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Bioresource Technology 85 (2002) 4349

Studies on the removal of dyes from a synthetic textile euent


using barley husk in static-batch mode and
in a continuous ow, packed-bed, reactor
Tim Robinson a, Bennett Chandran a, G. Sathya Naidu b, Poonam Nigam
a

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

Corresponding author. Tel.: +44-28-7032-4053; fax: +44-28-70324906.


E-mail address: p.nigam@ulst.ac.uk (P. Nigam).

dye-containing euents to be treated in an eective


manner before being discharged into natural waterways.
Industries employ many methods of dye removal with
activated carbon being the most widely used (Nasser
and El-Geundi, 1991). Although highly eective, activated carbon is expensive, mainly due to the need for
regeneration of the carbon after dye removal. Although
the dyes may have been eectively removed, industries
still face the problem of the disposal of this concentrated
sludge (Robinson et al., 2001a).
A number of biological processes for the removal of
dyes from textile euents have been explored, such as
decolourisation through liquid fermentations by whiterot fungi (Robinson et al., 2001b,c; Paszczynski and
Crawford, 1995) and bacterial cultures (Nigam and
Marchant, 1995; Pasti and Crawford, 1991). However,
the use of agro/industrial wastes residues for the adsorption of dyes has been highlighted as an eective and
cheap alternative for dye removal (Nigam et al., 2000;
Poots et al., 1976a,b). These dye adsorbed agro/industrial wastes were previously burnt for power generation,
but the potential exists for them to be fermented to
produce a high protein-content cattle feed.
We previously studied four dierent agricultural
waste residues at dierent initial dye concentrations
(C0 ), particle sizes, amount of sorbents and retention

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

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T. Robinson et al. / Bioresource Technology 85 (2002) 4349

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

times. The eect of various pretreatments on adsorption


were also explored and conditions were optimised for
barley husks. The barley husks were found to be the
most eective adsorbent for dye removal in static-batch
mode and also the best for dye-desorption (Robinson
et al., in press).
The present study investigated the use of barley husks
for dye removal in static-batch mode and in continuous

q
qexp
qpred
R
T
Xa
Xa pred
Xa exp
X =M

amount of dyes bound per g of substrate,


mg g1
experimental adsorption capacities, mg g1
predicted adsorption capacities, mg g1
gas constant, J mol1 K1
absolute temperature, K
fraction of dyes adsorbed, mg l1
fraction of dyes adsorbed (predicted)
fraction of dyes adsorbed (experimental)
amount of dyes adsorbed per unit weight of
sorbent, mg g1 (q)

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

ow, packed-bed, reactor (CFPBR, Scheme 1). Based on


the static-batch data we studied the adsorption process
in a continuous, packed-bed, reactor. Packed bed column reactors have been successfully used for the continuous removal of heavy metals onto biomass (Wang
and Reardon, 2001; Valdman et al., 2001; Lee and Suh,
2000; Chang and Chen, 1999). In this regard, the kinetics of dye adsorption in a continuous ow reactor

Scheme 1. Schematic diagram of the continuous packed bed column reactor.

T. Robinson et al. / Bioresource Technology 85 (2002) 4349

was studied using the design equation for a rst-order


process in a plug-ow reactor. The results showed that
barley husks could be used as an ecient adsorbent for
removal of reactive textile dyes.

ln Ct =C0 Kd t

45

2. Methods

Kd was calculated from the plot of lnCt =C0 ] vs. t. The


energy and entropy of adsorption can be estimated by
the use of absolute reaction states (Eyring, 1935). The
adsorption rate constant can be expressed in terms of
enthalpy and entropy by the following equation:

2.1. Preparation of adsorbent

kd jT =h expDS=R expDH =RT

The barley husks were obtained from Bushmills


Distillery, Co. Antrim, Northern Ireland, and dried to a
constant weight and roughly chopped to obtain a particle size of 1 mm  4 mm.

The plot of lnKd =T ) vs. 1=T gives slope of (DH =R)


and intercept of ln j=h DS=R from which the
enthalpy and entropy values were calculated. Another
thermodynamic parameter, which was considered when
examining the eect of temperature, is Arrhenius energy.
According to Arrhenius law:

2.2. Preparation of synthetic textile euent


The reactive dyes used in this study were Cibacron
Yellow C-2R, Cibacron Red C-2G, Cibacron Blue C-R,
Remazol Black B, and Remazol Red RB. The dyes were
a gift from Fruit of the Loom, Rep. of Ireland. The
synthetic euent was prepared by dissolving the above
ve dyes, in equal amounts, in deionised water to produce a stock solution of 1000 mg l1 (pH 7.2). This stock
solution was diluted in accurate proportions to produce
solutions of dierent initial concentrations.
2.3. Static-batch studies for dye removal
The static-batch studies were performed using 1 g (dry
weight) of barley husk in 100 ml of synthetic euent
with various dye concentrations at room temperature,
20  2 C. The eect of temperature on adsorption was
also studied. Euent samples were withdrawn at suitable time intervals and the remaining colour in solution
was monitored using a spectrophotometer at kmax .
The Langmuir isotherm model was used to predict
theoretically the saturation capacity of the barley husks
when soaked in the synthetic textile euent, and was
compared to the experimental saturation values. The
linear form of the expression can be expressed thus
(Weber, 1972):

 
1
1
1
1

1
X =M Q
bQ C
In order to study the eects of temperature on adsorption of dyes on barley husks similar experiments
were performed at 25, 30, 40, 50, 60 and 70 C. The rate
of adsorption can be described as being proportional to
the concentration of the dyes, if rst-order kinetics is
assumed:
dC=dt Kd Ca

Integrating and rearranging the above equation gives:

Kd A expE=RT

The values of E and A were calculated from the slope


and intercept of plot lnKd vs. 1=T .

2.4. Continuous packed bed reactor


Adsorption studies onto barley husks were also carried out in a continuous, packed-bed, column reactor,
made of glass, with an internal diameter of 10 and 300
mm in height. The bed depth of the column reactor was
varied in terms of height and weight of packing to
achieve various retention times (s). The ow rate was
regulated by a variable peristaltic pump, which was used
to percolate the synthetic factory euent through a bed
of barley husks. The experiments were continued until
saturation of the column was observed. The data presented constitute the average from a set of three replicates carried out at room temperature, 20  2 C.
The kinetics of the dye adsorption in a continuous
ow, packed-bed, reactor was also studied. Various
concentrations, heights and weights of packing and ow
rates were investigated. Samples were taken from the
outlet of the column and the Cout values measured.
Considering the assumption that the adsorption is a
rst-order process the design equation for packed bed
reactor is given as:
 ln1  Xa ks

where Xa is the concentration of dye after passing


through the column, which is given as Cin  Cout =Cin . s
is the retention time of the synthetic euent.
The slope of the plot of  ln1  a vs. s gave the
value of rate constant at room temperature. The kinetics
of experimental data was tested against the theoretical
predictions using the above formula.

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T. Robinson et al. / Bioresource Technology 85 (2002) 4349

3. Results and discussion


3.1. Eect of initial concentration on dye adsorption in
static-batch
Adsorption of dyes, from a synthetic euent, onto
barley husk was measured at given contact times for
four dierent C0 at an adsorbent dose of 1 g per 100 ml.
The eect of initial dye concentration on the rate of
adsorption is shown (Fig. 1). It is clear from the
graph that the dynamic equilibrium (Ce ) was achieved
after 24 h for 50 and 100 mg l1 , although the time taken
for 150 and 200 mg l1 to reach equilibrium was much
longer. The percentage of dye adsorbed at Ce was
highest (80%) at C0 of 100 mg l1 followed by 50, 150
and 200 mg l1 with a dye removal percentage of 76%,
75.2% and 67.2% respectively. The dye removal (%) was
low for lower dye concentrations of 10 mg l1 to 40
mg l1 (results not shown), when compared to that for
the higher concentration range for the same 24 h. From
this study a C0 of 100 mg l1 was selected for studies
in CFPBR, as it had the highest percentage of dye removal with equilibrium being reached in a 24 h retention period.
3.2. Langmuir isotherm studies
To establish the sorption capacity of the barley, the
Langmuir equation was applied to the adsorption
equilibrium at dierent C0 , as demonstrated by Low
et al. (2000). The Langmuir adsorption isotherm had
been successfully applied to sorption processes and it
was used in this study to explain the adsorption of dyes
onto barley husks. The Langmuir theory assumes that
adsorption takes place at specic homogenous sites

Fig. 1. Eect of various C0 on the removal of dyes from a synthetic


textile euent (1 g barley husk; batch). (r) 50 mg l1 , (j) 100 mg l1 ,
(N) 150 mg l1 , () 200 mg l1 .

Table 1
Experimental and predicted adsorption capacities for 1 g barley husks
in static-batch conditions
C0 (mg l1 )

qexp (mg g1 )

qpred (mg g1 )

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

Fig. 2. Eect of temperature on eective adsorption by 1g barley husks


(C0 100 mg l1 ; batch). ( ) 25 C; ( ) 30 C; () 40 C; (N) 50 C; (j)
60 C; (r) 70 C.

T. Robinson et al. / Bioresource Technology 85 (2002) 4349

47

Fig. 3. Eect of temperature on adsorption onto barley husks in


static batch conditions (t1=2 vs. Kd ) (r2 0:99; slope 0:0001;
intercept 0:0184).

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). A negative entropy value (DS 278:03


J mol1 K) was obtained for adsorption at higher temperatures. This indicated that the adsorption reaction
was not a spontaneous one (supported by positive free
energy values 111.6 kJ mol1 ) and that the system
gained energy from an external source. This energy was
probably obtained through an increase in temperature
meaning that the reaction was endothermic and this
argument was strengthened by a positive value of DH ;
20.94 kJ mol1 (Ho and Mc Kay, 1998). The slopes and
intercepts of the Arrhenius plot yielded an activation
energy of 4.69 kJ mol1 (Fig. 5). The value of E supports
the previous ndings that the rate of adsorption was
temperature dependent. Similar observations have been
recorded for stability and denaturation of biocatalysts
(Chen et al., 1994; Foster, 1980; Kapat and Panda,
1996).

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 .

Fig. 6. First-order kinetic plot for the determination of adsorption


rate constant in CFPBR. r2 0:98 (C0 100 mg l1 ; flow rate 0:51
ml min1 ; packing height 70 mm).

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T. Robinson et al. / Bioresource Technology 85 (2002) 4349

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

The values were measured after steady state attained.

3.4. Column eective adsorption


The focus of this study was to study the maximal
obtainable level of dye removal by varying the ow rates
of the synthetic euent in the column using a xed
packing height 70 mm, and weight (1 g), of barley husks
(Table 2). The results show that the adsorption of the
dyes onto the barley husks was very much dependent on
ow rate and that this parameter directly aected the
eective adsorbance of the barley in the column.
Aksu and Kutsal (1998), demonstrated that for a
metal solution, if the residence time of the solute in the
column is not long enough for adsorption equilibrium to
be reached at that ow rate, the metal ion solution
leaves the column before equilibrium occurs. In other
words, the ow rate of the synthetic euent into the
column was too high. An upper limit ow rate of 1.77
ml min1 removed only 44.8 mg l1 of the dyes from the
euent and had a q value of 4.5 mg g1 . With a low ow
rate of 0.51 ml/min1 , however, a high proportion of the
dyes was removed (80 mg l1 ) and the amount of dyes
bound per gram of substrate was 8 mg g1 at steady state
conditions ( 11 min). The time required for adsorption
in the column is comparable with that needed for the
static-batch studies (Fig. 1). It can be seen that in both
cases similar q values were achieved in the rst few
minutes of the adsorption process.
This study can be compared with the same weight of
barley in static-batch studies, C0 100 mg l1 . The time
taken to reach equilibrium was 24 h and had a similar q
value of 8.5 mg g1 . It can be seen that, during column
operation, a low ow rate oered a rapid rate of removal
and had the potential of reducing retention times for
eective removal.
The kinetics in the continuous, packed-bed, reactor
were studied using the rst-order design equation. This
assumption was valid because in a uniformly packed
reactor, at laminar ow conditions, the reactor performed as a plug-ow reactor. The plot of ln1  Xa ) vs. s
was a straight line passing through the origin, indicating
that the adsorption process was a rst-order reaction
(Fig. 6). It can be seen that the rate of the adsorption
reaction was dependent on the concentration of dyes in

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-

T. Robinson et al. / Bioresource Technology 85 (2002) 4349

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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