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Article history:
Received 21 February 2016
Received in revised form
28 June 2016
Accepted 26 July 2016
Available online 28 July 2016
Fox nutshell was used as a new precursor for the production of a high surface area activated carbon with
zinc chloride activator at 600 C activation temperature and 2.0 impregnation ratio. The Brunauer
eEmmetteTeller (BET) surface area of the prepared activated carbon was 2869 m2/g with total pore,
micropore and mesopore volume of 1.96, 1.68 and 0.28 cm3/g. Methylene blue and phenol were used as
adsorbates for adsorption experiment onto prepared high surface area activated carbon in batch and
column scale. Adsorption kinetics of methylene blue and phenol was studied by using commonly kinetic
models, i.e., the pseudo-rst-order model, the pseudo-second-order model, and the intraparticle diffusion model. The experimental adsorption isotherms of these adsorbates on the prepared activated carbon
were analysed using three isotherm models: the Langmuir, Freundlich and Tempkin. The equilibrium
adsorption (qe) of methylene blue was increased from 249.88 to 968.74 mg/g and for phenol was
increased from 19.84 to 75.37 mg/g when initial concentration was enhanced from 100 mg/L to 500 mg/
L. The negative values of the enthalpy change (DH0 2.93 kJ/mol for MB and 16.92 kJ/mol for phenol)
indicate that the MB and phenol adsorption process onto FNAC was exothermic in nature. In column
experiments, the effects of the bed height of the packing material and ow rate of methylene blue and
phenol onto prepared activated carbon were studied.
2016 Elsevier Ltd. All rights reserved.
Keywords:
Fox nutshell
Activated carbon
Adsorption
Methylene blue
Phenol
1. Introduction
Dyes and Phenols are widely used in industries such as the
textile, paper, pulp mill, leather, dye synthesis, printing, food, and
plastics industries (Altenor et al., 2009; Bazrafshan et al., 2012b).
The wastewaters from such industries are generating considerable
amounts of colored and phenolic pollutants. These pollutants are
toxic, causing allergy, skin irritation, and even carcinogenic, posing
a serious hazard to living organisms (Altenor et al., 2009; Cazetta
et al., 2011; Royer et al., 2009). Therefore, it is necessary to
remove them from wastewater before it is discharged. For this
purpose, many treatment methods, such as chemical oxidation,
solvent extraction, chemical coagulation, photocatalytic degradation, membrane ltration, electrochemical methods, adsorption,
and biological treatments, have been developed for treating dyes as
* Corresponding author.
E-mail addresses: arvindkr202@gmail.com (A. Kumar), hmjena@nitrkl.ac.in
(H.M. Jena).
http://dx.doi.org/10.1016/j.jclepro.2016.07.177
0959-6526/ 2016 Elsevier Ltd. All rights reserved.
1247
qe
C0 Ce V
;
ms
R%
(1)
C0 Ce
100;
C0
(2)
qt
C0 Ct V
;
ms
(3)
where C0, Ce, and Ct are the initial, equilibrium, and at time t (min)
of adsorbates concentration (mg/L), V the volume of solution (L)
and ms the dry weight of the added adsorbent (g).
qtot
Q
1000
tt
Z tot
Cad dt;
(4)
t0
1248
of the column (bed capacity), qbed (mg/g) is dened by Eq. (5) (Aksu
nen, 2004; Salman et al., 2011):
and Go
qbed
qtot
;
ms
(5)
mtot
C0 Qttot
;
1000
(6)
%rem
qtot
100;
mtot
(7)
Table 1
Product yields, proximate, ultimate analysis and Pore structure characterization of
prepared activated carbon FNAC.
Ultimate analysis
Pore structure
characteristics
C
H
N
S
Oa
89.77
2.33
0.43
0.06
7.41
SBET (m2/g)
VT (cm3/g)
Vmicro (cm3/g)
Vmeso (cm3/g)
Vmicro/VT (%)
Dp (nm)
By difference.
2869
1.96
1.68
0.28
85.71
2.75
1249
Fig. 2. (a) Nitrogen adsorptionedesorption isotherms and (b) pore size distribution for
prepared activated carbon FNAC.
The adsorption of MB and phenol onto the FNAC was studied for
three hours over a pH range of 3e12 and 3e9. The initial concentration of MB and phenol was 100 mg/L, and the adsorbent dose
was kept at 0.03 g and 0.05 for MB and phenol respectively. The pH
was adjusted by adding a few drops of diluted 0.1N NaOH or 0.1N
HCl. The mixture was agitated in an orbital shaker at an optimized
agitation speed of 150 rpm at 30 C.
MB is a cationic dye with the estimated dimensions of
1.43 nm 0.61 nm 0.4 nm and its adsorption by activated carbon
is very susceptible to solution pH (Gokce and Aktas, 2014). Fig. 5
shows the initial pH increases from 3 to 12 then increases the %
removal of MB. The low adsorption rate of MB on FNAC observed at
pH 3 was due to the positive charge on the surface, causing H ions
to compete effectively with MB cations. When the pH of the solution increases, the positive charge on the interface of the solution
decreases and the negatively charged appeared on the adsorbing
surface, thereby resulting in an increased adsorption of MB due to
Fig. 3. Field Emission Scanning Electron micrographs of samples: (a) of Fox nutshell, and (b) of FNAC.
1250
Fig. 6. Effect of adsorbent dosage (C0 100 mg/L, pH 11 for MB and 7 for phenol,
temperature 30 C, contact time (t) 3 h) on the % removal of (a) MB and (b) phenol.
1251
lnqe qt lnqe k1 t;
(8)
t
1
1
t;
qt k2 q2e
qe
(9)
Fig. 7. Effects of contact time on the adsorption capacity at different initial concentrations at mass of adsorbent: (a) 0.04 g for 100 mL MB solution, pH: 11 and (b) 0.5 g
for 100 mL phenol solution; pH: 7.
Fig. 8. (a) Pseudo rst-order model and (b) pseudo second-order model for the
adsorption of MB onto the FNAC.
1252
qt ki t 0:5 c;
(10)
Fig. 9. (a) Pseudo rst-order model and (b) pseudo second-order model for the
adsorption of phenol onto the FNAC.
Table 2
Kinetic constants obtained for the adsorption of phenol adsorption onto FNAC at 30 C.
C0 (mg/L)
Parameters
MB
1
qe,exp (mg g )
Pseudo rst-order
qe,cal (mg g1)
h0 (mg g1 min1)
K1 (min1)
R2
Dq (%)
Pseudo second-order
qe,cal (mg g1)
k2 (g (mg min)1)
h0 (mg g1 min1)
R2
Dq (%)
Intraparticle diffusion
Ki (mg g1 min1/2)
R2
C
Phenol
100
200
300
400
500
100
200
300
400
500
249.88
483.84
695.55
836.07
968.74
19.84
38.25
55.25
67.06
75.37
10.45
8.74
0.087
0.8915
31.94
85.63
7.93
0.079
0.9231
9.14
101.65
7.74
0.0774
0.9703
30.4
93.82
7.77
0.0773
0.8222
29.59
348.53
7.80
0.078
0.8885
2.06
2.07
4.10
0.041
0.9904
20.11
16.42
11.60
0.058
0.995
9.23
17.55
17.52
0.0584
0.994
9.18
32.37
23.40
0.0585
0.998
6.31
33.63
29.80
0.0596
0.996
6.38
250.00
0.031
1937.50
1
0.0025
487.80
0.0022
518.73
1
0.037
699.30
0.00296
1447.50
1
0.02
840.34
0.00264
1864.30
1
0.017
970.87
0.00094
886.03
1
0.0072
19.82
0.081
31.82
0.999
0.023
38.21
0.0101
14.75
0.999
0.017
55.23
0.0094
29.29
0.999
0.005
67.01
0.0051
22.90
0.999
0.009
75.33
0.0057
34.37
0.999
0.006
0.64
0.4904
243.19
10.91
0.3916
375.72
8.34
0.3718
612.13
9.34
0.3852
742.50
19.84
0.6204
763.88
0.17
0.766
17.98
1.48
0.667
22.85
1.52
0.7465
39.13
2.51
0.7545
40.37
2.41
0.7097
49.86
1253
Ce
1
Ce
;
kL qm qm
qe
(11)
RL
1
;
1 kL C0
(12)
qe kF Ce n ;
Fig. 10. Intraparticle diffusion model for the adsorption of (a) MB and (b) phenol onto
the FNAC.
(13)
1
ln qe ln kF ln Ce ;
n
(14)
qe B lnA B lnCe ;
(15)
1254
Table 3
Isotherms constants for adsorption of MB and phenol onto FNAC at 30 C.
Adsorbates
MB
Phenol
Freundlich
Langmuir
Tempkin
kF (mg/g (L/mg)1/n)
R2
qm (mg/g)
kL (L/mg)
R2
A (L/g)
R2
402.02
20.42
5.79
3.5
0.971
0.987
980.39
78.74
0.171
0.129
0.9863
0.996
28.85
212.24
188.67
4.26
0.8661
0.988
Fig. 12. Langmuir isotherms for the adsorption of MB and phenol onto the FNAC.
Fig. 13. Freundlich isotherms for the adsorption of MB and Phenol onto the FNAC.
The temperature effect on the MB and phenol adsorption process was investigated with the thermodynamic parameters like a
change in Gibbs free energy (DG0), change in enthalpy (DH0) and
change in entropy (DS0). Its original concept assumes that energy
cannot be gained or lost, where entropy change is the driving force.
The values of DH, DG, and DS were calculated according to the
following equations:
KC
qeW=V
Ce
(16)
DG RTlnKC ;
lnKC
DS
R
DH
RT
(17)
;
(18)
1255
Fig. 14. Thermodynamic studies of MB and phenol adsorption onto the FNAC.
the slope and intercept of the van't Hoff plot of lnKC versus 1/T
(Figs. 14(a) and (b)). The calculated thermodynamic parameter
values are tabulated in Table 4. Generally, a value of DG0 in between
0 and -20 kJ/mol indicates physical adsorption i.e., electrostatic
interaction between adsorption sites and the adsorbing ion while a
more negative DG0 value ranging from 80 to 400 kJ/mol indicates that the adsorption involves charge sharing or transferring
from the adsorbent surface to the adsorbing ion to form a coordinate bond (chemisorption) (AlOthman et al., 2014; Singh, 2000).
The MB and phenol uptake increased with increasing temperature
up to 40 C. From Table 4, the negative Gibbs free energy (DG0) of
the experimental value indicates a typical physical process. The
positive value of DS shows an increased randomness or disorder of
the adsorbed species during MB adsorption process by FNAC
(AlOthman et al., 2014). The negative value of DS of phenol
Table 4
Thermodynamic parameters for the adsorption of MB and phenol onto FNAC.
Adsorbents
T(K)
DG (kJ/mol)
DH (kJ/mol)
DS (J/mol K)
MB
298
303
308
313
318
298
303
308
313
318
7.80
8.002
7.98
8.06
8.18
0.23
0.29
0.92
0.97
0.11
2.93
16.46
16.92
57.35
Phenol
1256
Table 5
A comparison of textural and adsorption capacity of some ACs reported in literature.
ACs
Methylene blue
Coconut shell AC
NAC60
Activated carbon produced from New Zealand coal
Filtrasorb 400
Calgon (F-400) AC
Grapefruit AC (GAC)
VetP0.5
Grape industrial processing waste AC
Tomato processing solid waste AC
Activated carbon produced from Venezuelan bituminous coal
vet-H20
Commercial AC
Coffee grounds AC
Filtrasorb 400
Rattan sawdust AC
Norit
Buriti shells AC
Posidonia oceanica (L.) dead leaves AC
Picacarb
Oil palm shell AC
Cocoa shell AC
Cotton stalk
Pine Cone AC
FNAC
Phenol
Filtrasorb100 (commercial)
CS850A
PAC6 (commercial from PICA)
Rattan sawdust based activated carbon
Vet-H20
Rice husk char
VetP0.5
WTAC
CAC1 (commercial, from Norit)
CAC2 (commercial, from Norit)
Commercial activated carbon
Activated carbon-commercial grade (ACC)
Activated carbon-laboratory grade (ACL)
Tectona grandis AC
Activated coal
FNAC
SBET (m2/g)
Vt (cm3/g)
Qm (mg g1)
Reference
2825
524
857.14
1216.4
997
1198
1170
1455
1093
863.50
1185
1440
925
e
e
e
843
1483
e
596.20
85
e
939
2869
1.498
0.2855
8.211
4.695
e
0.65
0.76
2.318
1.569
4.67
0.69
0.713
0.718
e
e
e
0.490
1.022
e
0.34
0.058
e
e
1.96
916
683.6
588
476
470
456.28
423
417
400
380
375
370
367
299
294.12
276
275
270.03
246
243.90
213
193.50
60.97
968.74
(Ozhan
et al., 2014)
Present study
937
1026.0
1226
e
1185
230.09
1170
1417
1350
620
e
336.6
492
585
e
2869
0.494
0.5768
0.53
e
0.69
e
0.76
1.1866
0.713
0.637
e
e
e
0.442
e
1.96
206
205.8
154
149.25
145
142.8
122
108.4
104
73
49.72
30.2187
24.6458
2.82
1.481
75.37
(Ozkaya,
2006)
(Srivastava et al., 2006)
(Srivastava et al., 2006)
(Mohanty et al., 2005)
(Vazquez et al., 2007)
Present study
Table 6
A comparison of % removal of MB and phenol by adsorption and other techniques.
Adsorbates
Methods
Method description
% Removal
Reference
Methylene blue
Chemical oxidation
Decolorization
Electrochemical degradation
Electrochemical oxidation
Ozonation
Adsorption
Physico-chemical
Degradation
Degradation and mineralization
Biodegradation
Adsorption
Fenton-like reaction
Fe2.22Ti0.78O4
Pt/MnO2 electrode
e
e
FNAC
Coagulants (Al2(SO4)3, Fe2(SO4)3, FeSO4, FeCl3)
Iron phthalocyanine-graphene donor-acceptor hybrids
BiPO4 photocatalysis assisted with H2O2
Immobilized by entrapment in calcium-alginate gel beads
FNAC
98
98
90
80
95.3
99.95
94
77.1
70
>98
99.19
(Ozbelge
et al., 2002)
(Wang et al., 2016)
(Liu et al., 2013)
(Gonzalez et al., 2001)
Present study
phenolic compounds
Phenol
Phenol
Phenol
Phenol
Table 7
The estimated cost of 1 kg of prepared granular activated carbon from Fox nutshell (US$/kg).
Requirements
Raw materials
Zinc chloride
Power consumption
NaOH N2 gas HCl
Total
0.89
79.88
0.74
1.36
82.87
1257
Fig. 16. Breakthrough curves for a) MB and b) phenol adsorption on prepared activated
carbon (FNAC) at different ow rates (initial adsorbates concentration 100 mg/L, bed
height 4 cm).
Fig. 15. Breakthrough curves for a) MB and b) phenol adsorption on prepared activated
carbon (FNAC) at different bed heights (initial adsorbates concentration 100 mg/L,
ow rate 5 mL/min).
min with a constant FNAC bed depth of 4 cm and 100 mg/L initial
concentration of both adsorbates. The effects of ow rate on the BT
curves are shown in Figs. 16(a) and (b). These BT curves show that
the column performed better at a lower ow rate, which resulted in
longer BT, exhaustion times and percent removal (Table 8). At a
lower ow rate for both MB and phenol, the BT time is longer than
that at a higher ow rate because a longer time is required to reach
its effective bed load. As the ow rate increased, the BT curve
became steeper since a shorter time was required to attain the
effective bed load and hence the effective adsorption capacity of the
FNAC column reduced. This is attributed to the insufcient
4. Conclusions
The prepared activated carbon from Fox nutshell has large BET
surface area and more pore volume. FESEM conrmed the pores are
developed on the surface of prepared activated carbon. The
maximum % removal was observed at pH 11 for MB and 7 for
phenol. The maximum removal % of MB and phenol was 99.95 and
Table 8
Column data parameters obtained at different bed heights and ow rates.
Adsorbates initial concentration (100 mg/L) Bed height (cm) Flow rate (mL/min) Breakthrough time (min) Exhaustion time (min) Bed capacity, qeq (mg/g) % Removal
MB
Phenol
4
3
2
4
4
4
3
2
4
4
5
5
5
10
15
5
5
5
10
15
430
160
30
150
25
410
220
130
80
30
2310
1520
980
1440
880
1980
1440
1060
1320
850
126.16
71.38
37.74
71.11
35.85
76.26
35.34
18.62
51.84
28.00
61.54
52.87
39.72
28.45
14.94
42.37
38.40
25.45
27.19
20.68
1258
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