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abstract
Article history:
The adsorption of Cu(II) from aqueous solution by carbons prepared from rice husk
through pyrolysis and steam activation was studied. The rice husk carbon was charac-
terized by Fourier transform infrared spectroscopy (FTIR) and scanning electron micros-
23 August 2010
copy (SEM), and its pore structure was also examined. After comparing different
characteristics of the carbons prepared under different conditions and their adsorption
abilities of Cu(II), the optimum temperature for pyrolysis and steam activation was chosen
Keywords:
as 700 and 750 C, respectively, using 3% (V/V) steam as the best activation gas. It was
Carbon
found that the Cu(II) adsorption on the rice husk derived carbons was pH and temperature
Rice husk
Characterization
adsorption kinetics and isotherms of Cu(II) by the rice husk derived carbons were also
Adsorption
investigated under four different temperatures, and good correlation coefficients were
Cu(II)
obtained for the pseudo-second-order kinetic models, and the Langmuir isotherm model
fitted very well with the experimental data. The mean free energy E (kJ mol1) obtained in
the Dubinin-Radushkevitch (D-R) adsorption isortherm equation indicated a chemical ionexchange mechanism. Several thermodynamic parameters were also caculated to predict
the nature of adsorption process.
2010 Elsevier Ltd. All rights reserved.
1.
Introduction
b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
2.
2.1.
Adsorbent preparation
465
temperature, and it was aerated with the activation gas containing steam at a certain concentration while using nitrogen
as the carrier gas (2.5 m3 h1) for 1 h. Once the activation was
completed the activation gas was changed to nitrogen gas to
supply to the sample until it could be sealed in a container. In
this study, the carbon labeled with RHA-700-750 means it
was prepared with the pyrolysis temperature of 700 C and the
activation temperature of 750 C, and RH indicates the rice
husk which was used to obtain the carbon.
2.2.
Adsorbent characterization
2.3.
Chemicals
2.4.
Adsorption studies
Adsorption experiments were carried out in 250 mL Erlenmeyer flasks containing a certain amount of carbon prepared
previously and a 100 mL solution with known concentration,
pH value and temperature. The flasks were shaken in
a constant temperature beaker (Shanghai Yihen Scientific
Instrument Co. Ltd., China) at 90 rpm. After a preset contact
time, the samples were all filtrated through 0.22 mm pore-size
filters. The concentration of the residual copper ions in the
filtrate was analyzed by an atomic absorption spectrometer
(Shimdzu AA-6300, Japan). The amount of copper ions adsorbed on the carbon was calculated from the difference between
the initial concentration of Cu(II) and the residual Cu(II)
466
-1
465 cm
803 cm
1090 cm
-1
-1
1600 cm
1700 cm
-1
3431 cm
2920 cm
-1
-1
-1
b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
c
4000
3000
2000
1500
1000
500
-1
wave number(cm )
VC0 Ct
W
(1)
3.
3.1.
Characteristics of adsorbent
3.1.1.
3.1.2.
vP0 =P 1
vm c P0
vm c
where P and P0 are the equilibrium and the saturation pressure of adsorbates at the temperature of adsorption, respectively, v is the adsorbed gas quality, and vm is the monolayer
adsorbed gas quality, and c is the BET constant.
The values of vm and c can be obtained from linear
regression, and the specific surface area can be calculated
from the following equation:
SBET;total
(2)
SBET
vm Ns
V
(3)
Stotal
a
(4)
Table 1 e The pore structure properties of the carbon derived from rice husk at different preparation temperatures.
Sample
RHA-500-550
RHA-600-650
RHA-700-750
Vmicro/Vtotal (%)
Vmeso/Vtotal (%)
146.7
168.8
231.7
0.1034
0.1145
0.1466
0.0566
0.0670
0.0980
0.0468
0.0475
0.0485
54.73
58.52
66.89
45.27
41.48
33.11
467
b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
Table 2 e The pore structure properties of the carbon prepared with different amounts of steam in the activation gas.
Sample
RHA-700-750 (0%)
RHA-700-750 (3%)
RHA-700-750 (6%)
Vmicro/Vtotal (%)
Vmeso/Vtotal (%)
155.1
231.7
244.3
0.1047
0.1466
0.1556
0.0648
0.0980
0.1023
0.0399
0.0485
0.0534
61.89
66.89
65.70
38.11
33.11
34.30
3.1.3.
(5)
Elemental analysis
C (%)
O (%)
Si (%)
37.93
15.33
43.60
37.29
48.88
56.31
46.34
43.34
13.20
28.36
10.06
19.37
3.1.4.
Surface morphology
3.2.
468
b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
Fig. 2 e SEM micrographs of (a) the outer surface of RHA-700-750, (b) the outer surface of rice husk, (c) the inner surface of
RHA-700-750, (d) the inner surface of rice husk, (e) the section of RHA-700-750, and (f) RHA-700-750 treated with Cu(II)
aqueous solution.
3.3.
Effect of pH
The effect of initial pH on the Cu(II) adsorption was investigated over a pH range of 3.0e6.0. The variation of the amounts
of Cu(II) adsorbed by 4 g L1 carbon from 100 mL aqueous
solution of 64 mg L1 at the 30 C is shown in Fig. 4. It could be
observed that when the initial pH of the Cu(II) aqueous
469
b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
16
100
12
10
60
-1
Qt (mg g )
14
80
40
RHA-400-450
RHA-500-550
RHA-600-650
RHA-700-750
RHA-800-850
20
0.2
0.3
0.4
0.5
0.6
6
4
2
0
0.1
0.7
3.0
3.5
4.0
4.5
80
6.0
60
acidity, pH 5.0 was selected as the optimum value for conducting further experiment.
40
3.4.
activation without steam
activation with 3% (V/V) steam
activation with 6% (V/V) steam
20
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Effect of temperature
5.5
100
Qt (mg g )
5.0
Solution pH
10
8
25 C
o
30 C
o
35 C
o
40 C
6
4
2
0
10
15
20
25
Time (h)
470
b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
Table 4 e Adsorption kinetic constants and correlation coefficients for adsorption of Cu(II) at different temperatures.
Temperature ( C)
Pseudo-first-kinetic model
1
25
30
35
40
12.51
14.32
14.29
15.78
Qe,cal (mg g )
K1 (min )
K2 (g mg1 min1)
r2
10.76
12.64
12.88
14.22
1.0293
1.0320
0.9610
1.4543
0.730
0.793
0.858
0.859
12.94
14.64
14.68
15.95
0.0630
0.0677
0.0673
0.0906
0.995
0.997
0.999
0.999
3.5.
Qe
t
1
t
K2 Qe2 Qe
(7)
where Qe and Qt are the amount of Cu(II) ions absorbed (mg g1)
at equilibrium and time t, respectively; and K2 is the rate
constant of pseudo-second-order kinetic model (g mg1 min1).
The kinetics parameters obtained by using non-linear
regression are listed in Table 4. Fig. 6 illustrates the two kinetic
models at the temperature of 30 C. It can be seen from both
Table 4 and Fig. 6 that compared with pseudo-first-order
model, the pseudo-second-order model fitted the experimental data better with the correlation coefficients (r2) values
under four temperatures all above 0.995 and the calculated Qe
very close to the experimental values. Also some literatures
have reported that the adsorption of Cu(II) on the carbon
derived from some biomass follows the pseudo-second-order
model, which is based on the consumption that chemisorption is the rate-limiting step with the electron sharing and
exchanging between adsorbent and adsorbate [2,30].
3.6.
(8)
Qe KF Ce1=n
(9)
(10)
1
E p
2b
(11)
16
14
12
10
-1
(6)
1
Qm KL Ce
1 KL Ce
Qt (mg g )
and temperature were 0.4 g, 5.0 and 30 C, then the widely used
Langmuir isotherm [32] and Freundlich isotherm [33] were
applied to analyze experimental data. And the DubininRadushkevich (D-R) isotherm [34] was also used in this study.
The Langmuir equation can be expressed as:
Adsorption kinetics
Qt Qe 1 eK1 t
Pseudo-second-kinetic model
1
8
o
Experimental data at 30 C
Adsorption isotherms
4
2
0
0
10
15
20
Time (h)
Fig. 6 e Adsorption kinetics of Cu(II) on carbon derived
from rice husk at 30 C.
25
471
b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
Table 5 e Adsorption isotherm constants and correlation coefficients for adsorption of Cu(II) at different temperatures.
Temperature ( C)
Langmuir isotherm
1
25
30
35
40
1
Freundlich isotherm
1
KL (l mg )
KF (mg g )
Qm (mg g )
E (kJ mol1)
r2
21.01
21.88
23.09
25.25
0.250
0.154
0.116
0.152
0.998
0.995
0.995
0.998
6.049
4.626
5.512
6.329
3.943
3.179
3.730
3.782
0.861
0.885
0.908
0.905
36.47
38.6
36.77
40.22
14.7
13.3
14.3
14.6
0.917
0.903
0.936
0.923
3.7.
D-R isotherm
Qm (mg g )
Adsorption thermodynamics
1
as vs Qe
ae ve Ce
(12)
where as and ae are the activity of adsorbed Cu(II) ions and the
activity of Cu(II) ions in the solution at equilibrium, vs and ve
are the activity coefficient of adsorbed Cu(II) ions and the
activity coefficient of Cu(II) ions in the solution at equilibrium,
respectively. As the Cu(II) ions concentration in the solution
decreases and approaches to 0, K0 can be got by plotting
a straight line of ln(Qe/Ce) versus Qe based on a least-square
analysis, and then extrapolating Qe to 0, the intercept with the
vertical axis is the value of K0.
The free energy change (DG0), enthalpy change (DH0), and
entropy change (DS0) were determined by the following
equations:
DG0 RTln K0
DG0 DH0
TDS0
R
(13)
(14)
25
4.
-1
Qe (mg g )
20
15
o
Experimental data at 30 C
10
Langmuir fit
Freundlich fit
D-R fit
0
0
50
100
150
200
250
300
-1
Ce (mg L )
Conclusions
472
b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 4 6 4 e4 7 2
Acknowledgments
This research was supported by the National Water Pollution
Control and Management Project of China (No. 2008ZX07101006) and the Science and Technology Project of Zhejiang
Province, PR China (No. 2009C33120).
references