Journal of Colloid and Interface Science 281 (2005) 4955

www.elsevier.com/locate/jcis

A comparative adsorption study with different industrial wastes

as adsorbents for the removal of cationic dyes from water
Amit Bhatnagar ,1 , A.K. Jain
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, India
Received 31 May 2004; accepted 10 August 2004
Available online 1 October 2004

Abstract
Four adsorbents have been prepared from industrial wastes obtained from the steel and fertilizer industries and investigated for their utility
to remove cationic dyes. Studies have shown that the adsorbents prepared from blast furnace sludge, dust, and slag have poor porosity and
low surface area, resulting in very low efficiency for the adsorption of dyes. On the other hand, carbonaceous adsorbent prepared from
carbon slurry waste obtained from the fertilizer industry was found to show good porosity and appreciable surface area and consequently
adsorbs dyes to an appreciable extent. The adsorption of two cationic dyes, viz., rhodamine B and Bismark Brown R on carbonaceous
adsorbent conforms to Langmuir equation, is a first-order process and pore diffusion controlled. As the adsorption of dyes investigated was
appreciable on carbonaceous adsorbent, its efficiency was evaluated by comparing the results with those obtained on a standard activated
charcoal sample. It was found that prepared carbonaceous adsorbent exhibits dye removal efficiency that is about 8090% of that observed
with standard activated charcoal samples. Thus, it can be fruitfully used for the removal of dyes and is a suitable alternative to standard
activated charcoal in view of its cheaper cost.
2004 Elsevier Inc. All rights reserved.
Keywords: Rhodamine B; Bismark Brown R; Wastewater; Industrial solid wastes; Adsorbents

1. Introduction
Dyes are important water pollutants which are generally
present in the effluents of the textile, leather, food processing, dyeing, cosmetics, paper, and dye manufacturing industries. They are synthetic aromatic compounds which are embodied with various functional groups. The worldwide high
level of production and extensive use of dyes generates colored wastewaters which cause environmental pollution. The
colored dye effluents are generally considered to be highly
toxic to the aquatic biota [1] and affect the symbiotic process
by disturbing the natural equilibrium through reduced photosynthetic activity due to the coloration of the water in
* Corresponding author. Fax: +41-1-823-5210.

E-mail address: amit.bhatnagar@eawag.ch (A. Bhatnagar).

1 Present address: Water Resources and Drinking Water (W+T), Swiss

Federal Institute for Environmental Science & Technology (EAWAG), Postfach 611, Ueberlandstrasse 133, CH-8600, Duebendorf, Switzerland.
0021-9797/$ see front matter 2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2004.08.076

streams. The nonbiodegradable, toxic, and inhibitory nature

of spent dye baths has a considerable deleterious effect on
the environmental matrix (water and soil). Some dyes are
reported to cause allergy, dermatitis, skin irritation, cancer,
and mutations in humans [2,3]. Thus, the removal of dyes
from effluents before they are mixed up with unpolluted natural water bodies is important. Several treatment technologies exist for dye removal [4], but the process of adsorption
using activated carbon [58] has been found to be an efficient technology for decolorization of wastewater. Though
the removal of dyes through adsorption is quite effective,
its use is restricted sometimes due to the higher cost of activated carbon and difficulties associated with regeneration.
Attempts have therefore been made to utilize natural as well
as waste materials as alternative adsorbents. But the utilization of industrial waste materials is of vital concern over
the past few years because these wastes represent unused
resources and, in many cases, cause serious disposal problems. The aim behind using waste materials as adsorbents is

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A. Bhatnagar, A.K. Jain / Journal of Colloid and Interface Science 281 (2005) 4955

that it will provide a twofold advantage with respect to environmental pollution. First, the volume of waste materials
could be partly reduced, and second, the low-cost adsorbent,
if developed, can reduce the pollution of wastewaters at a
reasonable cost. In view of the low cost of such adsorbents, it
would not be necessary to regenerate spent materials. Thus,
a number of waste materials from different sources have
been investigated with or without treatment as adsorbents
for the removal of dyes from wastewater. Recently, Garg et
al. [9] have listed materials studied as adsorbents for dye removal from aqueous solutions.
A number of low-cost alternative adsorbents have been
explored but they have not been highly successful. In general
the limitations of such studies have been
(i) the surface area of alternative adsorbents developed has
been low in most cases, resulting in poor adsorptive
power;
(ii) comparative studies on different adsorbents have not
been carried out; and
(iii) the performance of alternative adsorbents has not been
assessed by comparing the results with those obtained
on activated carbon.
It is therefore still important to develop low-cost adsorbents
with good surface area, which may in turn exhibit good adsorption potential for the removal of aqueous pollutants.
Keeping the above points under consideration, a comparative adsorption study was carried out by us [10] using
carbon slurry waste obtained from a fertilizer plant and blast
furnace sludge, dust, and slag from steel plant wastes as adsorbents for the removal of two anionic dyes, methyl orange
and brilliant blue G. It was found that carbonaceous adsorbent prepared from a fertilizer plant exhibits good potential
for the removal of dyes as compared to the other three adsorbents prepared. In order to further test the versatility of
the carbonaceous adsorbent, investigations with regard to
the adsorption of another class of dyes, cationic dyes, were
also undertaken, and two important and widely used cationic
dyes, rhodamine B and Bismark Brown R, were studied on
all the adsorbents prepared. Further, a comparative study
with standard activated charcoal was also carried out and the
results are incorporated into the present communication.

2. Materials and methods

2.1. Materials
Rhodamine B and Bismark Brown R were procured
from S.D. Fine-Chem. Limited (India). The standard activated charcoal sample was obtained from E. Merck. Other
reagents used were of AR grade. Double-distilled water was
used in preparing solutions throughout these investigations.

2.2. Preparation of adsorbents

The adsorbents under investigation have been prepared
from fertilizer and steel plant wastes.
2.2.1. Preparation of carbonaceous adsorbent
In India, carbonaceous slurry waste is produced in fertilizer plants using fuel oil/LSHS (low sulfur heavy stock).
This slurry is available at a very cheap rate ($0.007 per kg)
and can act as a good adsorbent in view of its porous nature. The dried carbon slurry was procured from National
Fertilizer Limited (NFL), Panipat (India). It was found to
consist of small, black, greasy granules and treated [10,11]
with H2 O2 to oxidize the adhering organic material. It was
then washed with distilled water and heated at 200 C till
the evolution of black soot stopped. The activation of this
material was done in the range 300700 C in a muffle furnace for 1 h in the presence of air. After the activation, the
ash content was removed by treating the material with 1 M
HCl and washed with distilled water and dried. The surface
area of samples activated at temperatures of 300, 400, 500,
600, and 700 C was found to be 280, 363, 380, 374, and
367 m2 g1 , respectively. Thus, the activation at 500 C imparts maximum surface area and it was also seen that the
extent of adsorption was at a maximum for the sample activated at 500 C. Therefore, all studies reported in this paper
are on a sample activated at 500 C. The yield of the finished
product was found to be 90% and it is now called carbonaceous adsorbent. Different mesh sizes were obtained
after sieving and kept in a desiccator for further use.
2.2.2. Preparation of blast furnace sludge, dust, and slag
adsorbents
These adsorbents were prepared from wastes obtained
from Malvika Steels, Jagdishpur (India), by the method reported elsewhere [10]. The products were sieved and stored
in a desiccator.
2.3. Instrumentation
The spectrophotometric determination of dyes was done
on a Shimadzu 1601 UVvis spectrophotometer. The pH of
solutions was measured with an ELICO LI 127 pH meter.
A Vario EL III, C H N S elemental analyzer was used to
determine the carbon content of the adsorbents.
2.4. Adsorption studies
The adsorption of dyes on prepared adsorbents was studied at room temperature by employing the batch method.
A known volume (10 ml) of dye solutions of varying initial concentrations, taken in 50-ml stoppered glass tubes, was
shaken with a fixed dose of adsorbent (0.01 g) for a specified
period of contact time in a thermostated shaking assembly.
After equilibrium, the concentration of the adsorbate in the
residual solution was determined spectrophotometrically at

A. Bhatnagar, A.K. Jain / Journal of Colloid and Interface Science 281 (2005) 4955

max of 554.0 nm for rhodamine B and 460.0 nm for Bismark Brown R. The experiments were repeated a number
of times and average values are reported. Standard deviations were found to be within 3.0%. Furthermore, error
bars for the figures were smaller than the symbols used to
plot the graphs and hence are not shown. The pH of the solutions was adjusted using dilute sulfuric acid and sodium
hydroxide solutions. The pH of the solutions was measured
before and after the equilibration and a slight change in
pH was observed. However, after adjustment of the pH of
the adsorbentadsorbate system no further change was observed. The pH of solutions in contact with adsorbents was
found to be in the range from 5.5 to 6.5 for both dyes. The
adsorption was studied as a function of contact time, concentration, particle size, and temperature. Kinetic studies of
adsorption were also carried out at two concentrations of the
adsorbates where the extent of adsorption was investigated
as a function of time.

3. Results and discussion

3.1. Characterization of the prepared adsorbents
The BF sludge, dust, and slag were chemically analyzed
and it was found that BF slag is basically inorganic in nature;
i.e., it contains mainly inorganic constituents such as silica
(32.7%), calcium oxide (31.7%), magnesium oxide (6.8%),
and R2 O3 ; R = Fe, Al (22.8%). On the other hand, silica,
R2 O3 (mainly iron oxide), and carbon (due to the presence of
coke particles) are the prominent components of BF dust and
sludge. Although the inorganic constituents such as silica
(15.8% and 12.7%), R2 O3 (44.9% and 35.4%), MgO (4.2%
and 3.0%), and CaO (4.7% and 3.5%) in BF dust and sludge,
respectively, are present in major amounts, but the presence
of appreciable carbon content impart a partial organic character to BF sludge and dust. Of course, the partial organic
character of BF sludge (carbon content = 35.0%) is more
than that of BF dust (carbon content = 21.7%). We may
therefore say that BF sludge and dust is of mixed character,
with inorganic nature predominating over organic. However,
as compared to slag, dust, and sludge, the analysis of carbon
slurry indicates 0.9% ash and 89.8% carbon. Thus, due to
the presence of high carbon content, the carbon slurry may
be treated as organic in nature.
In order to assess the adsorption characteristics of these
four adsorbents, their surface area was determined by N2 gas
adsorption and given in Table 1 with other important adsorption characteristics of the adsorbents used. It is seen from Table 1 that surface area increases as carbon content increases
from BF slag to carbonaceous adsorbent, indicating that the
porosity of carbon is responsible for higher surface area. To
confirm it, SEM photographs of the four adsorbents were
taken which clearly showed that BF sludge, dust, and slag
possess very poor porosity whereas carbonaceous adsorbent
exhibits a significantly porous structure, giving rise to a com-

51

Table 1
Characteristics of adsorbents used
Standard Carbonaceous
activated adsorbent
charcoal
710
Surface area
(m2 g1 )
Methylene
198
blue number
Iodine number 635

BF sludge BF dust BF slag

380

28

13

90

330

24

11

paratively higher surface area. Further, the methylene blue

number and iodine number, important characteristics of an
adsorbent, also confirm that carbonaceous adsorbent would
be a better adsorbent for pollutants (dyes) removal than the
other three adsorbents.
3.2. Effect of contact time and concentration
The effect of contact time on the adsorption of Bismark
Brown R and rhodamine B is shown in Fig. 1. It is seen that
nearly 25 min are required for the equilibrium adsorption
to be attained for both the dyes. As such for all adsorption studies, the equilibration time was kept 3 h. It is further seen from Fig. 1 that adsorption is very fast initially,
showing that 50% adsorption in the case of both the dyes
is completed in 6 min. After that it slowly attains equilibrium adsorption. The effect of concentration on equilibrium
adsorption time was also investigated as a function of initial dye concentration and the results are shown in Fig. 1 (in
the case of rhodamine B). Similar plots were also obtained
for other dyes. These plots show that the time of equilibrium

Fig. 1. Effect of contact time on uptake of cationic dyes on carbonaceous adsorbent at different initial concentrations (temperature 25 C; particle size
200250 mesh).

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A. Bhatnagar, A.K. Jain / Journal of Colloid and Interface Science 281 (2005) 4955

Fig. 2. Effect of particle size on the uptake of rhodamine B on carbonaceous

adsorbent (temperature 25 C).

adsorption as well as the time required to achieve a definite

fraction of equilibrium adsorption is independent of the initial dye concentration. This type of behavior indicates that
the adsorption process is first-order, which is confirmed by
Lagergrens plots discussed later under dynamic modeling.
These results are similar to our previous studies with anionic
dyes.
3.3. Effect of particle size
The adsorption of both the dyes was also investigated at
three particle sizes, 100150, 150200, and 200250 British
Standard Sieve (BSS) mesh, and the results are shown in
Fig. 2 (in the case of rhodamine B). Similar plots were also
obtained for other dyes. It is seen that with decreased particle
size, the adsorption increases to some extent. This could not
be due to any substantial increase in surface area [12]. It
appears that large molecules of dyes are not able to penetrate
into some of the interior pores of the particles when their
size is large. Apparently access to all pores is facilitated as
particle size becomes smaller, resulting in higher adsorption.
Similar observations were also made by McKay et al. [13].
As particles of size 200250 BSS mesh exhibit maximum
adsorption capacity, all further detailed studies were done
with this fraction only.
3.4. Adsorption isotherms
To assess the adsorption potential of the four prepared adsorbents for cationic dyes, their adsorption isotherms were
drawn (Fig. 3 for rhodamine B). Similar type of plots were
also obtained for another dye. It is seen from these plots
that the extent of adsorption is in the order carbonaceous
adsorbent > BF sludge > BF dust > BF slag for both the
cationic dyes, which is parallel to the surface area of the adsorbents. Further, the maximum adsorption on carbonaceous
adsorbent, BF sludge, dust, and slag is found to be 71.5,
8.2, 4.6, and 2.7 mg g1 for Bismark Brown R and 82.8,

Fig. 3. Adsorption isotherms of rhodamine B on different adsorbents at

25 C (, standard activated charcoal; 5, carbonaceous adsorbent; *, BF
sludge; P, BF dust; ', BF slag).

10.0, 7.1, and 3.4 mg g1 for rhodamine B on carbonaceous

adsorbent, BF sludge, BF dust, and BF slag, respectively.
Broadly, this type of adsorption behavior is similar to that of
anionic dyes. However, the adsorption of cationic dyes onto
carbonaceous adsorbent and sludge is smaller than the adsorption of anionic dyes reported earlier. On the other hand,
the adsorption of these dyes onto BF dust and slag, though
very small, is found to be slightly higher than that observed
for anionic dyes. The slightly higher adsorption on these two
adsorbents could be due to some partially negative charge on
metal oxide constituents present in BF dust and slag. Thus,
these results again show that carbonaceous adsorbent, which
is of an organic nature, having higher porosity and surface area, is a suitable adsorbent for the removal of another
class of dyes, i.e., cationic dyes, whereas the other three adsorbents, which are mainly of an inorganic nature, having
poor porosity and surface area, are poor adsorbents. Out of
the four adsorbents prepared, only carbonaceous adsorbent
shows substantial potential for the removal of cationic dyes
(organics); its performance was evaluated by comparing the
results with those obtained on standard activated charcoal.
The adsorption isotherms of both the cationic dyes on standard activated charcoal were also determined and shown in
Fig. 3. A comparison of maximum adsorption capacity (as
obtained from adsorption isotherms) of the dyes on carbonaceous adsorbent and standard activated charcoal shows that
carbonaceous adsorbent is about 8090% as efficient as standard activated charcoal. Thus, it is reasonable to conclude
that prepared carbonaceous adsorbent is appreciably efficient in removing dyes from aqueous solutions and, therefore, all further studies were carried out on this adsorbent
only.

A. Bhatnagar, A.K. Jain / Journal of Colloid and Interface Science 281 (2005) 4955

53

Fig. 5. Langmuir adsorption isotherms of rhodamine B on carbonaceous

adsorbent at different temperatures.

Fig. 4. Adsorption isotherms of dyes on carbonaceous adsorbent at 45 C.

3.5. Effect of temperature

To determine the effect of temperature on the adsorption of dyes, experiments were also conducted at 45 C and
results are shown in Fig. 4. A comparison of adsorption
isotherms at 25 and 45 C shows that adsorption decreases
with increased temperature, indicating that the adsorption is
exothermic. The adsorption data were further analyzed and
found to conform best to the Langmuir equation
1
1
1
=
+
,
qe qm qm bCe

1
.
1 + bC0

Dyes

Temperature
( C)

qm
(mg g1 )

b
(l mol1 )

RL

Bismark Brown R

25
45

85.0
73.2

4.4 104
4.3 104

7.0 101
7.1 101

Rhodamine B

25
45

91.1
83.3

7.9 104
7.6 104

5.7 101
5.8 101

Table 3
Thermodynamic parameters for the adsorption of cationic dyes on carbonaceous adsorbent at different temperatures
Dyes

(1)

where qe is the amount adsorbed at equilibrium concentration Ce , qm the Langmuir constant representing maximum
monolayer capacity, and b the Langmuir constant related to
energy of adsorption. The plots between 1/qe and 1/Ce for
the adsorption of rhodamine B are drawn in Fig. 5. Similar plots were also obtained for other dye. The values of
monolayer capacity (qm ) and Langmuir constant (b) have
been evaluated from the intercept and slope of these plots
and given in Table 2. A perusal of Table 2 shows that monolayer capacity (qm ) of the adsorbent for the dyes is comparable to the maximum adsorption obtained from adsorption
isotherms (Fig. 3). As b values reflect equilibrium constant
for the adsorption process, it shows the affinity of the adsorbent for dye.
The effect of isotherm shape has been discussed [14] with
a view to predicting whether an adsorption system is favorable or unfavorable. The essential feature of the Langmuir
isotherm can be expressed in terms of RL , a dimensionless
constant referred to as separation factor or equilibrium parameter. RL is calculated using the following equation:
RL =

Table 2
Langmuir constants and separation factor for the adsorption of cationic dyes
on carbonaceous adsorbent at different temperatures

(2)

S 0
H 0
Temperature G0
(kJ mol1 ) (J mol1 K1 ) (kJ mol1 )
( C)

Bismark Brown R 25
45

26.5
28.2

86.2
86.2

0.81

Rhodamine B

27.9
29.7

89.9
89.9

1.12

25
45

The values of RL calculated per the above equation are incorporated into Table 2. As the RL values lie between 0 and 1,
the adsorption isotherm is favorable [14].
The values of free energy change (G0 ), enthalpy
change (H 0 ), and entropy change (S 0 ) for the adsorption process were calculated using the equations
G0 = RT ln(b),
ln(b2 /b1 ) =

H0
R

1
1
,

T2 T1

G0 = H 0 T S 0

(3)
(4)
(5)

and are summarized in Table 3. The small negative values

of H 0 indicate that the adsorption is physical in nature,
involving weak forces of attraction. Further, negative G0
values indicate the spontaneous nature of the adsorption
process and positive S 0 values indicate the affinity of the
adsorbent for dyes.

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A. Bhatnagar, A.K. Jain / Journal of Colloid and Interface Science 281 (2005) 4955

Fig. 7. Bangham plot for dyes on carbonaceous adsorbent.

adsorption studies was tested,





 k 0 m
C0
=
log
log log
+ log t,
C0 q  m
2.303V

Fig. 6. Lagergren plot for dyes on carbonaceous adsorbent.

3.6. Dynamic modeling

Kinetics of sorption is one of the important characteristics
in defining the efficiency of sorption. Various kinetic models
have been proposed by different workers where the adsorption has been treated as first-order [15,16], pseudo-first-order
[17,18], and pseudo-second-order processes [19]. Different
systems conform to different models. The Lagergren rate
equation [20] is the one most widely used [15,16,21] for the
sorption of a solute from a liquid solution. Thus this firstorder equation,
kads
t,
(6)
2.303
where qe and q are the amounts of the dye adsorbed at equilibrium and at time t, in mg g1 , and k ads the first-order rate
constant, was applied to the present studies of dye adsorption. As such, the values of log(qe q) were calculated from
the kinetic data of Fig. 1 and plotted against time in Fig. 6.
The plots are found to be linear, indicating that Lagergrens
equation is applicable to the dye adsorption on carbonaceous
adsorbent and the adsorption is a first-order process. The
first-order rate constants calculated from the slope of the
plots (Fig. 6) are found to be 1.24 101 min1 for rhodamine B and 1.54 101 min1 for Bismark Brown R.
The kinetic data were further used to learn about the slow
step occurring in the present adsorption system. The applicability of Banghams equation [22] to the present dye

log(qe q) = log qe

(7)

where C0 is the initial concentration of the adsorbate in

solution (mmol l1 ), V the volume of the solution (ml),
m the weight of adsorbent used per liter of solution (g l1 ),
q  (mmol g1 ) the amount of adsorbate retained at time t,
and (< 1) and k0 are constants. As such log log[C0 /(C0
q  m )] was plotted against log t in Fig. 7. The linearity of
these plots confirms the applicability of Banghams equation
and indicates that the adsorption is pore-diffusion-controlled
[17,22].

4. Conclusions
It is reasonable to conclude from the present investigations on the adsorption of cationic dyes on some adsorbents
prepared from industrial wastes that (i) carbonaceous adsorbent possessing an organic nature and consequently having
higher surface area and porosity is efficient for the removal
of dyes, whereas the other three adsorbents, BF sludge, dust,
and slag, possessing inorganic nature resulting in lower surface area and porosity, are poor materials for this purpose;
(ii) the adsorption of dyes on carbonaceous adsorbent is firstorder and pore-diffusion-controlled; and (iii) carbonaceous
adsorbent is about 8090% as efficient as standard activated
charcoal and thus can be used in its place for the removal of
dyes from effluents in view of its cheaper cost ($0.10 per kg).

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