Professional Documents
Culture Documents
a,*
School of Biomedical Sciences, University of Ulster, Coleraine BT52 1SA, Northern Ireland, UK
b
Department of Biochemistry, University of Wisconsin-Madison, WI 53706-1569, USA
Received 5 December 2001; received in revised form 20 February 2002; accepted 25 February 2002
Abstract
The adsorption of ve reactive dyes in a synthetic textile dye euent onto barley husks has been studied in static-batch mode and
in a continuous ow, packed-bed, reactor (CFPBR). Eective adsorption, thermodynamics and various initial concentrations (C0 )
were studied for static batch conditions. The eect of C0 and retention time (s), by varying height and weight of packing, along with
the kinetics of dye adsorption in CFPBR, were studied. The Langmuir isotherm was used to predict saturation capacities. The barley
husks were found to remove 8 mg g1 of dyes at C0 100 mg l1 in CFPBR with a residence of 11 min, with 90% adsorption being
achieved. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Adsorption; Barley husks; Batch mode; Continuous ow packed bed reactor; Textile dyes
1. Introduction
Ineciencies in the dyeing of textiles results in large
amounts of the dyestu being lost directly into wastewater and consequently having a detrimental eect on
ora and fauna. The presence of low concentrations of
dyes in euent is highly visible and undesirable, reducing light penetration and potentially inhibiting photosynthesis (McMullan et al., 2001; Mishra and Tripathy,
1993). Recently the textile industries have been required
to reduce the chemical content of their euents due to
the enforcement of government legislation in the European Union, EU (ONeill et al., 1999).
In the past municipal treatment systems were used for
the purication of textile dye euent, but due to the
xenobiotic and recalcitrant nature of many dyes, were
found to be ineective. The same is true when dyes are
released into aquatic systemsanaerobic bacteria in the
sediment are unable to mineralise dyes completely resulting in the formation of toxic amines (Nigam et al.,
2000; Banat et al., 1996). It is therefore necessary for
0960-8524/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 0 - 8 5 2 4 ( 0 2 ) 0 0 0 7 0 - 6
44
Nomenclature
A
b
C
Ca
Ce
Cin
C0
Cout
Ct
dC
dt
E
h
Kd
Q
Arrhenius energy
constant related to energy or net enthalpy
concentration of dyes remaining in solution
at equilibrium, mg l1
concentration of dyes at any particular time,
mg l1
equilibrium concentration of dyes, mg l1
concentration of dyes at inlet, mg l1
initial concentration of dyes, mg g1
concentration of dyes at outlet, mg l1
concentration of dyes at any time, mg l1
change in concentration of dyes, mg l1
change in time, min
Arrhenius energy, kJ mol1
Plancks constant, J s
adsorption rate constant, min1
amount of dyes adsorbed per unit weight of
sorbent in forming a complete monolayer on
surface, mg l1
q
qexp
qpred
R
T
Xa
Xa pred
Xa exp
X =M
Greek symbols
DG
free energy, kJ mol1
DH
enthalpy change during adsorption, kJ mol1
DS
entropy change during adsorption, J mol1 K1
j
Boltzmanns constant, J K1
kmax
maximum absorbance, nm
s
retention time of euent, min
ln Ct =C0 Kd t
45
2. Methods
Kd A expE=RT
46
Table 1
Experimental and predicted adsorption capacities for 1 g barley husks
in static-batch conditions
C0 (mg l1 )
r2
50
100
150
200
3.94
8.44
13.90
18.89
4.90
9.93
15.00
19.90
0.95
0.99
0.99
0.99
within the adsorbent and that once a dye molecule occupies a site, no further adsorption can take place at that
site. Theoretically, therefore, a saturation value is
reached beyond which no further sorption can take
place (Choy et al., 1999).
The monolayer saturation capacities are listed (Table
1). The theoretical saturation values, qpred and the experimental saturation points, qexp showed that 1 g of
barley in static-batch conditions conformed closely with
the predicted Langmuir saturation points. The r2 values
also shows that the experimental data and the predicted
data tted well with each other. From this data it was
concluded that the use of barley husks gave reasonably
uniform and predictable results for the removal of dyes
by adsorption and it was therefore decided to test its
eectiveness for dye removal in a column reactor.
3.3. Eect of temperature on eective adsorption in static
batch
The equilibrium sorption capacity increased with
temperature, indicating that a high temperature favoured dye removal by adsorption onto barley husks
(Fig. 2). This eect is characteristic of a chemical reaction or bond being involved in the sorption process with
the increase in temperature increasing the equilibrium
47
Fig. 5. Arrhenius plot of barley husk in static batch reactor (ln Kd vs.
1=T ); r2 0:92; from slope E=R 564:2; hence, E 4:69 kJ mol1 ;
from intercept A 0:053 min1 .
conversion. By increasing the temperature of the reaction from 25 to 70 C, the removal of dyes increased
from 6.8 to 8.6 mg g1 . The increase in adsorption could
be due to changes in pore size, an increase in kinetic
energy of the dye molecules, and the enhanced rate of
intraparticle diusion of sorbate (Low et al., 2000;
Sharma et al., 1991).
It can be seen that the adsorption coecient Kd increased with t1=2 -half life time (time taken for the dye
concentration to reduce to half of its initial value) decreasing with an increase in temperature (Fig. 3). It can
be seen that with a r2 value of 0.99, the experimental
data tted well with the model, allowing a better understanding of the rate of adsorption at various temperatures, when considering scale-up. The enthalpy of
entropy change during adsorption was calculated from
the slope and intercepts of plot ln (Kd =T ) vs. 1=T
Fig. 4. Plot for enthalpy and entropy (lnKd =T vs. 1=T ), r2 0:68.
From slope DH =R 251:8; DH 20:94 kJ mol1 . From intercept
lnk=h DS =R 9:684. Hence, DS 278:03 J mol1 K; average
DG calculated from Gibbs free energy equation 111:6 kJ mol1 .
48
Table 2
Eect of retention time (s) on synthetic textile dye removal in CFPBR
(packing height 70 mm, weight 1 g)
Flow rate
(ml min1 )
0.51
0.78
1.13
1.45
1.77
a
Synthetic euent
(mg l1 )
Inlet (C0 )
Outleta (Ce )
100
100
100
100
100
20.0
33.6
43.8
50.8
55.2
Eective adsorption
q (mg g1 )
8.0
6.6
5.6
4.9
4.5
Fig. 7. Linear regression of dye adsorption, Xa predicted and Xa experimental for CFPBR at a 95% condence limit; where Xa 1
Ct =C0 ; r2 0:99.
the articial factory euent. Initial small-scale experiments were conducted using 0.3 mg of dyes with 90%
adsorption using 0.3 g of barley husks. As a scale up
strategy, 0.76 mg of dyes using 1 g of barley husks was
carried out and a similar removal of 90% was observed.
These results clearly showed that Xa pred and Xa exp
correlate closely at a condence interval of 95% (Fig. 7).
This predictability of adsorption of dyes onto barley
husks in the column reactor means that the rate of adsorption should be easily calculated and obtained in
scale up. The conformity of these results indicated the
feasibility of this reactor for continuous dye removal in
a larger experimental setup.
4. Conclusions
Results obtained from this study showed that barley
husk in static batch and in a continuous packed bed
reactor was eective at removing dyes from the synthetic
factory euent. In the batch studies a C0 of 100 mg l1
was found to give the lowest Ce at a sorbent dose of 1 g.
Enthalpy and entropy calculations showed that the energy required for adsorption was obtained from the
surrounding temperature, with a higher temperature
yielding a higher percentage dye removal. The Langmuir
equation was used successfully to predict saturation
capacities of the barley husks, at various C0 , which will
be of great importance for any further work concerning
scale-up.
In the column studies an optimal ow rate of 0.51
ml min1 with a packing height of 70 mm (C0 100 mg l1 )
was found to be the most eective combination removing 90% of the dyes from the synthetic euent. As retention time was increased in the CFPBR the amount of
dyes adsorbed also increased, obeying the laws of rst-
order kinetics. Therefore, the potential exists for continuous dye removal in CFPBR in a larger scale and this
could be investigated in future work.
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