study
muir and Freundlich models.
Isotherms provide information on the interaction adsorbate/ad-
2. Experimental sorbent. The parameters obtained from the various models provide the
main data on the surface properties, the adsorption mechanisms and the
2.1. Materials and sample preparation anities of biomasses. Several models can be applied for tting the
equilibrium adsorption data, the most appropriate are those of
ACs was prepared from Robusta coee grounds which were abun- Freundlich and Langmuir. The batch adsorption tests were carried out
dantly washed with water to remove the impurities, constituted by in 100 mL Erlenmeyers under constant stirring (150 rpm) immersed in
water-soluble substances, and dried at 110 C. The coee grounds were a thermostated bath at 25 C. The adsorption was done with no pH
pyrolysed at 400 C for 1 h under N2 ow at a heating rate of buer in order to preclude the interferences with other ions in solution.
300 C h1, to eliminate the volatile compounds. The chemical pro- The dispersions were ltered, and the remaining concentrations of
ducts were of high analytical quality. phOH and MB, were measured with a Jasco V-630 a spectrophotometer.
Two techniques were employed for the ACs preparation. In the rst The curves for absorbance calibration were plotted versus the con-
one, we mixed 2 g of pyrolysed coee ground with the appropriate centration of phOH and MB respectively at 270 and 663 nm.
amount of KOH (1 g of KOH/g of precursor). The mixture was put into a
tubular furnace under N2 ow and calcined at 800 C (300 C h1), kept 2.3.1. Kinetic study
at 800 C for 1 h and furnace cooled down to ambient temperature. The The kinetic study was undertaken for the adsorption equilibrium
second method consisted in combining two activating agent, physical time according to the following procedure: 50 mg of AC samples were
(CO2) and chemical (KOH). The char was placed in a tubular furnace introduced in 50 mL of MB (or phOH) solutions at initial concentrations
under N2 ow and heated at 800 C, then N2 ow was switched to CO2 of 250 mg/L for MB and 100 mg/L for phOH, for pre-determined time
ow with the same rate for 1 h and nally CO2 ow was switched back intervals. The recording time began when AC was added to the solution.
to N2 ow to terminate the activation. The solutions were separated from adsorbent by vigorous centrifugation
The excess of KOH was neutralized in HCl solution (0.1 N). Then, (4000 rpm, 5 min). The amount adsorbed at time t, Qt (mol/g), was
the material was washed until negative test with AgNO3 i.e. absence of calculated by the relation:
Cl. The sample was heated at 110 C and nally grounded and sieved
to get particles in the range (300 500 m). Qt =
V
(Co Ct ) mol/ g
m (1)
2.2. ACs characterizations
where Co and Ct are respectively the liquid concentrations at initial time
(t = 0) and at time t, m the adsorbent mass of and V the solution vo-
The characterization of the porous texture of ACs was carried out by
lume.
analyzing the adsorption isotherms of N2 at 77 K. The porosity was
The mechanism which controls the adsorption kinetics was studied
investigated by BET and t-plot isotherms. The N2 adsorption/desorption
by tting both pseudo-rst and pseudo-second order models to ex-
isotherms were determined with a Micrometrics equipment (AZAP
perimental data; the kinetic rate is given by:
2010), the powders were degased under vacuum (12 h at 150 C) before
each test. The specic surface areas (SBET) of ACs were calculated using dQt
= kn (Qe Qt )n
the BET equation taking an area of N2 molecule of 0.162 nm2. The dt (2)
micropore volume and microporous surface area were determined by 1
Qe (mol g ) is the adsorbed amount per unit mass of adsorbent at
the t-plot method. The external surface area (i.e. surface covered by the
equilibrium and Qt at time t, kn the rate constant for the nth order
mesoporous and macroporous volume) was evaluated by dierence
(min1 for n = 1 and g.mol1 min1 for n = 2). The linearized forms
between the BET surface area and microporous surface. The total pore
after integration are:
volume was estimated as the liquid volume of nitrogen (N2) adsorbed at
Pseudo-rst order kinetic (n = 1):
relative pressure of 0.98. The functional groups on the surface were
analyzed by the Fourier Transform Infrared spectroscopy (FTIR) with a ln(Qe Qt ) = ln Qe k1 t (3)
FTIR spectrometer (Spectrum two Perkin Elmer). The Boehm titration
Pseudo-second order kinetics (n = 2):
method was used to determine the amount of surface functional groups
[26]. For this purpose, 0.1 g of each sample was placed during 48 h, in t 1 t
= +
25 mL of 0.1 N solutions of HCl, NaOH, Na2CO3 and NaHCO3. Then, Qt k2 Qe 2 Qe (4)

5062
H. Laksaci et al. Journal of Environmental Chemical Engineering 5 (2017) 50615066

Fig. 1. The FTIR spectra of ACK and ACKCO2.

ACK

2,2

2,0

1,8

1,6

1,4

1,2

1,0

0,8

0,6

0,4

0,2

0,0
500 1000 1500 2000 2500 3000 3500 4000

Fig. 2. N2 adsorption-desorption isotherms of prepared ACs.

ACK
700

600

500

400

300

200

100

0,0 0,2 0,4 0,6 0,8 1,0

The linear plots of ln(Qe Qt) and t/Qt versus t are used for evaluation the Freundlich (6) and Langmuir (7) nonlinear models [27]:
of kn and regression correlation coecients (R2) respectively for the
1
pseudo-rst and pseudo-second order kinetic models. The best-t model Qe = KF Ce n (6)
was chosen on the base of R2 and calculated Qe.

Qm KL Ce
2.3.2. Adsorption isotherms Qe =
1 + KL Ce (7)
The adsorption performance of ACs was evaluated by adsorption
isotherm experiments. 50 mg of ACs samples were introduced in 50 mL
The model of Langmuir remains valid for monolayer surface ad-
of solutions with initial concentrations in the range of 10 to 200 mg/L
sorption with equivalent sites. Qmax (mg g1) is the maximal adsorption
for phOH, and 50 to 500 mg/L for MB. The samples were maintained
capacity while KL (L mg1) is related to the adsorption energy. By
24 h under stirring (150 rpm) at 25 C. After centrifugation, the con-
contrast, the empirical Freundlich model can be applied for hetero-
centrations of phOH and MB at equilibrium were determined by spec-
geneous systems with interaction between adsorbed molecules. The
trophotometry. The adsorbed quantity at equilibrium (Qe) was de-
heterogeneity factor (n) permits to indicate whether the adsorption is
termined as follows:
linear (n = 1), chemically (n < 1), or physically favorable (n > 1).
V 1/n < 1 indicates a Langmuir model while 1/n > 1 is for a co-
Qe = (C0 Ce ) (mol/g)
m (5) operative adsorption [28].
Co being the initial concentration and Ce the concentration at equili-
brium of MB and phOH (mol/L); the equilibrium data were tted by

5063
H. Laksaci et al. Journal of Environmental Chemical Engineering 5 (2017) 50615066

Fig. 3. The pore size distribution of ACK and ACKCO2 using DFT method.
ACK

0,035

0,030

0,025

0,020

0,015

0,010

0,005

0,000

-0,005
0 200 400 600 800 1000 1200 1400

Table 2
Textural properties of synthesized ACs.

SBET (m2 g1) Smicro (m2 g1) Sext (m2 g1) Vtot (cm3 g1) Vmicro (cm3 g1) Vmeso (cm3 g1) Burn-O (%)

ACK 1668 1642 26 0.66 0.61 0.05 15

ACKCO2 1865 1818 47 0.96 0.87 0.087 35

an amphoteric acidicbasic character. In order to determine which

functional groups are present on ACs surface, FTIR analysis in solid
phase was performed on samples using KBr disks. These functional
groups are partially responsible for ACs adsorption ability. The pore
system and specic interactions, also account for the uptake process.
The FTIR spectra of ACs (Fig. 1) show four strong bands: a large ab-
sorption band in the range (3300 3600 cm1) due to the stretching
vibration of OeH groups originating from carboxyls, phenols or alco-
hols and adsorbed water onto ACs. The OeH stretching vibration ap-
pears in a large frequency region, due to hydroxyl groups and OeH
bands of eCOOH function [29,30]. The little band at around
1700 cm1 is generally attributed to CeO stretching vibrations of lac-
tones, aldehydes, ketones or carboxyl groups coming from xanthine
derivatives like caeine [31]. The band at 12501300 cm1 is assigned
to CeO stretching and OeH bending modes of alcoholic, phenolic and
carboxylic groups.

3.2. Textural structures of ACs

Fig. 2 depicts the N2 adsorptiondesorption isotherms of the studied

adsorbents. Both ACK and ACKCO2 present typical (I + IV) isotherms
according to the IUPAC classication. The major nitrogen adsorption
occurs at relative pressures less than 0.3. A horizontal adsorption pla-
teau is observed at higher P/Po ratios, suggesting that the micropores
are dominant in the two ACs where there exist some mesopores in both
activated carbons because of small hysteresis and low deviation from
the plateau region in the isotherm plots. Moreover, the curves of the
pore size distribution (Fig. 3) indicate that the pores have sizes smaller
than 20 , located in microporous region. The physical characteristics
Fig. 4. SEM images of ACK and ACKCO2.
obtained from the N2 isotherms are gathered in Table 1. The specic
surface areas and total pore volumes of ACs increase from ACK to A-
CKCO2 when activated under the same conditions i.e the same im-
3. Results and discussion pregnation ratio. Table 2 shows an enhancement of AC microporous
volume by CO2 activation. The BET surface areas (SBET = 1865 m2 g1)
3.1. FTIR spectrum reported in Table 2 can be favorably compared with those produced by
dierent methods. The micropore volume and specic surface area are
The results of the Boehm titration (Table 1) indicate that ACs have slightly improved when using CO2 ux. Nevertheless, we have used soft

5064
H. Laksaci et al. Journal of Environmental Chemical Engineering 5 (2017) 50615066

ACK
ACK 160 ACKCO2
350
140
300
120
250
100
200
80

Qt (mg/g)
150
60

100 40

50 20

0 0

-50 -20
0 2 4 6 8 0 20 40 60 80 10 0 12 0

Fig. 5. Eect of contact time on the uptake of MB (a) and phOH (b) on prepared ACs.

Table 3
Kinetics parameters of phOH and MB adsorption onto ACK and ACKCO2.

Pseudo-rst order kinetic model Pseudo-second order kinetic model

Experimental Qe (mg/g) Qe (mg/g) k1 R2 Qe (mg/g) k2 R2

MB ACK 164 94 0.0120 0.890 177 17.15 105 0.998

ACKCO2 342 171 0.0087 0.998 365 8.66 105 0.999
phOH ACK 144 56 0.0289 0.947 151 101.20 105 0.998
ACKCO2 131 28 0.0256 0.942 134 213.12 105 0.999

k1: min1 for phOH and h1 for MB. k2: g mg1 mn1 for phOH and g mg1 h1 for MB.

ACK ACK
ACKCO2
400 b
200
350

300
150

250
Q e ( mg/g)

200 100

150

100 50

50
0
0

-50 0 50 100 150 200 250 300 350 0 20 40 60 80 100

Fig. 6. Adsorption isotherms of MB (a) and phOH (b) on prepared ACs.

Table 4 chemical activation with KOH just enough to minimize the presence of
Isotherms parameters of phOH and MB adsorption onto ACK and ACKCO2. macropores, followed by physical activation with CO2 to increase the
pores diameter and to develop a narrow pore size distribution. As
Langmuir Freundlich
shown in Table 2 and Fig. 2, all ACs have a microporous structure. The
Qmax mg/g KL l/mg R 2
KF n R2 large contribution of micropores was obtained for the chemically acti-
vated carbons where the Vmicro/Vt ratios are 0.92 for ACK and 0.90 for
MB ACK 274 0.111 0.997 129 7.615 0.974 ACKCO2. The samples activated with CO2 possess a slightly higher
ACKCO2 390 0.256 0.998 676 11.044 0.980
phOH ACK 238 0.062 0.997 39 2.670 0.984
mesoporous volume, with a greater average pore diameter and a hys-
ACKCO2 211 0.048 0.995 48 1.820 0.938 teresis loop (Fig. 2). The carbons ACK and ACKCO2 show a narrow pore
size distribution, which are located mainly in the microporous domain
(pore diameter: Dp < 30 ) with Dp of 15.82 for ACK and 20.50 for

5065
H. Laksaci et al.
ACKCO2.
3.3. Morphology by MEB
The SEM images of prepared ACs are shown in Fig. 4; several cav-
ities are observed on the ACs surface. The micrographs exhibit a het-
erogeneous surface and porous nature of ACs: the images ( m range)
show the pores which act as channels for the microporous adsorbent
lattice. ACKCO2 exhibits large channels than ACK because of pores
widening due to CO2 utilization.
3.4. Adsorption studies
3.4.1. Kinetics studies
The kinetic curves for PhOH and MB are reported in Fig. 5. The
kinetic studies show that equilibrium times of 100 min (PhOH) and 6 h
(MB) are required for the adsorption on ACs. At rst, the kinetic plots
indicate a rapid elimination rate for both molecules. Then, the ad-
sorption rate slows down and a tendency toward saturation is observed.
The slow adsorption rate is due to the fact that in the beginning all
adsorbent sites on the surface are free while the solute concentration
gradient is high. Therefore, the extent of phOH and MB species removal
decreases over time, because of the decreased number of vacant sites on
the surface. The maximal phOH removal of ACKCO2 is smaller than
that obtained with ACK. On the contrary for MB, the maximal uptake
for ACKCO2 was higher than that for ACK in agreement with the BET
results which indicate that ACKCO2 has a greater surface area and
larger pores diameter. The rate constants determined from both kinetic
models are summarized in Table 3. The experimental data are better
tted with the pseudo-second-order model with R2 values close to unity
and perfect agreement between Qcal and Qexp. So, this model is suitable
to describe the adsorption of both phOH and MB on our prepared ACs.
3.4.2. Equilibrium studies
According to Fig. 6, the phOH and MB isotherms conrm the L-type
model. The experimental data are tted by the Langmuir and Freun-
dlich isotherms and the parameters are gathered in Table 4. On the
basis of the coecients R2, it can be concluded that the Langmuir
model provides the best tting for adsorption data, with a nite number
of equivalent sites on the monolayer surface. Table 4 shows also that
ACKCO2 produced by physic chemical activation (KOH/CO2) presents a
slightly higher anity toward MB, rather than phOH, this indicates that
ACKCO2 contains more mesopores and therefore its capacity to adsorb
molecules of similar molecular weight and size as MB. AC activated by
KOH (ACK) gives a better adsorption for phOH than for MB. This evi-
dence clearly indicates that ACK has mainly a microporous structure
and a preferential adsorption for medium size molecules such as aro-
matic compounds.
The coee grounds ACs have a high adsorption capacity for phOH
and MB comparable with those of other adsorbents [9,10,32]. Ac-
cordingly, considering the abundance of this natural waste biosorbent,
it can be employed as alternative material to minimize the concentra-
tion of molecules whose sizes are similar to phOH and MB.
4. Conclusion
The present work was focused on the valorization of coee grounds
5066
Journal of Environmental Chemical Engineering 5 (2017) 50615066
as raw material in the preparation of ACs for environmental purposes.
The combined activations by CO2 and KOH enhance considerably the
microporosity of ACs and increase the adsorption for organic molecules
with great size. The porous structure seems to be the most inuent
parameter controlling the uptake of both molecules. The Langmuir
model gave a better correlation with equilibrium experimental data for
the phenol and methylene blue adsorption. In addition, the adsorption
of both molecules obeys to a pseudo-second-order kinetic. These ad-
sorbents could be employed for the elimination of organic compounds
with similar sizes to phenol and methylene blue.
Acknowledgments
The authors are indebted to Pr A. Addoun for his helpful discussion.
The work was nancially supported by the Faculty of Chemistry
(Algiers).
References
[1] F. een, . Aktas, Activated Carbon for Water and Wastewater Treatment:
Integration of Adsorption and Biological Treatment, John Wiley & Sons, 2011.
[2] Y. Li, Q. Du, T. Liu, Y. Qi, P. Zhang, Z. Wang, Y. Xia, Appl. Surf. Sci. 257 (2011)
1062110627.
[3] M. Hejazifar, S. Azizian, H. Sarikhani, Q. Li, D. Zhao, J. Anal. Appl. Pyrolysis 92
(2011) 258266.
[4] A. Mittal, J. Mittal, A. Malviya, V. Gupta, J. Colloid Interface Sci. 340 (2009) 1626.
[5] J. Guo, A.C. Lua, Mater. Chem. Phys. 80 (2003) 114119.
[6] W. Tsai, C. Chang, S. Lee, Carbon 35 (1997) 11981200.
[7] N. Spahis, A. Addoun, H. Mahmoudi, N. Ghaour, Desalination 222 (2008)
519527.
[8] B. Belhamdi, Z. Merzougui, M. Trari, A. Addoun, J. Appl. Res. Technol. 14 (2016)
354366.
[9] S. Altenor, B. Carene, E. Emmanuel, J. Lambert, J.-J. Ehrhardt, S. Gaspard, J.
Hazard. Mater. 165 (2009) 10291039.
[10] J.M.R.R. Arana, R.R. Mazzoco, J. Hazard. Mater. 180 (2010) 656661.
[11] S.S. Brum, M.L. Bianchi, V. d. Silva, M. Gonalves, M.C. Guerreiro, L. Oliveira,
Quim. Nova 31 (2008) 10481052.
[12] M.G. Lussier, J.C. Shull, D.J. Miller, Carbon 32 (1994) 14931498.
[13] J.B. Castro, P.R. Bonelli, E.G. Cerrella, A.L. Cukierman, Ind. Eng. Chem. Res. 39
(2000) 41664172.
[14] O. Ylmaz, I.C. Kantarli, M. Yuksel, M. Saglam, J. Yanik, Conserv. Resour. Recycl. 49
(2007) 436448.
[15] G. Crini, Bioresour. Technol. 97 (2006) 10611085.
[16] W. Li, K. Yang, J. Peng, L. Zhang, S. Guo, H. Xia, Ind. Crops Prod. 28 (2008)
190198.
[17] M.H. Kasnejad, A. Esfandiari, T. Kaghazchi, N. Asasian, J. Taiwan Inst. Chem. Eng.
43 (2012) 736740.
[18] M.H. Mahaninia, P. Rahimian, T. Kaghazchi, Chin. J. Chem. Eng. 23 (2015) 5056.
[19] M.H. Mahaninia, T. Kaghazchi, M. Soleimani, Int. Rev. Chem. Eng. (IRECHE) 6
(2014) 7376.
[20] C. Pelekani, V.L. Snoeyink, Carbon 38 (2000) 14231436.
[21] F. Rozada, M. Otero, A. Morn, A. Garca, Bioresour. Technol. 99 (2008)
63326338.
[22] F. Banat, B. Al-Bashir, S. Al-Asheh, O. Hayajneh, Environ. Pollut. 107 (2000)
391398.
[23] Z. Hu, M.P. Srinivasan, Y. Ni, Adv. Mater. 12 (2000) 6265.
[24] J. Laine, A. Calafat, Carbon 29 (1991) 949953.
[25] L. Giraldo, J.C. Moreno-Pirajn, J. Chem. 9 (2012) 938948.
[26] H. Boehm, Carbon 40 (2002) 145149.
[27] W. Liu, J. Zhang, C. Zhang, Y. Wang, Y. Li, Chem. Eng. J. 162 (2010) 677684.
[28] A.M. Vargas, A.L. Cazetta, M.H. Kunita, T.L. Silva, V.C. Almeida, Chem. Eng. J. 168
(2011) 722730.
[29] M. Iqbal, A. Saeed, S.I. Zafar, J. Hazard. Mater. 164 (2009) 161171.
[30] R. Gnanasambandam, A. Proctor, Food Chem. 68 (2000) 327332.
[31] K. Kaikake, K. Hoaki, H. Sunada, R.P. Dhakal, Y. Baba, Bioresour. Technol. 98
(2007) 27872791.
[32] A.S. Franca, L.S. Oliveira, M.E. Ferreira, Desalination 249 (2009) 267272.