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Abstract
One kind of adsorbents with high adsorption capacity of anionic dyes was prepared using ionically and chemically
cross-linked chitosan beads. A batch system was applied to study the adsorption of four reactive dyes (RB2, RR2,
RY2, RY86), three acid dyes (AO12, AR14, AO7) and one direct dye (DR81) from aqueous solutions by the crosslinked chitosan beads. The adsorption capacities had very large values of 19112498 (g/kg) at pH 34, 30 C, which
were 3.415.0 and 2.727.4 times those of the commercial activated carbon and chitin, respectively. The Langmuir and
Freundlich adsorption models were applied to describe the equilibrium isotherms. The Langmuir model agreed very
well with experimental data (R2 > 0.9893). The kinetics of adsorption, the ADMI color value and decolorization eciency for dierent initial dye concentrations were evaluated by the pseudo rst-order and second-order models. The
data agreed very well with the pseudo second-order kinetic model. The adsorption capacity increased largely with
decreasing solution pH and adsorbent dosage. The free energy changes G0 for adsorption of anionic dyes in acidic
solutions at 30 C were evaluated. The negative values of G0 indicate overall adsorption processes are spontaneous.
# 2003 Elsevier Ltd. All rights reserved.
Keywords: Adsorption capacity; Anionic dyes; Cross-linked chitosan beads; Langmuir isotherm; Pseudo second-order model
1. Introduction
Various kinds of synthetic dyestus appear in
the euents of wastewater in some industries such
as dyestu, textiles, leather, paper, plastics, etc.
Since a very small amount of dye in water is highly
visible and can be toxic to creatures in water, the
removal of color from process or waste euents
becomes environmentally important. Among several chemical and physical methods, the adsorption process is one of the eective techniques that
* Corresponding author. Tel.: +886-37-352840x62; fax:
+886-37-332397.
E-mail address: chiou@mail.nuu.edu.tw (M.-S. Chiou).
0143-7208/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0143-7208(03)00140-2
70
71
72
Table 1
Details of anionic dyes
Anionic dyes
Reactive Blue 2 (RB2)
Reactive Red 2 (RR2)
Reactive Yellow 2 (RY2)
Reactive Yellow 86 (RY86)
Acid Orange 12 (AO12)
Acid Red 14 (AR14)
Acid Orange 7 (AO7)
Direct Red 81 (DR81)
lmax
(nm)
F.W.
(g/mol)
Supplier
614
534
402
416
484
514
484
508
774.20
615.34
872.97
596.01
350.33
502.44
350.33
675.61
Sigma
Aldrich
Aldrich
Sigma
Aldrich
Aldrich
Aldrich
Aldrich
QbCe
1 bCe
73
adsorption capacity when the surface is fully covered with dye molecules and assists in the comparison of adsorption performance. Q and b are
computed from the slopes and intercepts of the
straight lines of plot of Ce =qe vs. Ce.
The Freundlich isotherm is given as
qe Qf Ce1=n
74
Fig. 2. Equilibrium adsorption isotherm of (a) reactive dyes and (b) acid and direct dyes on cross-linked chitosan beads.
k1
t
2:303
t
1
t
q k2 q2e qe
75
Reactive dye
RB2
RR2
RY2 (pH4)
RY86
Acid dye
AO12
AR14
AO7 (pH4)
Direct dye
DR81 (pH4)
Freundlich
3
Qf
R2
0.9990
0.9990
0.9952
0.9977
907
1320
1646
884
6.38
9.82
15.95
8.75
0.5116
0.7528
0.6273
0.4899
0.092
0.138
0.152
0.9994
0.9893
0.9995
736
842
756
6.27
6.90
6.31
0.5433
0.6670
0.4961
0.182
0.9985
1316
10.78
0.2253
Q (g/kg)
b (m /g)
2498
2422
2436
1911
0.091
0.302
0.302
0.055
1954
1940
1940
2383
of plots of t=q vs. t were used to calculate the second-order rate constant k2 and qe. It is more likely
to predict the behavior over the whole range of
adsorption and is in agreement with the chemisorption mechanism being the rate-controlling
step [29,30].
Table 4 lists the results of rate constant studies
for dierent initial dye concentrations by the
pseudo rst-order and second-order models. The
correlation coecient R2 for the pseudo secondorder adsorption model has extreme high value
(> 0.9969 for reactive dyes, > 0.9983 for acid
dyes), and its calculated equilibrium adsorption
capacities qe,cal is consistent with the experimental
data. These suggest that the pseudo second-order
adsorption mechanism is predominant and that
the overall rate of the dye adsorption process
appears to be controlled by the chemisorption
process [29,30]. The similar phenomena have also
been observed in biosorption of dye RB2, RY2,
and Remazol Black B on biomass [13,31]. For the
pseudo second-order model in Table 4, in general,
the rate constant decreases with an increasing of
initial dye concentration.
According to the pseudo-second order model,
the adsorption rate dq=dt is proportional to the
second order of (qeq). Since the cross-linked
chitosan beads in our experiments have very high
equilibrium adsorption capacities qe, the adsorption rates become very fast and the equilibrium
times are short. Take dye RB2 in Fig. 3a for an
example. The adsorption density qt at 2 h for all
d kd 2 de2 de
kd1
t
2:303
6
7
76
Table 3
Comparison of the maximum monolayer adsorption capacities of some dyes on various adsorbents
Dyes
Adsorbent
Maximum monolayer
adsorption capacities
(g/kg)
Reference
RB2, RR2
RO14, RY86
AO12, AR14, AO7
DR81
Deorlene Yellow
Telon Blue
AB 25
BB 3
BR 22
BB 69
AB 25
Mordant Yellow 5
AB 25
AB 158
Direct Red 84
RR 222
RR 222
RR 222
RB 222
RY 145
Astrazone Blue
Astrazon Blue
Erionyl Red
RY 2
RB 2
Acid Brilliant Blue
Acid Orange 10
RY 2
RB 2
Congo Red
MO, MB, RB
CR, MV, AB
Acid Orange II
RR 222
RR 189
RR 189
Remazol Black B
Acid Violet 17
AB 29
BB 29
Disperse Red 1
2498, 2422
2171, 1911
19401954
2383
200
160
8399
448560
460520
184233
59
52
183
216
44
299380
100
50
5487
117179
25
160
48
52124
130
45
26
333
250
7
1421
618
12261678
10261106
16421936
1189
286588
20
1415
5446
2350
This work
This work
This work
This work
[1]
[1]
[2]
[2]
[2]
[4]
[4]
[5]
[5]
[5]
[5]
[6]
[6]
[6]
[6]
[6]
[7]
[8]
[8]
[9]
[10]
[11]
[12]
[13]
[13]
[15]
[16]
[16]
[17]
[18]
[24]
[24]
[31]
[32]
[33]
[33]
[33]
77
Fig. 3. Adsorption kinetics of (a) reactive dyes, (b) acid dyes on cross-linked chitosan beads at dierent initial dye concentrations.
3.3. Eect of pH
Fig. 5a and b shows the eect of pH on adsorption of the anionic dyes onto the cross-linked
chitosan beads (CLCB), the commercial activated
carbon (CAC) and chitin at 30 C. For the commercial activated carbon and chitin, the adsorption capacities of the anionic dyes are aected very
slightly by the pH, except for RR2 adsorbed by
chitin. However, the pH aects signicantly the
78
Table 4
Comparison of the rst-order and second-order adsorption rate constants, calculated qe and experimental qt values for dierent initial
dye concentrations (pH 3, 30 C, t=6 h)
First-order kinetic model
qt (g/kg)
k1 (min )
qe,cal (g/kg)
qe,cal
R2
2089
3086
3592
3962
5286
1031
1534
1766
1965
2434
0.0506
0.0596
0.0521
0.0185
0.0171
507
1812
2748
966
1428
0.9229
0.9172
0.9418
0.9377
0.9783
4.76
104
1.32
104
7.29
105
3.94
105
2.38
105
1037
1553
1799
2021
2524
0.9999
0.9995
0.9993
0.9995
0.9995
RR 2
2034
3218
3780
4391
5490
1015
1605
1883
2142
2386
0.0280
0.0409
0.0315
0.0186
0.0231
273
1281
1430
1459
1205
0.7955
0.9996
0.9986
0.9956
0.9535
2.80
104
1.10
104
5.98
105
2.54
105
4.35
105
1024
1627
1924
2228
2436
0.9999
0.9998
0.9997
0.9996
0.9996
RY 2 (pH 4)
2065
3178
3757
4305
5277
1024
1576
1864
2032
2294
0.0380
0.0159
0.0151
0.0082
0.0107
1292
772
1141
1431
1868
0.9885
0.9702
0.9966
0.9964
0.9978
8.05
105
4.05
105
2.53
105
9.43
106
8.35
106
1053
1633
1950
2280
2545
0.9989
0.9996
0.9996
0.9996
0.9991
RY 86
1980
2963
3383
3918
4750
946
1437
1626
1787
1932
0.0636
0.0864
0.0812
0.0648
0.0827
319
1283
2221
2320
4676
0.8489
0.9592
0.9974
0.9839
0.9394
4.76
103
3.62
104
2.03
104
1.62
104
2.38
104
948
1450
1648
1828
1971
0.9999
0.9997
0.9995
0.9988
0.9985
2192
3256
4258
5255
1084
1614
1883
1938
0.1077
0.0305
0.0303
0.0334
2004
1109
1808
1907
0.9886
0.9878
0.9803
0.9869
4.29
104
5.22
105
3.27
105
3.80
105
1095
1687
1994
2037
0.9997
0.9986
0.9984
0.9985
AR14
1996
3051
3879
5054
989
1481
1710
1878
0.0336
0.0203
0.0239
0.0174
586
904
1233
819
0.9832
0.9894
0.9444
0.7925
1.25
104
4.36
105
4.21
105
4.04
105
1020
1555
1784
1955
0.9991
0.9998
0.9998
0.9998
AO 7 (pH 4)
2233
3313
4163
5455
1105
1645
1847
1946
0.0331
0.0232
0.0198
0.0184
910
990
1497
1500
0.9974
0.9898
0.9955
0.9978
8.64
105
4.23
105
2.05
105
1.95
105
1152
1728
2006
2115
0.9984
0.9991
0.9985
0.9983
Dye
Reactive dye
RB 2
Acid dye
AO12
1
79
Fig. 4. The kinetics of ADMI and decolorization eciency of a mixture of reactive dyes (RB2, RR2, RY2, RY86) for dierent initial
concentrations at pH 3, 30 C.
80
Table 5
Comparison of the rst-order and second-order decolorization rate constants, calculated de,cal and experimental dt values for two
dierent initial concentrations of the reactive dye mixture (pH 3, 30 C)
First-order kinetic model
dt (%)
kd1 (min1)
de,cal (%)
R2
kd2 (min1)
de,cal (%)
R2
85,400
43,500
86.53(6 h)
98.23(3 h)
2.68
102
2.29
102
41.89
16.31
0.9452
0.6722
1.18
103
1.95
103
89.60
101.37
0.9993
0.9981
81
Fig. 7. The eect of adsorbent dosage on the adsorption capacity of reactive dyes onto cross-linked chitosan beads.
KC
CAe
Ce
DG 0 RT ln KC
8
9
82
Fig. 8. Change in free energy with respect to dierent equilibrium concentrations for the adsorption of anionic dyes on cross-linked
chitosan beads at 30 C.
4. Conclusions
This study investigates the equilibrium and the
dynamics of the adsorption of eight anionic dyes
on the chemically cross-linked chitosan beads. The
cross-linked chitosan beads had very high adsorption capacities to remove the anionic dyes, whose
maximum monolayer adsorption capacity ranges
from 1911 to 2498 (g/kg) at 30 C. The adsorption
capacities are aected signicantly by the dye
initial concentration, pH and adsorbent dosage.
Acknowledgements
The partial nancial support of this work by the
Lien Ho Industry, Commerce, and Education
Foundation, ROC, under the Grant No. 91-0-B1E3-01 is gratefully acknowledged.
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