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Abstract
Present investigation deals with the utilisation of bagasse y ash (BFA) (generated as a waste material from bagasse
red boilers) and the use of activated carbonscommercial grade (ACC) and laboratory grade (ACL), as adsorbents
for the removal of congo red (CR) from aqueous solutions. Batch studies were conducted to evaluate the adsorption
capacity of BFA, ACC and ACL and the eects of initial pH (pH0), contact time and initial dye concentration on
adsorption. The pH0 of the dye solution strongly aected the chemistry of both the dye molecules and BFA in an aqueous solution. The eective pH0 was 7.0 for adsorption on BFA. Kinetic studies showed that the adsorption of CR on all
the adsorbents was a gradual process. Equilibrium reached in about 4 h contact time. Optimum BFA, ACC and ACL
dosages were found to be 1, 20 and 2 g l1, respectively. CR uptake by the adsorbents followed pseudo-second-order
kinetics. Equilibrium isotherms for the adsorption of CR on BFA, ACC and ACL were analysed by the Freundlich,
Langmuir, RedlichPeterson, and Temkin isotherm equations. Error analysis showed that the RP isotherm best-ts
the CR adsorption isotherm data on all adsorbents. The Freundlich isotherm also shows comparable t. Thermodynamics showed that the adsorption of CR on BFA was most favourable in comparison to activated carbons.
2005 Published by Elsevier Ltd.
Keywords: Dye removal; Bagasse y ash; BFA; Congo red; CR; Adsorption kinetics; Isotherms; Error analyses
1. Introduction
Many dyes and pigments are toxic in nature with suspected carcinogenic and mutagenic eects (McKay et al.,
1985) that aect aquatic biota and humans (Gregory
et al., 1991). Congo red (CR) (1-naphthalenesulfonic
*
Corresponding author. Tel.: +91 1332 285319/285106; fax:
+91 1332 276535/273560.
E-mail address: id_mall2000@yahoo.co.in (I.D. Mall).
acid, 3,3 0 -(4,4 0 -biphenylenebis (azo)) bis (4-amino-) disodium salt) is a benzidine-based anionic disazo dye. This
dye is known to metabolize to benzidine, a known human carcinogen.
Dyes and pigments represent one of the problematic
groups; they are emitted into wastewaters from various
industrial branches, mainly from the dye manufacturing
and textile nishing (Janos et al., 2003) and also from
food colouring, cosmetics, paper and carpet industries.
Synthetic dyes have complex aromatic structures which
provide them physico-chemical, thermal and optical
493
The adsorbate CR dye [C.I. = 22 120, chemical formula = C32H22N6Na2O6S2, FW = 696.7, kmax = 500 nm]
was supplied by the Sigma Chemical Company, USA.
The structure of CR is illustrated in Fig. 1 (Fu and Viraraghavan, 2002). An accurately weighed quantity of the
dye was dissolved in double-distilled water to prepare
stock solution (500 mg l1).
NH2
NH2
SO3Na
SO3Na
494
Table 1
Characteristic of adsorbents
Adsorbent
Moisture (%)
Ash (%)
BFA
ACC
ACL
133.33
740.74
588.23
168.83
390.00
492.00
07.64
09.07
08.61
17.37
17.32
16.62
26.43
05.49
02.67
48.56
68.12
72.10
495
D-SO3 Na ! D-SO
3 Na
60
Pore volume
Pore area
0.044
50
40
0.033
30
0.022
20
0.011
0.055
10
0.000
10
100
0
10000
1000
100
With BFA
Without BFA
%Removal
80
60
40
20
0
2
10
12
14
pH0
496
100
%Removal
95
90
BFA
ACC
ACC
85
80
kf
t
2.303
Values of adsorption rate constant (kf) for CR adsorption on BFA, ACC and ACL were determined from
the plot of log(qe qt) against t (not shown). These values (kf = 0.022 min1 for ACL, 0.016 min1 for BFA
and 0.013 min1 for ACC) (Table 2) indicate that the
rate of removal was fastest by ACL followed by BFA
and ACC.
The reported kf values for the adsorption of CR on
coir pith and Azadirachta indica (neem) leaf powder
are 0.210 and 0.012 min1, respectively (Namasivayam
and Kavitha, 2002; Bhattacharyya and Sharma, 2004).
These values are close to the values obtained in the present work.
75
0
10
15
20
25
30
35
Fig. 5. Eect of initial adsorbate concentration on the adsorption of CR by various adsorbents at optimum dosages
(pH0 = 7, temperature = 30 C, t = 4 h, BFA dosage = 1 g l1,
ACC dosage = 20 g l1, ACL dosage = 2 g l1).
497
Table 2
Kinetic parameters for the removal of congo red by various adsorbents
kf (min1)
Pseudo-rst-order constants
BFA
0.016
ACC
0.013
ACL
0.022
h (mg g1 min1)
Pseudo-second-order constants
BFA
5.663
ACC
0.094
ACL
1.594
R2 (linear)
R2
2.073
0.203
1.471
0.9763
0.9702
0.9702
0.9881
0.9923
0.9850
ks (g mg1 min1)
qe (mg g1)
R2
0.061
0.413
0.069
9.638
0.477
4.789
0.9946
0.9935
0.9971
I (mg g1)
R2
I (mg g1)
R2
6.976
0.233
2.742
0.9797
0.9662
0.9473
0.041
0.008
0.024
9.177
0.365
4.435
0.9248
0.7739
0.9058
tk s q2e
1 tk s qe
k s q2e
to Eq. (6), did not yield satisfactory linear curves for the
CR removal by the adsorbents. This shows that the diusion of adsorbate into the pores of the sorbent was not
the only rate-controlling step (Tutem et al., 1998). It
may be that both the lm and pore diusion were important to dierent extents in the removal process.
3.6.4. Intra-particle diusion study
The possibility of intra-particle diusion resistance
aecting adsorption was explored by using the intra-particle diusion model as
qt k id t1=2 I
8
-1
qe (mg g1)
qt (mg g )
Adsorbent
6
4
2
0
0
10
15
20
(Time)1/2 (min)1/2
498
Ce
ln K R 1 ln aR b ln C e
qe
RT
lnK T C e
b
qe B1 ln K T B1 ln C e
To optimize the design of an adsorption system for
the adsorption of adsorbates, it is important to establish
the most appropriate correlation for the equilibrium
curves. Various isotherm equations like those of Freundlich, Langmuir, RP, and Temkin have been used to describe the equilibrium characteristics of adsorption.
The Freundlich isotherm is derived by assuming a
heterogeneous surface with a non-uniform distribution
of heat of adsorption over the surface. Whereas in the
Langmuir theory, the basic assumption is that the sorption takes place at specic homogeneous sites within the
adsorbent.
The RP isotherm (1959) can be described as follows:
K R Ce
1 aR C be
9
1
qm K L C e
1 K L Ce
10
K R Ce
1 aR
13
qe
12
11
where B1
RT
b
14
15
499
Table 3
Isotherm parameters and error analyses values for the removal of congo red by various adsorbents
KF ((mg g1) (mg l1)1/n)
Adsorbent
R2
HYBRID
0.9983
0.9936
0.9914
0.123
0.049
0.168
qm (mg g1)
R2
HYBRID
MPSD
11.885
0.635
1.875
0.924
0.968
0.956
2.216
0.199
0.652
14.888
4.469
8.074
1/n
Freundlich constants
BFA
8.162
ACC
0.402
ACL
0.939
0.288
0.234
0.341
KL (l mg1)
Langmuir constants
BFA
3.334
ACC
1.867
ACL
1.378
KR (l g1)
RedlichPeterson constants
BFA
15 864.8
ACC
5.56
ACL
205.12
Temkin constants
BFA
ACC
R2
HYBRID
MPSD
1935.376
12.749
217.516
0.712
0.804
0.662
0.9973
0.9937
0.9912
0.121
0.035
0.221
3.483
1.883
4.027
KT (l mg1)
B1
R2
HYBRID
MPSD
52.951
39.614
2.161
0.110
0.9747
0.9921
0.733
0.043
8.560
2.066
clear from this gure that the RP and Freundlich isotherms show very good t with the data.
ln (KR Ce/qe - 1)
BFA
ACC
ACL
5
4
3
2
-3
-2
-1
ln Ce
16
14
1, 3
4
12
qe (mg g-1)
3.483
2.048
4.004
aR (l mg1)
7
6
MPSD
10
Experimental
Freundlich, 1
Langmuir, 2
R-P, 3
Temkin, 4
6
4
2
0
-1
Ce (mg l )
500
e;exp
e;calc
MPSD 100t
17
qe;exp
n p i1
i
18
4. Conclusion
The present study shows that the bagasse y ash
(BFA) is an eective adsorbent for the removal of CR
from aqueous solutions. Higher CR removal by BFA,
ACC and ACL is possible provided that the initial adsorbate concentration is low in the solution. Equilibrium
adsorption was practically achieved in 4 h. Adsorption
kinetics followed pseudo-second-order rate expression
with initial sorption rate being highest for adsorption
on BFA. Freundlich and RP isotherms show very good
t with the experimental adsorption equilibrium data for
CR on all the adsorbents studied. Thermodynamic study
showed that CR adsorption will be most favoured on
BFA.
Acknowledgement
The authors thank the reviewers of the manuscript
for their useful comments and suggestions.
References
Aharoni, C., Sideman, S., Hoer, E., 1979. Adsorption of
phosphate ions by colloid ion-coated alumina. J. Chem.
Technol. Biotechnol. 29, 404412.
Allen, S.J., Mckay, G., Khader, K.Y.H., 1989. Intraparticle
diusion of a basic dye during adsorption onto sphagnum
peat. Environ. Pollut. 56, 3950.
Bailey, S.E., Olin, T.J., Bricka, R.M., Adrian, D.D., 1999. A
review of potentially low cost sorbents for heavy metals.
Water Res. 33, 24692479.
Banat, I.M., Nigam, P., Singh, D., Marchant, R., 1996.
Microbial decolorization of textile-dye-containing euents:
a review. Bioresour. Technol. 58, 217227.
Barret, E.P., Joyer, L.G., Halenda, P.P., 1951. The determination of pore volume and area distributions in porous
substances: 1. Computations from nitrogen isotherms. J.
Am. Chem. Soc. 73, 373380.
Bhattacharyya, K.G., Sharma, A., 2004. Azadirachta indica leaf
powder as an eective biosorbent for dyes: a case study with
aqueous congo red solutions. J. Environ. Manage. 71, 217
229.
Chern, J.-M., Wu, C.-Y., 2001. Desorption of dye from
activated carbon beds: eects of temperature, pH, and
alcohol. Water Res. 35, 41594165.
Coates, E., 1969. Aggregation of dyes in aqueous solutions.
J. Soc. Dyers Colour. 85, 355368.
Fu, Y., Viraraghavan, T., 2002. Removal of congo red from an
aqueous solution by fungus Aspergillus niger. Adv. Environ.
Res. 7, 239247.
Gregory, A.R., Elliot, S., Kluge, P., 1991. Ames testing of
direct black 3B parallel carcinogenicity. J. Appl. Toxicol. 1,
308313.
Ho, Y.S., McKay, G., 1999. Pseudo-second order model for
sorption processes. Process Biochem. 34, 451465.
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