Bangladesh Pharmaceutical Journal 16(1): 93-98, 2013

Removal of Remazol Red from Textile Waste Water Using

Treated Sawdust - An Effective Way of Effluent Treatment
Nargish Jahan Ara, Md. Abu Hasan, Mohammad Arifur Rahman, Md. Abdus Salam,
Abdus Salam and A. M. Shafiqul Alam
Department of Chemistry, University of Dhaka, Dhaka-1000, Bangladesh

Abstract
Activated carbon prepared from sawdust is endeavored as adsorbent for the removal of reactive dye, namely
Remazol Red (RR) from aqueous media. The adsorption of RR has been studied onto activated sawdust at various
particle size, adsorbent dose, temperature and pH values. The adsorptions of the above mentioned dye were
designed for the Langmuir and Freundlich Isotherms. Pseudo first and second order kinetic models were used to
calculate the amount adsorbed at equilibrium (qe). The calculated values of qe for pseudo-second order equation
were found to be in good agreement with those of experimental values. The monolayer capacity (qm) for treated
sawdust (8.00 mg g –1) is greater than commercial charcoal (0.074 mg g –1). It is established that treated sawdust
has been used as a better adsorbent for the removal of RR as compared to commercial charcoal. This process may
eventually be used to get industrial waste free purified water.
Key words: Sawdust, Remazol Red, Adsorption Isotherm, Adsorption Kinetics.

Introduction
Industrial effluents are one of the major pollutants of Adsorption is one of the cheapest and most effective
water. Many dyes are carcinogenic and affect the life of techniques (Cotoruelo et al., 2007; Dee et al., 2006).
aquatic organisms (Baughman et al., 1998; Hassan et al., Different adsorbents are used for the removal of dyes from
2009). Removal of azo dyes from the effluent generated by aqueous solutions such as alumina, crushed bricks, peat,
textile industries is rather difficult. Azo dyes represent a sand, charcoal bentonite, silica, apricot etc (Hu et al.,
major class of synthetic colorants that are both mutagenic 2006; Jain et al., 2009; Mon, 2004; Senthilkumaa et al.,
and carcinogenic (Waghmode et al., 2012). Reactive dyes 2006 ). The most widely used adsorbent for the removal of
are extensively used in textile industry and due to their dyes are charcoal prepared from saw dust which is
large size they have high affinity to bind with cellulosic inexpensive and easily available. Therefore, the interest is
fiber. The worldwide annual growth rates of reactive dyes growing to find out an alternative adsorbent to commercial
are four times as much as for conventional dyes charcoal.
(Zollinger, 2003). Vinyl sulfone dyes are a class of
reactive dyes effectively used for cotton, silk and wool.
They are also known as remazol dyes after the
trademarked name under which they were first introduced.
Vinyl sulfone dyes are less reactive than other dyes and
therefore major part of these dyes remains in dyeing bath
or drained off as industrial effluents. It has been reported
that up to 30% of the used dyestuff remains in the spent Figure 1. Structure of Remazol Red.
dye-bath after the dying process (Ozacar et al., 2005). The objective of this work is to study the feasibility of
Presence of such dyes in effluents causes a lot of pollution activated sawdust as alternate adsorbents to commercial
in water. Various challenges have been made to remove charcoal (Ahmadpour et al., 1997; Arivoli et al., 2010) for
these harmful dyes from industrial wastes (Ho et al., 2005; the removal of Remazol Red (RR) (Figure 1). The
Mohanty et al. 2006; Sousa et al., 2012). adsorption results of RR onto saw dust are also compared
with that of commercial charcoal.
Correspondence to: Mohammad Arifur Rahman, Department of Chemistry, University of Dhaka, Dhaka-1000, Bangladesh
E-mail: [email protected]
94 Ara et al. / Bangladesh Pharmaceutical Journal 16(1): 93-98, 2013

Materials and Methods 1000 ppm RR was prepared by dissolving appropriate

Preparation of activated charcoal: There are two amount of dye in water. The required concentration was
different methods for the preparation of activated carbon: prepared for the various steps of the investigation by
physical activation and chemical activation (Ho et al.,  dilution.
2005). In comparison to physical activation, chemical Study of batch adsorption process: Equilibrium
activation provides a number of advantages. The process isotherms for adsorption onto the selected carbons
of dye removal was applied in batch mode. Adsorption determined by using 1 g of adsorbent per 50 ml of aqueous
experiments were performed by suspending sawdust in the solution for initial dye concentrations in the range of 50-
effluent and analyzing the supernatant by spectroscopic 200 ppm. For these experiments, the bottles were shaken
method. at constant temperature (25oC) and agitation speed (120
Sawdust (Shegun, Tectona grandis) was collected rpm), for the minimum contact time required to attain
from nearby Sawmill (Rampura, Dhaka, Bangladesh). equilibrium, as determined from the kinetic
This was washed with double distilled water to remove measurements. The effectiveness of the treatment was
water-soluble impurities and surface-adhered particles. evaluated by measuring concentration by UV-Visible
Then the adsorbent was oven-dried at 60oC to remove the spectroscopic method at 541.5 nm.
moisture and other volatile impurities. Then, part of the The influence of pH was studied by adjusting the
dried sawdust was soaked in concentrated H2SO4 in an reaction mixture to different initial pH values and
amount sufficient to cover the material completely, analyzing the residual color at the equilibrium contact
agitated at 120 rpm in a shaking incubator for 30 min, and time. The pH values were adjusted with dilute sulfuric
then left for 2h. After being mixed, the slurry was acid and sodium hydroxide solutions. Then the percentage
subjected to vacuum-drying at 100o C for 24 h. Chemical of dye removal was calculated by,
activation of the sawdust was performed with ZnC12. Ten (Co - Ce)
R= Co x 100% ………………. (1)
grams of sawdust was mixed well with 100 ml of 10% of
ZnC12 solution. The mixing was performed at 50o C for 1 The amount of dye adsorbed onto the activated
h. After mixing, the slurry was subjected to vacuum- carbons, qe (mg/g), was calculated according to:
drying at 100o C for 24 h (Mohanty et al., 2006; (Co - Ce)V
qe = W ………………….(2)
Ahmadpour et al., 1997).
where C0 and Ce are the initial and the final dye
The resulting impregnated solids was placed in a
concentrations (mg/l), respectively, and W is the amount
stainless steel tubular reactor and heated (5o C min-1) to a
of adsorbent (g), V is the volume of the solution (L).
temperature of 300o C under nitrogen flow at a rate of 150
cm3 min-1 at STP for 1 h. Nitrogen entering the reactor
was first heated to 250-300oC in a preheater. The products Results and Discussion
were washed sequentially with 0.5 M HCI, hot water and The physical properties of treated sawdust: The
finally with cold distilled water to remove residual organic physical properties of the treated sawdust have been
and mineral materials and then dried at 110o C. In all shown in the Table 1. From the table it is found that the
experiments, the heating rate and nitrogen flow were kept BET surface area (Rabolli et al., 2010) is 5.69 m2/g and
constant. the average pore diameter is 99.60 A0. The point of zero
Preparation of dye solution: Remazol Red (RR) was charge (pzc) of the above mentioned adsorbent is 5.5.
used in the experiment. It is a reactive dye supplied by Optimization of contact time: The contact time
Dye Star Ltd., Dhaka, Bangladesh. This dye form covalent between dye and adsorbent is of significant importance in
bond with the fiber, usually cotton, although itis used to a waste water treatment by adsorption methods. A rapid
small extent on wool and nylon. This class of dyes first removal of pollutants and establishment of equilibrium in
introduced commercially in 1956, made it possible to a short period signifies the efficacy of the adsorbent. The
achieve extremely high washing fastness properties by effect of shaking time for the adsorption of dye onto
relatively simple dyeing methods. A stock solution of charcoal prepared from sawdust was determined at 25oC.

 
 Ara et al. / Bangladesh Pharmaceutical Journal 16(1): 93-98, 2013 95

The fixed concentration of RR was shaken after adding 1g

of adsorbent in each time. Color removal was rapid at 120

initial stage but decreased with the increase of time (Fig.

100

Removal Efficiency (%)

2). Initially rapid increase was due to the presence of large
number of vacant site and with the passage of time, 80
number of active sites decreased which were responsible
for the reduction of adsorption rate. The optimum contact 60

time was observed 12 hours for all the adsorbents.

40

Table 1. Physical properties of treated sawdust.

20

Properties value
0
Particle size (µm) <140 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
BET surface area (m2/g) 5.69 Amount of Adsorbent (g)
Average pore diameter (A0) 99.60
Figure 3. Effect of adsorbent amount on the removal of RR.
Micro pore volume(cc/g) 0.014 Particle size: 140 µm; Initial concentration: 50 mg/l; Initial
Micro pore area (m2/g) 2.37 volume: 50 ml; pH: 7.0; Contact time: 12 hours; Temp.: 250C.
Bulk density (g/ml) 0.84
pzc 5.5
Influence of initial pH: Hydrogen and hydroxy1 ions
are usually adsorbed quite strongly on the surface of the
Optimization of adsorbent amount: For optimizing the adsorbents due to their smaller size as compared to the dye
amount of adsorbents,experiments were performed using molecules and therefore adsorption of other ions is
50 ml aqueous solution of RR and was shaken for 120 affected by pH of the solution. The pH primarily affects
minutes after adding different amount of adsorbents (0.5- the degree of ionization of the dye as well as surface
3.0 g). Absorbance of the filtrate was noted using properties of the adsorbents. Adsorption of RR decreased
spectrophotometer at λ max of the dye. It was observed that with increase in pH (Figure 3). This can be explained on
the basis that positively charged surface is formed on the
adsorption of dye increased with the increase of the
adsorbents at lower pH due to adsorption of hydrogen ions
amount of adsorbents and then attained constant value at
on the surface of adsorbents.
equilibrium (Fig. 3). The optimum amount was found to
be 1.0g which was used for all subsequent adsorption 100
studies.
90
100
Removal Efficiency (%)

80
95
Removal Efficiency (%)

90 70

85 60

80
50
75
40
70
30
65 2 4 6 8 10 12
pH
60
0 10 20 30 40 50 60 Figure 3. Effect of pH on the adsorption capacity of saw dust for
Contact Time (hour) Remazol red at 250C.
Figure 2. Effect of contact time on the removal of RR. Particle
size: 140µm; Adsorbent amount: 1.0 g; Initial conc.: 50 mg/l;
Initial volume: 50 ml; pH: 7.0; Temp.: 250C.

 
 
96 Ara et al. / Bangladesh Pharmaceutical Journal 16(1): 93-98, 2013

It has been reported that the positively charged ions Adsorption data for Remazol Red onto activated
prefer to adsorb at higher pH value and negatively charged sawdust was fitted to the linear forms of Freundlich (4)
ions prefer lower pH. As pH of the system increases, and Langmuir (5) equations
number of positively charged site on the surface of 1
adsorbents decreases. As the dye is in dissociated form the log( qe) = log(Ce ) + log( KF ) ……………(4)
n
anion (Equation 3) and as a result adsorption of dye
Where qe(mg/g) is the amount adsorbed per unit mass
decreased at higher pH values.
of the adsorbent,Ce is the equilibrium concentration, KF
H+ – OH– and 1/n are constants, being indicative of the extent of
ASO2 Na ASO2- Na+ ……………(3) adsorption and degree of non-linearity between solution
The decrease in the amount of dye adsorbed on concentration and amount of dye adsorbed respectively.
surface of the adsorbents with increase in pH is in good From Freundlich plot (Figure 5), the constants KF and
agreement with the data reported earlier (Ahmadpour et n are calculated from the intercepts and slopes of linear
al., 1997) plots of log(qe) versus log(Ce), respectively and their
Adsorption isotherms: The adsorption isotherms values are given in Table 2. If n = 1, adsorption is
of RR on sawdust were found to be L-type in each case homogeneous and there is no interaction between the
(Ho et al., 2005). The initial sharp rise in the degree of adsorbed species. If n < 1, the adsorption is unfavorable
adsorption with increasing dye concentration is due to the and if n > 1, then the adsorption is favorable. In present
availability of higher adsorption sites on the surface of the studies, we have found that n is greater than unity for the
adsorbents. When the concentration of dye solution given adsorbents which indicates that adsorption is
increases, adsorption sites are decreased. As a result, the favorable. It has also been reported that the value of KF
dye molecules find difficulty to access the remaining gives rough estimation about the degree of adsorption. In
vacant surface. Adsorption of RR is found to be slightly the present studies it was observed that the value of KF for
increased with increase in temperature then remain almost the adsorption of RR onto saw dust (1.71 mgg-1) is greater
constant (Figure 4). This indicates that desorption process than those for charcoal (5.91 mg g-1) (Table 2). Greater
is more favorable at lower temperature and is expected to value of KF for activated sawdust reflects that it is better
be an endothermic process. adsorbent for the removal of RR than commercial
charcoal.

100
0.9

0.8
95
Removal Efficiency %

0.7
90
0.6
log qe

85 0.5

0.4
80
0.3

75 0.2
15 20 25 30 35 40 45 50 55 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Temperature
log Ce
Figure 5. Freundlich isotherms of Remazol Red on saw dust at
Figure 4. Effect of temperature on the removal of RR. Particle
size: 140µm; Adsorbent amount: 1.0 g; Initial conc.: 50 25ºC.
mg/L; Initial volume: 50 ml; pH: 7; Contact time: 12 hours.

 
 Ara et al. / Bangladesh Pharmaceutical Journal 16(1): 93-98, 2013 97

Table 2. Freundlich parameters for Remazol red on Sawdust Table 3. Langmuir parameters and separation factor RL for
and commercial charcoal at 250C. adsorption of RR on treated sawdust.

Adsorbents n KF R2 Adsorbent Ka/ qm/ R2 RL

Prepared activated saw dust 2.85 1.71 0.991 dm3mg-1 mgg-1
Prepared 0.105 8.00 0.988 0.045
Commercial activated 1.79 5.91 0.998 activated saw dust
carbon
Commercial 7974.8 0.074 0.9448
activated carbon
Langmuir equation is given as
Adsorption kinetics: In order to investigate the
Ce 1 Ce adsorption processes of Remazol Red onto sawdust two
qe = qmKa + qm ……………………(5) kinetic models were used. Pseudo-first order kinetic
equation is given as (Ho et al., 2005): 
A plot of Ce/qe versus Ce should indicate a
k1
straight line of slope 1/qm and an intercept of 1/ (Kaqm), log (qe – qt) = log qe – t …………… (6)
1.202
where Ce is the equilibrium concentration (mg/dm3), qeis
the amount of dye sorbed (mg/g), qm is qe for a complete Where, qt is the amount of dye adsorbed at time t
monolayer (mg/g), and Ka is the sorption equilibrium (mgg-1),qeis the amount adsorbed at equilibrium (mg g-1),
constant (dm3/mg).The essential characteristics of k1is the pseudo-first order rate constant (min-1) and t is the
Langmuir eqn. can be expressed in terms of separation contact time (min).
factor RL(Rao et al., 2008),   Values of the constants, k1 and qe for the adsorption
Where RL = 1/(1+Ka.Co) of dye on the adsorbents were determined from the slopes
and intercepts of the plots log(qe – qt) against t,
* RL > 1; Unfavorable.
respectively and their values are given in Table 4.
* 0< RL< 1; Favorable.
Pseudo-second order model can be represented in the
* RL = 1; Linear.
following form
* RL = 0; Irreversible.
t 1 Ce
qt = 2 + q t ……………………… (7)
k2(qe) t

10
Where,k2 is the Pseudo-second order rate constant
(gmg-1min-1). The values of the qe and k2 were determined
8
by potting a graph between t/qt and time.
10
6
Ce/qe

8
4

6
2
t/qt

4
0
0 10 20 30 40 50 60 70
2
Ce
Figure 6. Langmuir isotherms of RemazolRed on sawdust at
0
25ºC. 2 4 6 8 10 12 14
t(h)
Figure 7. Pseudo– second order kinetics plot for the adsorption
of Remazol Red on saw dust at 25ºC.

 
 
98 Ara et al. / Bangladesh Pharmaceutical Journal 16(1): 93-98, 2013

Theoretical and experimental data for the adsorption Cotoruelo, M.L., Marques, M.D. and Rodriguez, J.J. 2007.
Adsorption of aromatic compounds on activated carbons
kinetics are given in table 4. The experimental values of qe
from lignin: Equilibrium and thermodynamic study.Ind. Eng.
are closer to the calculated values for second order Chem. Res. 46, 4982-4990.
kinetics than those of first order kinetics. The value of Dee, A.K. Environmental Chemistry. 2006. 6thed. New Delhi:
correlation coefficient (R2) for second order is also closer New age International (P) Ltd. p. 208.
to unity as compared to that of first order (Table 4). Hassan, S.M.S., Awwad, N.S. Aboterika, A.H.A. 2009. Removal
of synthetic reactive dyes from textile wastewater by Sorel's
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sawdust and charcoal, more appropriately followed pseudo Ho, Y.S., Chiu, W.T. and Wang, C.C. 2005. Regression analysis
second order kinetic model. for the sorption isotherms of basic dyes on sugarcane dust,
Bioresour. Technol. 96, 1285-1291.
Table 4. Kinetic parameters for the adsorption of remazol Hu, Q.H., Qiao, S.Z. and Haghseresht, F., Wilson, M.A. and Lu,
red on sawdust. G.Q. 2006. Adsorption study for removal of basic red dye
using bentonite. Ind. Eng. Chem. Res. 45, 733-738.
Pseudo first order kinetic qe exp. Pseudo second order kinetic
Jain, R., Sharma, N. and Radhapyari, K. 2009. Electrochemical
model mg/g model
treatment of pharmaceutical azo dye amaranth from waste
qe K1 R2 qe K2 R2 water. J. Appl. Electrochem. 39, 577-582
(mg/g) (h-1) (mg/g) (h , g/mg) Mohanty, K., Naidu, J.T., Meikap, B.C. and Biswas, M.N. 2006.
2.62 0.83 2.36 2.73 0.092 0.96 Removal of crystal violet from waste water by activated
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Conclusion
Mon, J. 2004. Sorption and its Effects on Transport of Organic
In the present investigation activated saw dust was Dyes and Cesium in Soils. Ph.D. Thesis, Washington State
found to be better adsorbent for the removal of Remazol University, USA, pp. 28-36.
Red from aqueous media as compared to commercial Ozacar M. and Singel, A. 2005. Adsorption of metal complex
dyes from aqueous solutions by pine sawdust. Bioresour.
charcoal. Adsorption of the investigated dye decreases Technol. 96, 791-795.
with the increase in pH and slightly increases with Rabolli, V., Thomassen, L.C., Princen, C., Napierska, D.,
temperature of the solution. It was observed that Gonzalez, L., Kirsch-Volders M., Hoet, P.H., Huaux, F.,
adsorption process followed pseudo-second order kinetic Kirschhock, C.E., Martens, J.A. and Lison, D. 2010.
Influence of size, surface area and microporosity on the in
model. Values of qe calculated from pseudo second order
vitro cytotoxic activity of amorphous silica nanoparticles in
plots are in good agreement with the experimental values. different cell types. Nanotoxicology 4, 307-318.
Future investigations should be conducted with a view to Rao, M.M., Rao, G.P.C., Seshaiah, K., Choudary, N.V. and
selectively separating the present dye contaminants, Wang, M.C. 2008. Activated carbon from Ceibapentan-
regenerating the exhausted biomass, recovering the sorbed drahulls, an agricultural waste, as an adsorbent in the
removal of lead and zinc from aqueous solutions. Waste
dye and designing to continuous dye treatment systems.
Mange. 28, 849-858.
These studies can further ameliorate the economic aspects Senthilkumaa, S., Kalaamani, P., Porkodi, K., Varadarajan, P.R.
of dye wastewater treatment which will get better and Subburaam, C.V. 2006. J. Biores. Techn. 97, 1618-1625.
opportunity for the water related pollution remediation in Sousa, M.L. de, Moraes, P.B.de, Lopes, Paulo R.M.,
pharmacology. Montagnolli, R.N., Angelis, D.de F.de and Bidoia, E.D.
2012. Contamination by Remazol Red Brilliant Dye and its
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