Journal of Industrial and Engineering Chemistry 21 (2015) 635643

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

The removal of heavy metals in a packed bed column using

immobilized cassava peel waste biomass
Geoffrey S. Simate *, Sehliselo Ndlovu
School of Chemical and Metallurgical Engineering, University of the Witwatersrand, P/Bag 3, Wits, Johannesburg 2050, South Africa

A R T I C L E I N F O A B S T R A C T

Article history: Several studies on the removal of heavy metals in batch systems using cassava waste biomass have been
Received 8 January 2014 reported in literature. However, for practical and large scale operations, packed bed columns are
Received in revised form 6 March 2014 preferred. This study investigated the biosorption of heavy metals (Cr3+, Co2+ and V3+) onto immobilized
Accepted 17 March 2014
cassava peel waste in a packed bed column. Experiments were conducted with 100 mg/L of combined
Available online 25 March 2014
metal ion solutions under different ow rates (0.831.61 mL/s) and bed depths (515 cm). The dynamic
behaviour of the process was described in terms of the breakthrough curves. The results showed that the
Keywords:
removal efciency was favoured by low ow rate and high bed depth. Biosorption efciency was found
Heavy metals
Wastewater
to increase in the order V3+ > Cr3+ > Co2+ for all conditions tested. Amongst the two well-established
Biosorption column models tested, the bed depth service time (BDST) model with biosorption capacities of 99.6,
Immobilized cassava peel waste biomass 116.2 and 132.8 mg/L for Co2+, Cr3+ and V3+, respectively, tted experimental data very well. The column
Packed bed was regenerated and reused six times consecutively without signicant loss in biosorbent capacity
Breakthrough curve signifying its appropriateness for commercial application.
2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction competitiveness, effectiveness and low cost is biosorption [3,6,8

The presence of heavy metals in water and wastewater efuents
is one of the greatest challenges in our time. This is because a
variety of physiological and neurological damage to the human
body are associated with heavy metal exposure [1]. As a result
tough regulatory laws that restrict levels of heavy metals present
in water or wastewater have been imposed by several nations in
the past decades. Therefore, in order to decrease the levels of heavy
metals in the environment, it is necessary to treat wastewaters
before discharge [2]. At the moment, a wide range of physical and
chemical techniques are available for removal of heavy metals [3].
However, these traditional water and wastewater treatment
processes have shown to be prohibitively expensive and
ineffective for very low metal concentrations [48]. Therefore,
the need to nd effective and economical alternative techniques
for removal of heavy metals is taken as a priority in the water and
wastewater treatment industry. One such alternative technique
that has attracted a lot of attention in recent years because of its
* Corresponding author. Tel.: +27 11 717 7570/ +27 76 112 6959(mob.);
fax: +27 11 717 7599.
E-mail addresses: simateg@yahoo.com, simateg@gmail.com (G.S. Simate).
15]. Furthermore, biosorption exhibits several other advantages,
such as high selectivity and low energy consumption [16]. In recent
past, a wide range of biosorbents such as rice husks [17], neem saw
dust [8], beer yeast [18], green algae [19] and y ash [20] have been
investigated. More recently [6], we investigated the removal of
some heavy metals from waste efuents using cassava peel waste
in a batch system.
The biosorption capacity of the cassava peel waste [6] and many
other biosorbents obtained from batch equilibrium experiments is
useful in providing fundamental information about the effective-
ness of metal-biosorbent system [21]. However, data obtained
from batch systems may not be applied directly to most treatment
systems (such as column operations) where contact time is not
sufcient for the attainment of the equilibrium [8,2123].
Furthermore, batch systems are usually limited to the treatment
of small quantities of wastewater [21]. Therefore, for practical and
large scale operations, a packed column is preferred to a batch
system [8,19,22]. This is because a packed column makes the best
use of the concentration difference known to be the driving force
for heavy metal biosorption. This allows for more efcient
utilization of biosorbent capacity and also results in better quality
of the efuent [8,22,24]. Hence, a column packed with immobilized
cassava peel waste pellets was used in our study. In such systems,

http://dx.doi.org/10.1016/j.jiec.2014.03.031
1226-086X/ 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
636 G.S. Simate, S. Ndlovu / Journal of Industrial and Engineering Chemistry 21 (2015) 635643
the concentration proles in the liquid and biosorbent phases vary
in both space and time [19,25]. This makes the design and
optimization of a packed bed difcult to perform without a
quantitative modelling approach [19,25].
Models have an important role in technology transfer from
laboratory-scale to industrial-scale [24]. Appropriate models can
help to analyze and explain experimental data, identify process
mechanisms, predict answers to changing operational conditions
and optimize processes [24,26]. From the perspectives of process
modelling, the dynamic behaviour of a packed column is described
in terms of a breakthrough curve [8,19,25]. A breakthrough curve,
which is S-shaped, is a plot of efuent solute concentration versus
time. Breakthrough is the point on the S-shaped curve at which the
efuent solute concentration reaches its maximum allowable
value [8,22]. On the other hand, the point where the efuent solute
concentration reaches 95% of the inuent concentration is called
the point of column exhaustion [8,22,27].
The shapes of breakthrough curves depend on the nature of the
wastewater being treated. If there is only a single adsorbable
component in wastewater, the adsorption will be short and the
breakthrough curve will be steep [8,22]. If there is a mixture of
components having different adsorption capabilities, the sorption
zone will be deep and the breakthrough will be atter. Residence
time is the major design parameter for the adsorption systems. The
optimum residence time determines the size of the adsorbing
column and amount of adsorbent.
As stated earlier, the potential of utilising cassava peel waste as
a biosorbent for the removal of some heavy metals from aqueous
solutions was investigated in our previous study using a batch
process [6]. Although the use of cassava biomass had shown much
potential in the development of several bioprocesses in the past,
there were still some questions that required answers. Therefore,
some of the parameters tested in our previous study [6] included
biomass modication, and its reusability. Furthermore, the choice
of cassava peel waste was also made from an economic standpoint.
Since cassava peel waste has no economic value its conversion into
an effective biosorbent is expected to increase its market value and
ultimately economically benet the millions of cassava producers
[6]. Therefore, the aim of the current study was to use immobilized
cassava peel waste pellets as a biosorbent for the removal of heavy
metal ions from water and wastewater in a column mode.
2. Materials and methods
2.1. Preparation of heavy metal solutions
All chemicals used were of analytical grade and were obtained
from Merck, South Africa. Synthetic solutions (100 mg/L) with
combined metal ions of Cr3+, Co2+ and V3+ were prepared by
dissolving required salt quantities of Cr(NO3)39H2O, CoSO47H2O
and VCl3, respectively, in distilled water according to the
procedure outlined by American Public Health Association [28].
Relatively low metal ions concentrations of 100 mg/L were used so
as to obtain gentle breakthrough curves [29]. It must be noted,
however, that industrial efuents usually contain higher values
than used in many studies [6]. In the previous study by Ndlovu et
al. [6], the average optimum pH for biosorption of the heavy metals
was 4.0. Therefore, the pH of inuent solution was adjusted to 4.0
with a pH meter (827 Metrohm) by using 0.1 M H2SO4 and/or 0.1 M
NaOH accordingly.
2.2. Preparation of immobilized cassava peel waste biosorbent
The preliminary preparation of cassava peel waste biomass was
described in our earlier study [6]. The thiolation (a process of
introducing sulfhydryl group (or thiol group), SH) procedure of
the cassava waste was done as described by Abia et al. [9]. Initially,
the cellulose biomass was thoroughly washed with 0.3 M HNO3
and was then ltered afterwards. The ltrate was discarded and
the residue was washed with distilled water until a pH of 7.0 was
obtained. Later, the paste obtained was air-dried.
The air-dried biomass was divided into 3 equal portions. The
rst portion was left untreated. The other two portions were
treated with 0.5 M and 1.0 M thioglycollic acid, respectively, as
follows: a 25 g portion was mixed with 250 mL of the required
concentration of thioglycollic acid solution in the presence of
hydroxylamine (NH2OH). The mixture was mechanically stirred for
6 hours at 30 8C. This allowed the thiolation of the methylene
hydroxyl group of the cellulose pyran ring [9]. In other words, the
process led to the exchange of the hydroxyl groups by the
sulfhydryl groups in the presence of hydroxylamine (NH2OH) as
follows:
B  CH2 OH HSCH2 CO2 H NH2 OH ! B  CH2  SH
CH2 CO2 H HONH H2 O (1)
where B represents the biomass. The mixture was then allowed to
settle overnight and then centrifuged at 2500  g for 10 min. The
supernatant was discarded and the paste was air-dried.
It must be noted, however, that although grinding of dried
biomass may yield stable biosorbent particles, generally the free
biomass has low mechanical strength not suitable for use in
column applications [30]. Furthermore, whilst excessive hydro-
static pressures are required to generate suitable ow rates in
packed columns, high pressures can disintegrate the free biomass.
These problems can be avoided by the use of immobilized biomass
systems [31,32]. Immobilized biomass offers many other advan-
tages including better regeneration and reusability, high biomass
loading and minimal clogging in continuous ow systems [3336].
Therefore, in this study, immobilized cassava peel waste
biomass was used. Cassava peel waste biomass was immobilized
into small sized pellets by, rstly, mixing the free biomass with
250 mL distilled water and left to hydrate for 10 min at room
temperature. Secondly, the slurry was mixed with equal volume of
3% (w/v) sterile sodium alginate. Finally, the sodium alginate-
biomass mixture was added drop wise through a syringe into 0.2 M
calcium chloride (CaCl2) solution so as to get even-sized pellets.
The sodium alginatebiomass mixture droplets solidied upon
contact with CaCl2, forming pellets and thus entrapping biosorbent
particles. The pellets were allowed to harden for 30 min and were
then washed with 0.9% sodium chloride (NaCl) solution to remove
excess calcium ions [37]. The generated pellets had a diameter
ranging from 3 to 4 mm.
2.3. Characterization tests
In order to identify the functional groups responsible for the
biosorption in the immobilized cassava peel waste biomass,
Fourier transform infrared (FT-IR, Bruker Tensor 27) spectroscopy
analysis was carried out. Scanning electron microscopic (SEM, FEI
Quanta 400F) studies were also conducted to observe the surface
morphology of the biosorbent.
2.4. Packed bed column tests
The column experiments were conducted in a glass column
with an inner diameter of 5 cm and height of 50 cm packed with
immobilized cassava peel waste pellets. The column was packed
with immobilized cassava peel waste pellets between two
supporting layers of glass wool. The combined metal solution of
100 mg/L concentration at a pH of 4 was pumped upward through
the column using a peristaltic pump (Watson Marlow 504S) with
 [(Fig._1)TD$IG]
G.S. Simate, S. Ndlovu / Journal of Industrial and Engineering Chemistry 21 (2015) 635643 637

variable speed adjustment. To study the effect of bed height and

ow rate on biosorption, xed bed studies were carried out with
various bed depths of 5, 10 and 15 cm and at ow rates of 0.83, 1.25
and 1.61 mL/s. Samples were collected at the exit of the column at
different time intervals and analyzed for metal ion concentrations
using ame atomic absorption spectrophotometer (FAAS) (Varian
SpectrAA-55B, Varian Techtron (Pty) Ltd.). The columns were run
till exhaustion of the biosorbent.

2.5. Regeneration and reusability studies

After exhaustion of the immobilized cassava peel waste pellets,

it was necessary to regenerate the column for further use.
Regeneration was carried out by pumping 0.1 M H2SO4 solution
through the bed in the upward direction for 3 h to allow Cr3+, Co2+
and V3+ to be eluted from the biosorbent. Subsequently, the
column was washed and rewashed with distilled water and 0.3 M
HNO3, respectively. The biomass was rewashed with 0.3 M HNO3
to ensure that there were no traces of ions that remained attached
(or adsorbed) to the biomass. The column was again fed with
inuent and sorption studies were carried out. The cycles of
sorption followed by desorption, washing and rewashing were
repeated to evaluate the biomass sorption capacity.

3. Results and discussion

3.1. Characterizations of immobilized cassava peel waste biomass

The FT-IR and SEM were the two techniques used in

characterization of immobilized cassava peel waste biomass.
The FT-IR spectra before and after thiolation of cassava peel waste
biomass are shown in Fig. 1. It can be seen from Fig. 1(a) and (b)
that the major difference between the two biomass samples is the
presence of the sulfhydryl group (SH). The presence of sulfhydryl
group conrmed with FT-IR proves that thiolation process adds
sulfhydryl functional groups on the immobilized cassava peel
waste biomass. Though COO, C5 5O and other functional groups
present in cassava biomass do adsorb metal ions, our previous
study showed that the thiolation process improved the metal ion
sorption [6]. It was thus concluded that the metal ions were
incorporated within the biosorbent through interaction with the
active sulfhydryl functional groups. In other words, the presence of
sulfhydryl functional groups enhanced biosorption.
The FT-IR of immobilized cassava peel waste biomass before
biosorption is shown in Fig. 2. The gure clearly shows that there
were no signicant changes in the peaks compared to Fig. 1(b)
which indicates the presence of the same kind of functional groups
in the biosorbent. Fig. 3 shows the FT-IR spectra of immobilized
cassava peel waste biomass after biosorption of metal ions. The FT-
IR spectra of Fig. 3 (after biosorption) show shifts of several peaks
compared to the FT-IR spectra of Fig. 2 (before biosorption). In
other words, the FT-IR spectra of Co2+, Cr3+ and V3+ sorbed
immobilized cassava waste biomass showed that the peaks
expected at 3363, 2974, 2563, 1653, 1443, 1320, 1029 and
Fig. 1. Fourier transform infrared spectra of cassava biomass: (a) before thiolation,
(b) after thiolation [6].
concentration would be the one that would release bound metal
from the surface without altering the surface characteristics of the
biomass. The SEM is one of the useful techniques applied in the
examination of the surface morphology of biosorbents [21] thus it
was employed in this study. Fig. 4 depicts the surface morphology
of immobilized cassava peel waste biomass before and after
desorption with different concentration of H2SO4. The pictures
indicate that the biosorbent has a rough, irregular and porous
surface thus providing large area for metalsurface interaction and
biosorption [22]. It is clearly seen that desorption with H2SO4 has
[(Fig._2)TD$IG]
1.2
1
0.8
Free -SH
Absorbance

0.6 OH- stretch

613 cm1 had shifted to 3394,2981, 2630, 1637, 1438, 1325, 1028 OH- strech -C=O strecth
and 615 cm1. This shift may be attributed to the changes in -C-O strecth
0.4
counter ions associated with carboxylate, hydroxylate and -SH
-COO strecth
anions suggesting that acidic groups such as carboxyl, hydroxyl
and thiol are responsible for metal ion uptake. In other words, the 0.2
changes observed in the spectrum indicate the possible involve-
ment of the stated functional groups found on the surface of the 0
biomass in biosorption process. The shifts (or disappearance) of 0 500 1000 1500 2000 2500 3000 3500 4000 4500
some peaks in the FT-IR spectra is in agreement with ndings of
Wavenumbers ( cm-1)
similar studies reported in literature [21,38,39].
Desorption of heavy metals from metal-laden biomass was Fig. 2. Fourier transform infrared spectra of immobilized cassava biomass before
tested by utilizing various concentrations of H2SO4. The best biosorption.
[(Fig._3)TD$IG]
638 G.S. Simate, S. Ndlovu / Journal of Industrial and Engineering Chemistry 21 (2015) 635643

1.2 were noted after elution with 0.1 M H2SO4 such that the biomass
remained suitable for reuse. The 1.5 M and 2 M H2SO4, however,
1 resulted in signicant changes in the structure of immobilized
cassava peel waste biomass, thus was not suitable for reuse.
0.8 Free -SH In addition to the SEM images, the FT-IR spectra of the biomass
Absorbance

desorbed with different concentrations of H2SO4 are presented in

OH- stretch
OH- stretch -C=O stretch Fig. 5. The biomass that was exposed to 0.1 M H2SO4 (Fig.s 5(a))
0.6
was similar to the original immobilised biomass (Fig. 2), this means
-C-O stretch
that the desorption with low acid concentration did not change the
0.4 -COO stretch binding sites of biomass and thus it remained suitable for
subsequent cycles. As the concentration of H2SO4 increased from
0.2 0.1 M to 2 M (Fig. 5(a)(c)), the structure of the biomass changed
and there was a complete loss of SH group at 2 M H2SO4
0 concentration. The damage or removal of SH groups at high
0 500 1000 1500 2000 2500 3000 3500 4000 4500 concentration of H2SO4 is expected to reduce the sorption capacity
Wavenumbers (cm-1) of cassava. Therefore, all desorption and regeneration studies (in
Section 3.6) were carried out using 0.1 M H2SO4.
Fig. 3. Fourier transform infrared spectra of immobilized cassava biomass after
biosorption.
3.2. Effect of column bed depth

brought some visible changes (ake like structures) on the surface
of the biosorbent. From the gure it can be seen that as H2SO4
concentration increases, the pellets of immobilized cassava peel
waste biomass cluster together resulting in the overall reduction of
the surface area. No signicant changes in the biosorbent surface
[(Fig._4)TD$IG]
The retention of metals in a packed bed column depends,
among other factors, on the quantity of the solid sorbent used or,
on the bed depth of the column [29,4042]. Therefore, the
breakthrough curves (at constant inuent ow rate of 0.81 mL/s)
shown in Fig. 6 were plotted to illustrate the effect of bed depth on

Fig. 4. SEM micrograph of cassava biomass:(a) before desorption, (b) 0.1 M H2SO4 eluent, (c) 1.5 M H2SO4 eluent, (d) 2 M H2SO4 eluent.
[(Fig._5)TD$IG] [(Fig._6)TD$IG]
G.S. Simate, S. Ndlovu / Journal of Industrial and Engineering Chemistry 21 (2015) 635643 639

(a) 1.2 (a)

1
0.9
1
0.8
0.7
0.8 0.6

Ce/Co
Free -SH
Absorbance

0.5
5 cm
0.4
0.6 OH- stretch -C=O stretch 0.3 10 cm
OH- stretch
-C-O stretch 0.2
15 cm
0.4 -COO stretch 0.1
0
1 10 100 1000
0.2 t (min)
(b) 1.2

0 1
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Wavenuber (cm-1) 0.8
5 cm

Ce/Co
0.6
(b) 10 cm
1.2 0.4
15 cm
0.2
1
0
0.8 1 10 100 1000
Free -SH
Absorbance

(c) t (min)
0.6 -C=O stretch 1.2

1
0.4 -COO stretch -C-O stretch OH-stretch
0.8
Ce/Co
0.6 5 cm
0.2
OH- stretch 0.4 10 cm

0 0.2 15 cm
0 500 1000 1500 2000 2500 3000 3500 4000 4500 0
Wavenumber (cm-1) 1 10 100 1000

t (min)
(c) 1.2
Fig. 6. Breakthrough curves for metal ions adsorption at different bed depth: (a)
1 Co2+, (b) Cr3+, (c) V3+.

0.8 proles remained almost identical for different bed depth

investigated, probably because uptake capacity strongly depends
Absorbance

0.6
0.4
0.2
-COO stretch
0 exhaustion; the adsorbing zone then moves through the column
0 500 1000
Fig. 5. Fourier transform infrared spectra of cassava biomass for: (a) 0.1 M H2SO4,
(b) 1 M H2SO4, (c) 2 M H2SO4.
heavy metal biosorption characteristics of immobilized cassava
peel waste pellets. The breakthrough curves for the column were
determined by plotting the dimensionless concentration (Ce/C0)
against time (where Ce and C0 are the metal ions concentration in
the efuent and inuent, respectively). From the gure, it can be
seen that the breakthrough time and exhaustion time increased
with an increase in bed depth. Therefore, the uptake of heavy
metals increased with the increase in the bed depth from 5 to
15 cm. The increase in the metal uptake capacity with the increase
in bed depth of the column was due to the availability of more
binding sites for sorption [23,29] and an increase in the contact
time [1]. In other words, as the bed height increased, more binding
sites were available and the ions had more time to contact with the
biosorbent resulting in higher removal efciency of metals in the
column thus leading to a decrease in the solute concentration in
the efuent. The gure also shows that though the metal uptake
on the amount of sorbent available for sorption [22,29]; the slope
-C=O stretch
of breakthrough curve decreased with increasing bed depth, which
OH- stretch
resulted in a broadened mass transfer zone [23,42]. It must be
noted that the mass transfer zone in a packed bed column moves
from the entrance of the bed and proceeds towards the exit [43],
i.e., the rst portion of the column will adsorb ions until
-C-O stretch
1500 2000 2500 3000 3500 4000 4500 until it reaches the outlet. Hence for the same inuent concentra-
Wavenumber (cm-1) tion in a packed bed system, an increase in bed height would create
a longer distance for the mass transfer zone to reach the exit,
subsequently, resulting in an extended breakthrough time [43].
These results are in agreement with the ndings of similar studies
reported in literature [1,23,29,4043].
3.3. Effect of inuent ow rate
Inuent ow rate is one of the most important parameter for
evaluating the performance of an adsorption process, particularly
for continuous treatment of wastewater at an industrial scale
[8,44,45]. The effect of inuent ow rate on the sorption of Co2+,
Cr3+ and V3+ metals from synthetic solution by immobilized
cassava peel waste in a xed bed column was studied by varying
the ow rate from 0.83 to 1.61 mL/s, while the bed depth (10 cm)
and initial metal ion concentration (100 mg/L) were kept constant.
The effect of the ow rate on the biosorption of heavy metals is
shown by the breakthrough curves in Fig. 7. The breakthrough
curves were determined by plotting the dimensionless concentra-
tion (Ce/C0) against time (where Ce and C0 are the metal ions
concentration in the efuent and inuent, respectively).
[(Fig._7)TD$IG]
640 G.S. Simate, S. Ndlovu / Journal of Industrial and Engineering Chemistry 21 (2015) 635643

(a) 1 seen from Figs. 6 and 7, V3+ has delayed breakthrough and
0.9 exhaustion time compared to the other ions; the hierarchy of metal
0.8 ions followed the order V3+ > Cr3+ > Co2+. This means the
0.7
biosorption efciency increased is in the order V3+ > Cr3+ > Co2+.
0.6
These results are in agreement with our previous batch studies [6].
Ce/Co

0.5 0.83 mL/s

0.4
The differences (or variations) are attributed to the metal ions
1.25 mL/s
0.3 afnity towards the biosorbent [1], and it depends on the ionic
0.2 1.61 mL/s radius and electropositive charges on the ions [49].
0.1 Previous studies have also shown that the presence of other
0 ions in a wastewater system decreases biosorption of a particular
1 10 100 1000
ion. Vimala et al. [22] studied the behaviour of breakthrough
t (min)
curves for biosorption of cadmium (Cd2+) in single and mixed
(b) metal systems. The breakthrough and exhaustion points were
1.2
found to be earlier for biosorption of Cd2+ in mixed metal system
1 than in a single system. This is due to the competition of co-ions
0.8
with Cd2+ for the biosorption sites on the biosorbent. We obtained
similar results in our batch system studies [6].
Ce/Co

0.6
0.83 mL/s

0.4 1.25 mL/s

3.5. Mathematical modelling of column adsorption

0.2 1.61 mL/s

Successful design of a column adsorption process requires
0 prediction of the concentrationtime prole or breakthrough
1 10 100 1000
curve for the efuent [29,50,51]. Therefore, various mathematical
t (min)
models have been developed for evaluation of efciency and
(c)
applicability of packed beds to large-scale operations. Among
1.2
these, the bed depth service time (BDST) model and the Thomas
1 model were used in this study to analyze the behaviour of the
0.8 packed column.
Ce/Co

0.6 0.83 mL/s

0.4
1.25 mL/s
0.2 1.61 mL/s
0
1 10 100
t (min)
Fig. 7. Breakthrough curves for metal ions adsorption at different ow rates: (a)
Co2+, (b) Cr3+, (c) V3+.
As can be seen from Fig. 7, an increase in the ow rate reduced
both the breakthrough and exhaustion times resulting in steeper
breakthrough curves and shorter zones of mass transfer. The
relatively reduced breakthrough and exhaustion time at higher
ow rates resulted in comparatively less metal uptake and percent
removal. In other words, the biosorption efciency was lower at
higher ow rate. The reduction in metal uptake is attributed to
insufcient residence time of the metal ions in the column
[22,23,46] and the diffusion limitations of the solute into the pores
of the sorbent at higher ow rates [29,47]. In other words, if the
residence time of the solute in the column is not large enough for
adsorption equilibrium to be reached at the given ow rate, the
metal solution leaves the column before the equilibrium occurs [8].
Just like on the effect of bed depth, these results are also in
agreement with the ndings of similar studies reported in
literature [8,22,23,29,46,47].
3.4. Competitive biosorption of the metal ions
Pollution of the environment with toxic metals is essentially a
result of many human activities such as mining and metallurgy,
thus efuents from such activities would carry admixtures of
heavy metal ions in solution [48]. Therefore, when adsorption
technique is employed in the removal of heavy metals from
industrial wastewater, the adsorbent adsorbs more than one metal
which are usually present in the wastewater [22]. This section
discusses competitive biosorption of Cr3+, Co2+ and V3+. As can be
3.5.1. Bed depth service time (BDST) model
The BDST is one of the most applied models for adsorption of
heavy metals in column studies [8]. This model was rst proposed
by Bohart and Adams [52] and later modied by Hutchins [53]. The
1000
BDST is a simple model based on physically measuring the capacity
of the bed at different breakthrough values [22,47]. However, the
model ignores the intraparticle mass transfer resistance and the
external lm resistance such that the sorbate is sorbed onto the
sorbent surface directly [22,47], i.e., it is based on the surface
reaction rate theory [17].
The BDST model states that the bed height and service time of a
column bears a linear relationship and the equation can be
expressed as,
   
N0 Z 1 C0
t  ln 1 (2)
C0v K aC0 Cb
where t is the service time at breakthrough point (h); N0 is the
adsorption capacity of the bed (mg/L); Z is the bed depth of column
(cm); C0 is the inuent or initial concentration of solute (mg/L); Cb
is the breakthrough metal ion concentration (mg/L); Ka is the
adsorption rate constant (L/mg h); v is the linear ow velocity of
feed to bed (cm/h). Eq. (2) can be rewritten in the form of a straight
line,
t mZ  n (3)
where m and n are the slope and intercept of the BDST line. From
Eq. (3), it can be seen clearly that the bed depth (Z) and the service
time of a column are linearly related.
In this study, the column service time was selected when the
normalized concentration, Ce/C0 reached 0.05. The plot of service
time against bed depth at the ow rate of 0.83 mL/s was found to
be linear (results not shown here). The high correlation coefcient
values (R2 = 0.871, R2 = 0.942 and R2 = 0.923 for Co2+, Cr3+ and V3+,
respectively) indicates the validity of the BDST model to represent
the biosorption of heavy metals ions in this study. Assuming that
initial concentration (C0) and linear velocity (v) are constant during
 G.S. Simate, S. Ndlovu / Journal of Industrial and Engineering Chemistry 21 (2015) 635643 641

Table 1 Table 2
The BDST model parameters for the biosorption of Co2+, Cr3+ and V3+ on Thomas model parameters for the adsorption of Co2+, Cr3+ and V3+ on immobilized
immobilized cassava waste biomass. cassava waste biomass at different ow rates and a bed depth 10 cm.

Metal ions N0 (mg/L) Ka (L/mg min) R2 Metals Flow rate (mL/s) q0(mg/g) KTH(mL/s mg)  (104) R2
2+ 2+
Co 99.6 0.013 0.871 Co 0.83 54.62 1.94 0.805
Cr3+ 116.2 0.011 0.942 1.25 52.95 2.19 0.733
V3+ 132.8 0.005 0.923 1.61 45.81 2.30 0.608
Cr3+ 0.83 45.13 2.26 0.818
1.25 40.65 1.95 0.771
1.61 37.78 1.83 0.705
V3+ 0.83 36.26 1.70 0.842
the column operation, the value of N0 and Ka were evaluated from 1.25 30.91 1.80 0.716
1.61 17.88 2.30 0.690
the slope (N0/C0v) and intercept ((1/KaC0)ln[(C0/Cb)  1]) of the
BDST plot. It must be noted that Ka parameter is very important. It
characterizes the rate of transfer from the liquid phase to the solid
phase and it largely inuences the breakthrough phenomenon in Eqs. (5) and (6) below are the linearized form of the Thomas
any column study [8,29,54]. Generally, for smaller values of Ka, a model.
relatively longer bed is required to avoid breakthrough whereas      
C0 K TH q0 M K TH q0 M
the breakthrough can be eliminated even in a smaller bed when the ln 1  (5)
Ce Q V ef f
value of ka is high [8,29,54].
The BDST model constants can be helpful to scale up the process    
for different ow rates and different initial concentrations without C0 K TH q0 M
ln 1  K TH C 0 t (6)
further experimentation [1,8,29]. For example, if a value is Ce Q
determined for one ow rate, values for the other ow rates can
The experimental data was tted to the Thomas model by
be calculated by multiplying the original slope m by the ratio of the
plotting ln[C0/Ce  1] versus t at a given ow rate (results not
original and the new ow rates [55]. It is not necessary to adjust n
shown here). The value of the rate constant (KTH) and the
value, since this term is assumed to be insignicantly affected by
maximum capacity (q0) were evaluated from the slope and
changing ow rates [55].
intercept of the plots, respectively. The model parameters are
The values of BDST model parameters in this study are
listed in Tables 2 and 3.
presented in Table 1. From Table 1, it can be seen that the value
From the consistently low values of the regression coefcient
of N0 was higher for V3+ compared to that for Co2+ and Cr3+. This
(R2) in Tables 2 and 3, it can be concluded that the experimental
was attributed to the competitive biosorption towards the active
data did not t well with the Thomas model. Thus the Thomas
site between the metal ions. The V3+ ions may have a strong
model will not be appropriate for describing the sorption process
afnity towards the active sites of the sorbent compared to Co2+
in this study. However, it can be seen from the tables that R2
and Cr3+. Furthermore, the table also shows that V3+ has a lower
increased with an increase in bed depth and decrease in ow rate.
rate constant (Ka) which means that V3+ had more contact time
Furthermore, the results show that as the ow rate increased q0
with the biosorbent, which resulted in the greater removal of V3+
values decreased for all the metal ions which is consistent with
ion. These results are also in agreement with the ndings of our
similar studies by other researchers [42,43,50]. The decrease in q0
batch studies (i.e., V3+ ions had the highest biosorption rate
with an increase in ow rate may be attributed to reduced
amongst the other two ions) [6].
residence time or premature saturation of the active sites.
However, as the ow rate increased KTH values increased for
3.5.2. Thomas model
Co2+ and V3+, but a reverse trend was observed for Cr3+. An increase
Thomas model (or reaction model) is based on the assumption
in KTH with an increase in ow rate is also in agreement with the
that the process follows Langmuir kinetics of adsorption-
studies by Chowdhury et al. [43] and, Malkoc and Nuhoglu [50].
desorption with no axial dispersion and mass transfer kinetics
However, Yahaya et al. [42] observed a decrease in KTH with an
[43,56,57]. It is derived with the assumption that the rate driving
increase in ow rate. Table 3 shows that q0 and KTH increased with
force obeys second-order reversible reaction kinetics [19,43,57].
an increase in bed height. The effect of bed depth on KTH is in
This is the primary weakness of the Thomas modelits derivation
agreement with the studies by Chowdhury et al. [43], but
being based on second-order reaction kinetics [19]; adsorption is
contradicts that by Yahaya et al. [42] and Saadi et al. [61].
usually not limited by chemical reaction kinetics, but is often
Comparing the results from this study and those of similar
controlled by interphase mass transfer. This discrepancy can lead
studies shows a lot of differences. These differences are expected
to some error when this method is used to model adsorption
considering the fact that the Thomas model assumes that
process [19,58,59]. Thomas model also assumes a constant
adsorption is limited by chemical reaction kinetics. It is actually
separation factor, but it is applicable to either favourable or
unfavourable isotherms [19].
Table 3
The expression of the Thomas model for an adsorption column
Thomas model parameters for the adsorption of Co2+, Cr3+ and V3+ on immobilized
is as follows [19,60]: cassava waste biomass at different bed depths and a ow rate of 0.83 mL/s.

Ce 1 Metals Bed depth (cm) q0 (mg/g) KTH (mL/s mg)  (104) R2

(4) 2+
C 0 1 expK TH =Q q0 M  C 0 V eff Co 5 33.164 1.8 0.621
10 46.499 2.2 0.732
15 86.458 2.3 0.805
where KTH is the Thomas rate constant (L/mg h); q0 is the Cr3+ 5 25.523 2.1 0.705
maximum solid-phase concentration of the solute (mg/g); M is the 10 37.437 2.4 0.770
amount of adsorbent in the column (g); Q is the volumetric ow 15 61.255 2.6 0.817
rate through the column (L/h); Veff is the volume of efuent; C0 is V3+ 5 28.596 1.9 0.689
10 34.975 2.1 0.715
the initial metal ion concentration (mg/L) and Ce is the efuent
15 61.760 2.3 0.841
metal ion concentration (mg/L) at any time t (min).
[(Fig._8)TD$IG]
642 G.S. Simate, S. Ndlovu / Journal of Industrial and Engineering Chemistry 21 (2015) 635643

120 the biosorbent/binding sites. It must be noted, however, that loss of

biosorption performance is not mainly due to biosorbent damage,
100
but due to difculty in accessing binding sites as the cycles
progress [63]. Furthermore, the performance is also strongly
80
depended on the previous elution step, since prolonged elution
Adsorpon %

may destroy the binding sites or inadequate elution may allow

60 Co
metal ions to remain on the sites [29].
Cr
Fig. 8 also shows that biosorption efciency is increased in the
40 V
order V3+ > Cr3+ > Co2+ which is in agreement with the order of
20
service times in Figs. 6 and 7. However, it is noticed from Fig. 9 that
desorption efciency is in the reverse order to the biosorption
0
efciency trends, i.e., Co2+ > Cr3+ > V3+. This means that weaker
1 2 3 4 5 6 bonds were formed between the Co2+ ions and the biosorbent
Cycle number compared to that for Cr3+ and V3+. In other words, Co2+ ions have a
lower afnity to the biosorbent so they are easily displaced.
Fig. 8. Adsorption efciency of immobilized cassava waste biomass for the
adsorptiondesorption cycles.
4. Conclusions

this assumption that leads to some error when this method is used
to model adsorption processes [50,58,59]. Therefore, it may be
argued that the external and internal diffusion are the limiting
steps in the biosorption process in this study.
3.6. Regeneration and reusability studies
The regeneration and subsequent reuse of a biosorbent is very
important in industrial practices [38]. It guarantees the continued
usage of the biosorbent and thus reduces process costs [36].
Therefore, attempts were made in this study to regenerate and
reuse the immobilized cassava peel waste biomass. This was
evaluated by comparing the sorption performance of regenerated
biomass with the original biomass [29,45]. The immobilized
cassava peel waste biomass regeneration studies were carried out
on six consecutive sorptiondesorption cycles using column
mode operation. In other words, six cycles of sorptiondesorption
were performed to study the reusability of the biosorbent.
However, in practical industrial applications, the operation of the
biosorption column would have been discontinued (and the
biosorbent is replaced) as soon as the concentration of heavy
metals (Cr3+, Co2+ and V3+) in the efuent exceeded the regulatory
limit [38,62].
Figs. 8 and 9 show the efciencies of the biosorption and
desorption cycles, respectively. Fig. 8 shows that biosorption
efciency remained reasonably constant irrespective of the
number of cycles. However, Fig. 9 shows that desorption efciency
was initially constant (rst 3 cycles), but declined slightly over the
subsequent cycles. The consistent biosorption performance shows
that despite repeated usage, there was minimal deterioration of
[(Fig._9)TD$IG]
100
90
80
70
Desorpon eciency
The purpose of this study was to investigate the removal
efciency of V3+, Cr3+ and Co2+ by immobilized cassava peel waste
biomass in a packed bed column. The performance of the packed
bed was analyzed using the efuent concentration versus time
curves. The packed bed column was found to perform better with
lower inuent rate and higher bed depth. The uptake analysis
revealed a high selectivity for V3+ over Cr3+ and Co2+ at all
conditions tested. The study showed that the experimental data
best tted with BSDT model than with the Thomas model for all the
conditions tested. The biosorptiondesorption results showed that
the biosorbent can be used repeatedly without signicant loss in
sorption capacity reecting its feasibility for commercial applica-
tion. Furthermore, the easy availability and low cost would make
immobilized cassava peel waste biomass an attractive biosorbent
option for heavy metals.
Disclaimer
The contents of this paper reect the views of the authors who
are responsible for the facts and accuracy of the data presented
herein and do not necessarily reect the ofcial views or policies of
any agency or institute. This paper does not constitute a standard,
specication, nor is it intended for design, construction, bidding, or
permit purposes. Trade names were used solely for information
and not for product endorsement.
Acknowledgements
The authors are thankful to all those who provided nancial
[NRF Scholarship (South Africa) and Friedel Sellschop Award
(University of the Witwatersrand, South Africa)] or technical
support in the course of this research work. In particular, special
thanks are due to the Lizzy Seepe for her help with laboratory
testing.

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