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abstract
Article history:
A novel biosorbent derived from agricultural residue e walnut shell (WS) is reported to
remove cesium from aqueous solution. Nickel hexacyanoferrate (NiHCF) was incorporated
into this biosorbent, serving as a high selectivity trap agent for cesium. Field emission
5 February 2013
analysis (TG-DTA) were utilized for the evaluation of the developed biosorbent. Determi-
nation of kinetic parameters for adsorption was carried out using pseudo first-order,
pseudo second-order kinetic models and intra-particle diffusion models. Adsorption
Keywords:
Walnut shell
analysis parameter c2 between the experimental and predicted values of the Freundlich
Cesium adsorption
Integrated analysis
adsorption. Thermodynamic studies were conducted under different reaction temperatures and results indicate that cesium adsorption by NiHCF-WS is an endothermic (DH > 0)
and spontaneous (DG < 0) process.
2013 Elsevier Ltd. All rights reserved.
1.
Introduction
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w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 5 6 3 e2 5 7 1
widely used. However, due to the high cost of materials, largescale application of solvent extraction is limited. In the case of
ion exchange process, inorganic ion exchangers are found to
be superior over organic ion exchangers due to their thermal
stability, resistance to ionizing radiation and good compatibility with final waste forms (Nilchi et al., 2002; Plazinski and
Rudzinski, 2009). Natural occurring clay minerals such as
zeolite, bentonite and montmorillonite are usually used as
low cost adsorption materials for Cs removal from aqueous
solution, however the main disadvantage is the competitive
interactions of other monovalent cations, in particular Na
and K that can considerably block Cs adsorption (Borai
et al., 2009; El-Naggar et al., 2008; Goni et al., 2006; Lehto and
Harjula, 1987; Plazinski and Rudzinski, 2009).
Transition metal hexacyanoferrates, especially nickel
hexacyanoferrate (NiHCF) is known as a highly selective agent
for Cs adsorption (Chen et al., 2013; Plazinski and Rudzinski,
2009). It possesses a special cubic structure with a channel
diameter of about 3.2
A, through which only small hydrated
ions like Cs can permeate. Larger hydrated ions like Na get
blocked (Plazinski and Rudzinski, 2009; Pyrasch et al., 2003).
However, the very fine particle size of NiHCF restricts its direct
use in practice, thus proper support materials are necessary.
Recently, several kinds of low cost biosorbents have been
investigated for the removal of heavy metals (Figueira et al.,
2000; Plazinski and Rudzinski, 2009; Reddad et al., 2002).
Walnut shell, an abundant agricultural residue with good
stability has been successfully used in removing heavy metals
by adsorption (Altun and Pehlivan, 2012; Saadat and KarimiJashni, 2011; Zabihi et al., 2010). To the best of our knowledge, however, few studies have focused on equilibrium, kinetic and thermodynamic modeling of Cs adsorption using
walnut shell. This study presents the first low cost biosorbent
derived from walnut shell (WS) as support material incorporated into NiHCF (NiHCF-WS), fabricated for Cs adsorption.
2.
2.1.
Materials
2.2.
Reagents
2.3.
2.4.
Kinetic studies
(1)
k2 qe t
1 k2 qe t
(2)
w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 5 6 3 e2 5 7 1
(3)
1
2.5.
Equilibrium studies
A fixed amount of NiHCF-WS was mixed with 20 mL Cs solution in a 50 mL-polypropylene tube (VIOLAMO, Japan) at a
shaking speed of 200 rpm. Resultant supernatants were
withdrawn after 24 h prior to the Cs concentration
determination.
2.5.1.
Adsorption isotherms
To optimize the design of an adsorption system, it is important to establish the most appropriate correlation for equilibrium conditions (Parab and Sudersanan, 2010). According to
different adsorption mechanisms, there are currently several
different adsorption isotherms used for fitting experimental
adsorption results. Among these, Langmuir (1918), Freundlich
(1907) and Dubinin et al. (1947) isotherms are widely used and
therefore are applied in this study. The nonlinear forms of
these isotherms are given as follows:
Langmuir isotherm : qe
qm bCe
1 bCe
ACs
RK
Ce Cb V
1000
39
DeR isotherm : qe qm exp b2
(6)
1
RTln 1
Ce
(7)
where, qe (mg g1) is the amount of Cs adsorbed at equilibrium, Ce (mg L1) is the equilibrium concentration of Cs. b
(L mg1) is a constant related to the free energy or net enthalpy
of adsorption (bfeDG/RT) (Mohan and Singh, 2002), and qm
(mg g1) is the adsorption capacity at the isotherm temperature. kf and n are equilibrium constants indicative of adsorption capacity and adsorption intensity respectively. b (mol2/
kJ2) is the constant related to the adsorption energy, R
(8.314 J mol1 K1) is the gas constant and T (K) is the absolute
temperature of the aqueous solution.
(8)
(9)
2.6.
Thermodynamic studies
In order to obtain the thermodynamic nature of the adsorption process, 0.2 g NiHCF-WS was added into 20 mL Cs solutions with an initial concentration of 10 mg L1 (adsorbent
dosage of 10 g L1) at different temperatures (298, 308 and
318 K) for 24 h. Thermodynamic parameters, namely, standard Gibbs free energy (DG ), standard enthalpy (DH ) and
standard entropy (DS ) changes were also determined in order
to obtain the thermodynamic nature of the adsorption process. The amounts of DH and DS could be calculated from the
slope and intercept of the straight line obtained from plotting
lnKd versus 1/T, respectively using the following equation
(Nilchi et al., 2011; Tsai et al., 2009):
lnKd
(5)
C0 Ce V
1000
133
where ACs (mmol) is the amount of Cs adsorbed by NiHCFWS, C0 (mg L1) is the initial concentration of Cs, Ce
(mg L1) is the equilibrium concentration of Cs, V (L) is the
volume of solution and 133 is the molar mass of Cs.
(4)
Freundlich isotherm : qe kf Ce
2.5.2.
2565
DS DH
R
RT
(10)
2.7.
(11)
Analysis
2566
w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 5 6 3 e2 5 7 1
2.8.
Calculation
C0 Ct V
1000M
(12)
C0 Ct V
Ct
M
(13)
2.9.
3.
3.1.
Characterization of biosorbent
3.1.1.
The FE-SEM images of walnut shell before and after modification are shown in Fig. 1. It can be seen that the raw
walnut shell has a complex and multilayer structure
including the obvious fibrous lignocellulosic (Fig. 1a). After
modification, there is a remarkable difference in the surface structure of walnut shell with NiHCF particles
attached on the surface of walnut shell, as depicted by the
arrows in Fig. 1b.
w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 5 6 3 e2 5 7 1
2567
Fig. 2 e TG-DTA results of walnut shell and nickel hexacyanoferrate incorporated walnut shell obtained at the heating rate
of 10 C minL1 in air atmosphere. (Pan: Al-Pan; Reference: Open-Al-Pan; Upper limit temperature: 550 C; Gas flow rate:
200 mL minL1).
3.2.
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w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 5 6 3 e2 5 7 1
Fig. 3 e Application of non-linearized pseudo first (solid line) and second (dash line) order kinetic models for cesium
(10 mg LL1) adsorption by walnut shell (square) and nickel hexacyanoferrate incorporated walnut shell (circle) at 25 C
(20 g LL1). (Fig. (b) shows the enlarged dark part in Fig. (a).).
3.3.
Equilibrium studies
3.3.1.
2
X qexp
qcal
e
e
qcal
e
(14)
Table 1 e Sorption rate constants associated with pseudo first and second order kinetic models.
Pseudo first-order kinetic model
WS
exp
qe a
1
(mg g )
k1 (min1)
b
(mg g1)
qcal
e
2
R
0.11 0.04
0.37 0.39
0.10 0.01
0.492
exp
qe
1
(mg g )
k2 (g mg1 min1)
1
qcal
e (mg g )
2
R
a means the equilibrium sorption capacity estimated from the experimental data.
b means the equilibrium sorption capacity calculated from the kinetic model.
WS
NiHCF-WS
0.11 0.04
(3.8 4.0) 1045
0.099 0.01
0.483
0.52 0.004
0.23 0.03
0.54 0.01
0.981
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w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 5 6 3 e2 5 7 1
3.3.2.
where qcal
(mg g1) is the equilibrium uptake amount calcue
exp
lated from the isotherm and qe (mg g1) is the experimental
equilibrium uptake amount. A smaller c2 value indicates a
better fitting isotherm.
In addition, the values of normalized standard deviation
(NSD (%)) were also calculated to validate the fitness of
isotherm
to
experimental
data
(Karamanis
and
Assimakopoulos, 2007), which is defined as:
s
exp 2
P exp
qe qcal
qe
e
NSD% 100
N1
(15)
Table 2 e Adsorption isotherm constants of cesium adsorption process on nickel hexacyanoferrate incorporated walnut
shell.
Langmuir isotherm
1
Freundlich isotherm
qm (mg g )
4.94 0.5
b (L mg1)
R2
c2
NSD (%)
0.06 0.02
0.93
21.1
57.3
kf (mg g
1
1/n
n
R2
c2
NSD (%)
1/n
mg
DeR isotherm
1
1.12 0.2
qm (mg g )
4.43 0.4
0.27 0.04
0.93
0.96
60.7
b (mol2/kJ2)
R2
c2
NSD (%)
(3 0.8) 105
0.92
1.3 10281
310.2
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w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 5 6 3 e2 5 7 1
Table 3 e Relation between the cesium adsorbed and potassium released during the cesium adsorption on nickel
hexacyanoferrate incorporated walnut shell.a
No.
1
2
3
4
5
6
7
Dosage (g L1)
5
10
15
20
20
20
20
10
10
10
10
100
200
400
Cs adsorbed (mmol)
0.5
0.9
1.4
1.4
10.3
12.3
14.6
K released (mmol)
0.02
0.002
0.001
0.001
0.07
0.01
0.1
0.1
1.5
4.6
4.7
13.4
16.7
19.6
0.0
0.06
0.3
0.2
0.2
0.02
0.1
a Samples were tested in 50 mL polypropylene tubes with 20 mL Cs solutions at room temperature and 200 rpm for 24 h.
Table 4 e Thermodynamic study of cesium adsorption by nickel hexacyanoferrate incorporated walnut shell.
Temp. (K)
298
308
318
3.4.
Kd (mL g1)
171.4
757.1
2264.3
12.9
16.8
20.6
101.8
0.385
Thermodynamic study
4.
Conclusion
Acknowledgments
This work was supported in part by Scientific Research (A)
22248075 from the Japan Society for the Promotion of Science
(JSPS). The authors also want to give thanks to the Environmental Diplomatic Leader (EDL) writing center, University of
Tsukuba, for proofreading.
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