J. Chem. T ech. Biotechnol.

1997, 69, 9399

Removal of Some Organic Dyes by

Hexane-Extracted Spent Bleaching Earth
Chnoong-Kheng Lee,* Kun-She Low & Lai-Ching Chung
Chemistry Department, Universiti Pertanian Malaysia, 43400 Serdang, Selangor, Malaysia
(Received 22 July 1996 ; revised version received 10 October 1996 ; accepted 21 October 1996)

Abstract : The removal of some organic dyes from aqueous solution by hexaneextracted spent bleaching earth, a waste material from the palm oil industry, was
investigated. It was noted that the material had better affinity for basic than acid
dyes. Various parameters aecting the removal process were studied. These were
pH, initial dye concentration, sorbent dosage, temperature and agitation rate in
the batch process. Experimental data show that both the boundary layer and
intraparticle diusion eect play important roles in the rate of dye removal.
Maximum sorption capacities for some basic and acid dyes studied compare
favourably with those reported using other low-cost sorbents.
Key words : basic dyes, acid dyes, hexane-extracted spent bleaching earth, sorption

INTRODUCTION

waste and disposed of in landll.10 This is, however, not

a desirable practice in view of the foul smell from degradation and also the risk of spontaneous ignition. Carbonization and activation of SBE has been reported to
yield materials which could be used for the stabilization
and solidication of mixed waste streams and as sorbents for organic compounds.11h13 The oil in SBE,
though of low quality, can be recovered through solvent
extraction using hexane. The resulting material, hexaneextracted spent bleaching earth (HSBE), is thus of no
more commercial value. In our continued eort to
utilize low-lost materials to remove pollutants from the
aqueous environment, the potential of HSBE as an
adsorbent for the removal of organic dyes was investigated. This paper reports the results of such an investigation.

The disposal of dye wastewater poses one of the textile

industrys major problems. Although dyes impart only a
small fraction of the total organic load in wastewater,
their high degree of colour is easily recognizable and
damages the aesthetic nature of the environment.
Among the various techniques used in treating aqueous
effluents, adsorption is becoming increasingly popular.
The most efficient and commonly used adsorbent is
activated carbon.1,2 However activated carbon is costly
and regeneration is a problem. Recent investigations
have focused on the use of low-cost materials such as
rice hulls, coconut husk, maize cobs, banana pith, activated alumina, sawdust, diatomite, y ash and chrome
sludge to remove dyes with varying degrees of
success.3h9
Bleaching earth, a montmorillonite mineral, is used
extensively to remove trace metals, chlorophylls, carotenoids, soap residues, residues of phosphorus compounds and peroxides in the palm oil industry in
Malaysia. Although the spent bleaching earth (SBE) still
contains 2030% of oil, it is generally discarded as a

2 EXPERIMENTAL
Spent bleaching earth obtained from a palm oil processing plant was extracted several times with hexane to
remove as much oil as possible and the resulting earth
was dried at 80C, ground and sieved to less than

* To whom correspondence should be addressed.

93
J. Chem. T ech. Biotechnol. 0268-2575/97/$17.50 ( 1997 SCI. Printed in Great Britain

C. K. L ee, K. S. L ow, L . C. Chung

94
150 km in size. The removal of oil from SBE was conrmed by recording the infra-red spectrum of the
solvent-treated SBE. The absence of the characteristic
bands at 2928, 2845 cm~1 (CwH stretching) and
1746 cm~1 (CxO) for triglyceride in HSBE indicates
that palm oil has been successfully removed from the
SBE. The basic dyes used were Basic Blue 3 (CI 51004,
80% purity Sigma) and Methylene Blue (CI 52015, 85%
purity BDH), whereas the acid dyes used were Acid
Blue 25 (CI 62055, 45% purity Sigma), Acid Blue 29 (CI
20460, 40% Sigma), Reactive Blue 2 (CI 61211, 60%
purity Aldrich) and Reactive Yellow 2 (CI 18972, 60%
purity Sigma). All the dyes were used without further
purication. Standard solutions of 500 mg dm~3 were
prepared and subsequently diluted when necessary. The
concentration of dye in the solution was determined
using a Shimadzu 160 double-beam UV spectrophotometer with a 10 cm quartz light cell. The wavelength
was selected so as to obtain maximum absorbance for
each dyestu and the j
values were 654 (Basic Blue
max
3), 664 (Methylene Blue), 600 (Acid Blue 25), 602 (Acid
Blue 29), 607 (Reactive Blue 2) and 403 nm (Reactive
Yellow 2).
All the experiments were carried out in duplicate.
Sorption was measured by equilibrating 01 g of HSBE
with 25 cm3 of dye solution of concentration
500 mg dm~3 at an agitation rate of 200 rpm for 6 h
unless otherwise stated. At the end of equilibration the
sorbentdye mixture was centrifuged at 3000 rpm for
phase separation and the dye concentration of the
supernatant determined.
To study the eect of pH on sorption, the pH of the
dye solution was adjusted to the range of 2 to 10 by
addition of 01 M HCl or 01 M NaOH prior to experimentation. The eect of initial dye concentration was
investigated using dye solutions of concentrations
ranging from 500 to 2000 mg dm~3. In the study of
temperature eect, a thermostatted water bath was used
and the temperature was varied between 10 and 50C.
The concentration of the dye solutions were 1000 and
500 mg dm~3 for Basic Blue 3 and Methylene Blue
respectively.

Fig. 1. Comparative study of the uptake of various dyes by

HSBE.

3.2. Eect of pH
The eect of pH on the uptake of Basic Blue 3 and
Methylene Blue by HSBE is shown in Fig. 2. Sorption
capacity increased with increasing pH. This could be
attributed to the increase in electronegative charge on
the surface of the sorbent as the pH of the solution
increased. The surface hydroxyl groups of HSBE at different pH values can be represented as :
SOH` \ SOH ] H` \ SO~ ] 2H`
Protonated

Neutral

Deprotonated

At high pH, sorption for positively-charged molecules is

expected to be more favourable as the surface of HSBE
is deprotonated.14 The surface hydroxyl groups cannot,
however, solely account for the uptake of dyes as a sig-

3 RESULTS AND DISCUSSION

3.1 Comparative study on the sorption of various dyes
by HSBE
The results of the comparative study (Fig. 1) show that
HSBE is a better sorbent for basic than for acid dyes.
All the acid dyes except Acid Blue 25 had sorption of
less than 10% compared with greater than 80% sorption exhibited by the two basic dyes. This is probably
due to the negatively-charged surface of HSBE which
has higher affinity for cationic dye molecules.

Fig. 2. Eect of pH on the uptake of Basic Blue 3 and Methylene Blue by HSBE.

Dye removal by hexane-extracted spent bleaching earth

nicant amount of dye was sorbed even at pH 2. This
indicates that other binding sites exist, probably due to
the activated carbon formed during the bleaching
process at elevated temperature. As sorption was sufficiently high at the natural pH of the dye solutions (56
and 65 for Basic Blue 3 and Methylene Blue
respectively), no adjustment of pH was carried out in
subsequent experiments.

3.3 Eect of initial dye concentration

Figure 3 shows the eect of initial dye concentration in
a contact time experiment for Basic Blue 3. The initial
rate of uptake was rapid, irrespective of the initial dye
concentration. Pseudo-equilibrium was achieved after
120 min, thereafter a more gradual process was
observed. A similar trend was observed for the Methylene BlueHSBE system. The rapid uptake at the early
stages of sorption means that HSBE could be useful in
the continuous ow studies where the contact time
between sorbate and sorbent is generally short. The
uptake of Basic Blue 3 increased from 525 to 864% as
the
concentration
decreased
from
1000
to
500 mg dm~3.

3.4 Sorption isotherm

The sorption data for the dierent dyeHSBE systems
were tted into a modied Langmuir equation :
C /N \ 1/N*b ] C /N*
e e
e
where C is the concentration of the dye solution at
e
equilibrium (mg dm~3), N the amount of dye sorbed
e
by HSBE at equilibrium (mg g~1), b the equilibrium

Fig. 3. Eect of initial concentration on the uptake of Basic

Blue 3 by HSBE.

95
constant related to the sorption energy between the
sorbate and sorbent (dm3 mg~3) and N* the maximum
sorption of the dyeHSBE system. The linearity of the
plots for Basic Blue 3, Methylene Blue and Acid Blue 25
in Fig. 4 shows the applicability of the above model,
indicating the possible formation of monolayer coverage. The values of N* obtained from the plots are
shown in Table 1. N* values obtained from some earlier
studies using carbonized spent bleaching earth and biosorbents are included for comparison. The sorption
values obtained in the present study compared favourably with values obtained using other sorbents. It
appears that for spent bleaching earth, hexane extraction may be more advantageous than carbonization as
it is more economical and yields sorbents of higher
sorption capacity. A brief economic comparison
between these two sorbents prepared under laboratory
conditions is shown in Table 2. The relative cost to
remove 1 g of basic dye by CSBE is approximately
three times that of HSBE.
3.5 Sorption dynamics
In a well-agitated system, the colour removal can be
considered as consisting of three steps : (i) mass transfer
of dye molecules from the solution to sorbent surface (ii)
intraparticle diusion and (iii) sorption at an interior
site. The last step is assumed to be rapid while steps (i)
and (ii) are the rate determining steps, either singly or in
combination.
Determination of the rate-determining steps in sorption is important as it provides useful information on
rate parameters for design purposes. If mass transfer of
dye molecules is an important factor in controlling the
rate, then the rate of agitation would have an eect on
the uptake. Increasing agitation speed decreases the lm
resistance to mass transfer surrounding the sorbent particles and increases the mobility of the system. It was

Fig. 4. Langmuir isotherms of the dyeHSBE systems. Initial

dye concentrations ranged from 100 to 1000 mg dm~3.

C. K. L ee, K. S. L ow, L . C. Chung

96

TABLE 1
Maximum Sorption Capacity, N*, of Some DyeSorbent Systems
Sorbent

Dye

N* (mg g~1)

Reference

HSBE
HSBE
HSBE
CSBEa
CSBE
Cotton waste
Coconut husk
Hydrilla verticillata
Hydrilla verticillata
Water hyacinth root
Maize cob
Wood
Chrome sludge

Basic Blue 3
Methylene Blue
Acid Blue 25
Basic Blue 3
Methylene Blue
Methylene Blue
Methylene Blue
Basic Blue 3
Methylene Blue
Methylene Blue
Acid Blue 25
Acid Blue 25
Acid Blue 25

1580
1205
210
1026
945
2400
990
1270
1980
1289
414
83
323

Present study
Present study
Present study
Low et al.13
Low et al.13
McKay et al.19
Low and Lee4
Low et al.20
Low et al.20
Low et al.17
El-Guendi21
Poots et al.22
Lee et al.9

a CSBEcarbonized spent bleaching earth.

noted that a higher agitation rate resulted in higher percentage uptake for both Basic Blue 3 and Methylene
Blue, as shown in Fig. 5 for the former. The importance
of mass transfer or boundary layer eect can be further
tested using the Boundary Model which assumed that
the surface concentration of the sorbate is negligible at

time t \ 0, and consequently, intraparticle diusion

would be negligible.15 In a well-agitated system where
both the sorbent and sorbate particle concentrations in
the liquid phase are assumed to be uniform, the solid
concentration, m, is dened as :
m \ w/v
where w is the amount of HSBE and v, the volume of
the solution.
The boundary layer eect is tested using the equation :

Fig. 5. Eect of agitation rate on the uptake of Basic Blue 3

by HSBE.

ln[C /C [ 1/(1 ] mk)] \ ln[mk/(1 ] mk)]

t 0
[(1 ] mk)b St/mk
L
where k is the product of N* and b obtained from the
langmuir isotherm plot, S the surface area for mass
transfer and b the liquidsolid mass transfer coefficient.
L
A straight line plot of ln[C /C [ 1/(1 ] mk)] versus t
t 0
would indicate the applicability of the above equation.
This equation was developed for the study of the surface
mass transfer processes during the removal of Astrazone
Blue dye from effluents using silica.15 It illustrated the
importance of the surface mass transfer of dye from the
bulk liquid across the boundary layer to the surface of

TABLE 2
Relative Cost of Dye Removal
Dye

Basic Blue
Basic Blue
Methylene
Methylene

3
3
Blue
Blue

Sorbent

Sorption
capacity
(mg g~1)

Mass (g) of
sorbent to
remove 1 g
of dye

Relative cost
per kg of
sorbent

Relative cost
to remove 1 g
of dye

HSBE
CSBE
HSBE
CSBE

1580
1026
1205
945

6
10
8
10

1
2
1
2

1
333
133
333

Dye removal by hexane-extracted spent bleaching earth

97

the sorbent particle during the initial stages of dye

removal. Figure 6 shows such plots for Basic Blue 3
and Methylene BlueHSBE systems. The plots are
linear in the initial stages of the sorption process, thereafter deviation is observed. This indicates that the
boundary layer eect was important for up to 30 and
60 min for the Basic Blue 3 and Methylene Blue
HSBE systems respectively.
In order to determine the importance of intraparticle
diusion in the sorption process, the amount of dye
sorbed at time t, q , was plotted versus the square root
t
of time, t1@2, according to the equation q \ Kt1@2.16 If
t
intraparticle diusion is the rate determining step, a
linear plot would be obtained and the intraparticle diffusion rate parameter, K, could be estimated from the
slope of the straight line. Figure 7 shows such plots for
the Basic Blue 3 and Methylene BlueHSBE systems.
In both cases, an initial curve is followed by a straight
line, indicating that more than one mode of sorption
mechanism was in operation in the uptake of the dyes.
The initial curve (30 and 60 min duration for Basic Blue
3 and Methylene Blue system respectively) can be
explained by the boundary layer eect while the linear
portion corresponds to intraparticle diusion. The
intraparticle diusion rate parameters for the two
systems are calculated from the linear portion of the
Fig. 7. Sorption of (a) Basic Blue 3 and (b) Methylene Blue
onto HSBE for the determination of intraparticle diusion
coefficient at various initial dye concentrations.

plots and listed in Table 3. The values are comparable

to those reported for the dyewater hyacinth root
system.17
3.6 Eect of temperature
The variation of uptake with temperature for Basic Blue
3 and Methylene Blue on HSBE is shown in Table 4.
The percentage uptake of both dyes increased as temperature increased, probably due to an increase of the
mobility of the dye molecules in solution. As diusion
was an endothermic process, the rate of sorption would
increase with increasing solution temperature when
intraparticle diusion is the rate determining step.16
Thus the importance of intraparticle diusion in the
TABLE 3
Intraparticle Diusion Rate Parameters of Dyes
Dye concentration
(mg dm~3)

Fig. 6. Mass transfer of (a) Basic Blue 3 and (b) Methylene

Blue on the surface of HSBE at various initial dye concentrations.

500
750
1000
2000

Rate parameter, K , (mg g~1 min~1@2)

d
Basic Blue 3

Methylene Blue

180
271
274

279

319
392

C. K. L ee, K. S. L ow, L . C. Chung

98
TABLE 4
Eect of Temperature on the Uptake of Dyes
T emperature (K)

Uptake (%)
Basic Blue 3
(C \ 1000 mg dm~3)
0

Methylene Blue
(C \ 500 mg dm~3)
0

3747
5342
5975
6317

5137
7530
8608
9158

283
303
313
323

C , Initial concentration of dyes.

0

sorption process is further substantiated. The endothermic nature of the process can be conrmed by the
calculation of enthalpy (*H) using the vant Ho equation :

obtained from the vant Ho plots (Fig. 8), are 2073

and 4484 kJ mol~1 for Basic Blue 3 and Methylene
Blue respectively.
3.7 Eect of sorbent dosage

log K \ *S/2303R [ *H/2303RT

d
where K , the distribution coefficient, is dened as q
d
e
(mg g~1 dye sorbed at equilibrium)/C (equilibrium dye
e
concentration, mg g~1). The values of enthalpy,

The eect of sorbent dosage on the uptake of both the

basic dyes under equilibrium conditions was studied. It
follows the expected pattern of increasing percentage
sorption as the dosage increases. With an initial dye
concentration of 550 and 450 mg dm~3 for Basic Blue 3
and Methylene Blue respectively, saturation occurred at
02 g sorbent where further increase of dosage had no
eect on sorption (Table 5). Such a study is useful in
establishing the optimum amount of sorbent to be used
in the removal of dyes. The eect of sorbent dosage on
kinetics was not investigated in the present study.
However, earlier studies have shown that increasing
sorbent dosage increased the rate of dye sorption in the
adsorption of Astrazone Blue onto red clay18 and
adsorption of Telon Blue, Deorlene Yellow and Disperse Blue 7 onto activated carbon.1
4 CONCLUSION

Fig. 8. vant Ho plots of sorption of Basic Blue 3 and

Methylene Blue on HSBE.
TABLE 5
Eect of Sorbent Dosage on the Uptake of Dyes
Mass of
sorbent (g)

005
008
010
015
020
030
040

Uptake (%)
Basic Blue 3
(C \ 550 mg dm~3)
0

Methylene Blue
(C \ 450 mg dm~3)
0

5433
7859
9040
9910
9971
9990
9994

5032
6995
8188
9826
9992
9996
9997

C , Initial concentration of dye.

0

The results show that HSBE is a useful sorbent in the

removal of organic dyes, especially basic dyes. The rate
controlling step appears to be a combination of boundary layer and intraparticle diusion eect. The use of
HSBE to remove dyestu from wastewater is a programme aiming at cleaning up the environment by the
use of waste material. It is economical on a large scale
as SBE is inexpensive and easily available.
ACKNOWLEDGEMENT
The nancial support of the Malaysian Government
under Research Grant No. IRPA 04-07-05-017 is
acknowledged.
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