Bioresource Technology 100 (2009) 5633–5640

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Modeling, simulation, and experimental validation for continuous Cr(VI)

removal from aqueous solutions using sawdust as an adsorbent
Suresh Gupta, B.V. Babu *
Chemical Engineering Department, Birla Institute of Technology and Science (BITS), Vidya Vihar Campus, Pilani 333031, Rajasthan, India

a r t i c l e i n f o a b s t r a c t

Article history: Continuous adsorption experiments were performed in a fixed-bed adsorption column to evaluate the
Received 28 March 2009 performance of low-cost adsorbent (sawdust) developed for the removal of Cr(VI) from aqueous solu-
Received in revised form 8 June 2009 tions. The effects of influencing parameters such as flow rate, mass of adsorbent, initial Cr(VI) concentra-
Accepted 9 June 2009
tion were studied and the corresponding breakthrough curves were obtained. The fixed-bed adsorption
Available online 1 July 2009
process parameters such as breakthrough time, total percentage removal of Cr(VI), adsorption exhaustion
rate and fraction of unused bed-length were obtained. A mathematical model for fixed-bed adsorption
Keywords:
column was proposed by incorporating the effect of velocity variation along the bed-length in the exist-
Adsorption
Sawdust
ing model. Pore and solid diffusion models were used to describe the intra-particle mechanism for Cr(VI)
Cr(VI) removal adsorption. The proposed mathematical model was validated with the literature data and the experimen-
Mathematical modeling tal data obtained in the present study and the model was found to be good for explaining the behavior of
Continuous studies breakthrough curves.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction adsorbent is identified, the cost also could be further brought

Hexavalent chromium [Cr(VI)] is considered as a major pollu-
tant in water pollution and has a dominant presence in most of
the effluent streams. Cr(VI) is present in many compounds that
have a variety of industrial applications and used in various indus-
tries such as glass, ceramics, fungicides, rubber, fertilizers, tanning,
mining, metallurgical, etc. (Namasivayam and Yamuna, 1995; San-
kararamakrishnan et al., 2006; Kumar et al., 2007; Babu and Gupta,
2008a). Cr(VI) is highly mobile and is considered acutely toxic, car-
cinogenic and mutagenic to living organisms, and hence more haz-
ardous than the other heavy metals (ATSDR, 1993; Babu and
Gupta, 2008b). Concentration of Cr(VI) present in industrial efflu-
ent streams are in the range of 50–200 mg L1 (Contreras-Ramos
et al., 2004; Kumar et al., 2007). The permissible limit of Cr(VI)
in potable water is 0.05 mg L1 (Selvaraj et al., 2003).
In order to comply with the permissible limit, it is essential that
industries treat their effluents to reduce the Cr(VI) concentration in
water and wastewater to the acceptable levels before its disposal
or recycling into the natural environment. Adsorption is proved
to be an efficient and cost effective method for the removal of
Cr(VI) (Kumar et al., 2007; Babu and Gupta, 2008a). The advantages
of the adsorption process prompt to extend the use of other low
cost and abundantly available materials. If a suitable low-cost
* Corresponding author. Tel.: +91 01596 245073x259; fax: +91 01596 244183.
E-mail addresses: sureshg@bits-pilani.ac.in (S. Gupta), bvbabu@bits-pilani.ac.in
(B.V. Babu).
down.
Adsorption is an important step in the industrial downstream
processing. At an industrial scale, the time of stopping the opera-
tion (breakpoint time) must be determined after an economic
and, eventually, environmental evaluation of the process. As not
only the amount of solute adsorbed, but also the operating time
has an important impact on the effective use of the column and
on the final throughput of the process. The dynamic behavior of
a fixed-bed adsorption column can be better explained and the
characteristic breakthrough curve of the adsorption phenomena
can be obtained through mathematical models.
It is observed from the literature that the few past studies have
included the work on continuous adsorption studies for the Cr(VI)
removal (Malkoc et al., 2006; Mungasavalli et al., 2007; Yan et al.,
2001; Gode and Moral, 2008). Continuous adsorption studies are
required to collect the experimental data for the design of adsorp-
tion column and for subsequent scale-up from pilot plant to indus-
trial scale operation. Researchers mainly focused on analytical
approach of solving the dynamics of fixed-bed adsorption column
(Liao and Shiau, 2000; Bautista et al., 2003; Sotelo et al., 2004; Li
et al., 2008). The mathematical models that were reported in the
literature, exclude some of the important physical aspects such
as axial dispersion, intra-particle resistances and velocity variation
along the bed-length. Ahmad et al. (in press) evaluated the com-
bined Cr(VI) removal capacities of nonliving (untreated rubber
wood sawdust, URWS) and living biomass (URWS-immobilized
Acinetobacter haemolyticus) in a continuous laboratory scale

0960-8524/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.06.025
5634 S. Gupta, B.V. Babu / Bioresource Technology 100 (2009) 5633–5640

Nomenclature

aP equivalent particle diameter, m Q flow rate, mL min1

Ac area under the breakthrough curve, m2 r radial distance, m
b Langmuir isotherm constant, L g1 Ra adsorption exhaustion rate, g mL1
c adsorbate concentration inside the pellet, mg L1 S percentage removal of Cr(VI) in fixed-bed adsorption
Cad concentration of Cr(VI) adsorbed, mg L1 column, – qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi2
P ðC exp C model Þ
Cb adsorbate concentration in mobile phase, mg L1 s.d. standard deviation, –, s:d: ¼ N
Cb0 initial Cr(VI) concentration, mg L1 t time, s
Ce concentration of Cr(VI) at equilibrium, mg L1 tb breakthrough time, s
Cexp experimental Cr(VI) concentration in mobile phase, tf final time of adsorption, s
mg L1 tt time equivalent to stoichiometric capacity of the col-
Cmodel model values of Cr(VI) concentration in mobile phase, umn, s
mg L1 V superficial velocity, m s1
DL axial dispersion coefficient, m2 s1 V0 initial superficial velocity, m s1
Dp pore diffusivity, m2 s1 W weight of adsorbent, g
Ds solid diffusion coefficient, m2 s1 y fraction of unused bed-length
EBRT empty bed residence time, s z axial coordinate, m
kf external mass transfer coefficient, m s1
L bed-height, m Greek symbols
mt total amount of Cr(VI) sent to the column, mg H fractional coverage, –
N number of data points, – e bed porosity, –
qp average solid phase adsorbate concentration, mg g1 ep particle porosity, –
qe equilibrium solid phase concentration, mg g1 qb bed density, kg m3
qt amount of adsorbate adsorbed at time, t, by the adsor- ql liquid density, kg m3
bent, mg g1 qs density of adsorbent, kg m3
qm maximum monolayer adsorption capacity, mg g1

downward-flow two column system. Preconcentration and separa- and solution volume was made up to 1000 mL. This solution was
tion of Cr(III) and Cr(VI) using sawdust as a sorbent was carried out diluted as required to obtain standard solutions containing 50–
by Memon et al. (2005). The adsorption of Cr(VI) from aqueous 100 mg L1 of Cr(VI).
solutions on sawdust (SD), base extracted sawdust (BESD) and tar- Continuous fixed-bed experiments were performed to remove
taric acid modified sawdust (TASD) of Turkish red pine tree (Pinus Cr(VI) from aqueous solutions using sawdust as an adsorbent.
nigra), a timber industry waste, was studied by Gode et al. (2008). The schematic diagram of the experimental setup is shown in
Yu et al. (2003) conducted batch studies for adsorption of Cr(VI) Fig. 1. The fixed-bed column was made of a glass of 1.5 cm internal
from aqueous solutions using maple sawdust as an adsorbent. diameter. The adsorbent bed was packed with the sawdust in a
In the present study, sawdust, a low-cost adsorbent was used
for Cr(VI) removal. Continuous adsorption experiments were con-
ducted to understand and quantify the effect of influencing param-
eters such as flow rate, mass of adsorbent, initial Cr(VI)
5
concentration on breakthrough curve. A mathematical model for
fixed-bed adsorption column was proposed which takes into ac- 1 Stored Cr(VI) solution
count of both the external and internal mass transfer resistances 2 Outlet collection tank
3 Pump
as well as of non-ideal plug flow behavior and velocity variation 4 Fixed-bed column
along the column. The mathematical model proposed was vali- 5 Feed of Cr(VI) solution
6 Outlet control valve
dated with the data reported in the literature and the obtained 9 7 Inlet control valve
experimental results of the present study with the application of 8 Base
solid and pore diffusion resistances. 7 9 Liquid Rotameter

2. Methods

2.1. Adsorbent preparation

Sawdust (yellow brownish) was collected from the carpentry 4

section of the institute’s workshop (BITS – Pilani, India). It was
washed repeatedly with distilled water to remove dust and soluble
impurities. It was then kept for drying at a room temperature of
25–30 °C in shade for 8 h. The specific surface area, bulk density 6
and average particle diameter of sawdust were 0.86 m2 g1,
0.125 g cm3 and 1.84 mm, respectively. 1 2

2.2. Continuous experiments 3

8
1
A stock solution of 1000 mg L of Cr(VI) was prepared by dis- Fig. 1. Fixed-bed continuous adsorption experimental setup for Cr(VI) removal
solving 2.8287 g of 99.9% potassium dichromate (K2Cr2O7) in water from wastewater.
 S. Gupta, B.V. Babu / Bioresource Technology 100 (2009) 5633–5640 5635

stepwise procedure. Initially, 2 g of adsorbent was transferred into 3. Mass transfer across the boundary layer surrounding the solid
the column and was shaken manually in order to have dense pack- particles is characterized by the external-film mass transfer
ing. This procedure was continued till the complete amount of coefficient, kf.
adsorbent was transferred into the column. After following this 4. The linear velocity of the liquid phase varies along the column.
procedure, 500 mL of distilled water was passed through the 5. The macro porous adsorbent particles are spherical and homo-
packed bed to make the packing more compact packing. Stock geneous in size and density.
solutions of Cr(VI) were allowed to flow in down flow mode
through the fixed-bed of sawdust controlled by a valve. The con- Based on the preceding assumptions, the net rate of accumula-
stant level of feed of Cr(VI) solution in overhead tank was main- tion or depletion is given by Eq. (1):
tained by pumping the solution from the tank containing stock  
@2Cb @C b @V @C b 1e @q
solution of Cr(VI) as shown in Fig. 1. The parameters varied in DL þV þ Cb þ þ qs p ¼ 0 ð1Þ
the continuous experiments were flow rate, mass of adsorbent @z @z @z @t e @z
(bed-height), and inlet Cr(VI) concentration. The flow rate was The initial conditions considered are given by Eqs. (2) and (3):
maintained constant using a liquid rotameter (0–15 L min1). The
fixed mass of the adsorbent and the stock solution of initial Cr(VI) C b ¼ C b0 ; z ¼ 0; t ¼ 0 ð2Þ
concentration was used to maintain the higher accuracy in column
C b ¼ 0; 0 < z 6 L; t ¼ 0 ð3Þ
experiments. The continuous experiments were carried out at an
optimum pH value of 1 obtained by batch experiments (Gupta The contour conditions at both ends of the column are given by Eqs.
and Babu, 2009). The selection of this low pH was also based on (4) and (5):
the actual pH value of industrial effluents such as chromium plat-
@C b
ing effluent (at pH 1) (Selvaraj et al., 2003), tannery effluent (at pH DL ¼ V 0 ðC b0  C b Þ; z ¼ 0; t > 0 ð4Þ
2) (Contreras-Ramos et al., 2004) and electroplating effluent (at pH
@z
2.2) (Kumar et al., 2007) and the experimental studies reported in @C b
the literature (Malkoc et al., 2006; Sarin et al., 2006). ¼ 0; z ¼ L; t P 0 ð5Þ
@z
In the present work, di-phenyl carbazide method was used for
the analysis of Cr(VI) ions in the aqueous solutions which only The superficial velocity, V, in fixed-bed adsorption is not con-
measures the amount of Cr(VI). This method has been reportedly stant because of adsorption of Cr(VI). For liquid adsorption, assum-
used in several studies for analysis of Cr(VI) at low pH (Malkoc ing the liquid density to be constant, the total mass balance is
and Nuhoglu, 2007). The concentration of Cr(VI) ions in the effluent given by Eq. (6), which was used to estimate (dV/dz), i.e. the vari-
was determined spectrophotometrically by developing a purple- ation of velocity of bulk fluid along the axial direction of the bed.
violet color with 1,5-di-phenyl carbazide in acidic solution as a @V @qp
complexing agent (APHA, 1985). The absorbance of the purple-vio- ql ¼ ð1  eÞqs ð6Þ
@z @t
let colored solution was measured at 540 nm. The deviation of ana-
lytical method of Cr(VI) concentration was calculated by preparing Velocity boundary conditions are given by Eqs. (7) and (8):
the calibration curve from standard solutions. The standard devia- V ¼ V 0; z ¼ 0; t > 0 ð7Þ
tion obtained for the calibration curve was 0.00453 which is indic-
ative of a good fit of the data and within the error limits of ±1.64%. @V
This ensured high confidence limits of the experimental
¼ 0; z ¼ L; t > 0 ð8Þ
@t
measurements.
For adsorption in spherical pellets, the inter-phase mass trans-
fer rate may be expressed by Eq. (9):
3. Mathematical modeling and simulation @qp 3kf
qs ¼ ðC b  C e Þ ð9Þ
@t ap
The dynamics of a fixed-bed was described by a set of convec-
tive diffusion equations, coupled with source terms due to adsorp- The intra-pellet adsorbate transport mechanism is defined by
tion and diffusion inside the adsorbent particles. The molecules pore diffusion and solid diffusion resistances and the associated
from the bulk interstitial phase were transported via axial convec- isotherm for the system considered was Langmuir isotherm, which
tion and Fickian diffusion (film diffusion) onto the particle surface. are discussed in Sections 3.1–3.3.
Inside the particle, the molecules can diffuse via solid diffusion, or
pore diffusion, or both. This study was focused on understanding 3.1. Pore diffusion
the surface and pore diffusion mechanisms. The linear velocity var-
iation along the bed was important, which affect the design of an Intra-particle mass transport is due to Fickian diffusion, and it is
adsorption column significantly (Babu and Gupta, 2005). In the characterized by the pore diffusion coefficient, DP. The mass bal-
present study, the linear velocity variation along the bed was ance equation for the pore fluid phase in a spherical particle can
incorporated in the mathematical model for fixed-bed adsorption be written as Eq. (10):
!
column. The proposed model is generalized by addressing the lim- @c @qp @ 2 c 2 @c
itations of earlier models. This model can be widely used for under-
ep þ ð1  ep Þqs ¼ Dp þ ð10Þ
@t @t @r 2 r @r
standing the dynamics of fixed-bed adsorption column for the
adsorption of organic and inorganic (metal ions) compounds. Assuming instantaneous equilibrium as given by Eq. (11):
To formulate a generalized model to predict the fixed-bed @qp @c @qp
¼ ð11Þ
adsorption dynamics which include external film diffusion fol- @t @t @c
lowed by internal diffusion, following assumptions were made: Eq. (10) is rearranged to get Eq. (12):
  2 !
1. The system is operated under isothermal conditions. @c 1 Dp @ c 2 @c
¼h   i þ ð12Þ
2. The equilibrium of adsorption is described by Langmuir iso- @t 1 þ q 1eP
@qp ep @r2 r @r
s eP @c
therm (a non-linear isotherm).
5636 S. Gupta, B.V. Babu / Bioresource Technology 100 (2009) 5633–5640

The initial condition considered was given by Eq. (13): shape of the adsorption wave front, which determine the operation
life span of the bed. The designs of fixed-bed adsorption column in-
c ¼ 0; qp ¼ 0; 0 < r < ap ; t ¼ 0 ð13Þ
clude the estimation of the shape of the breakthrough curve and
The symmetry condition at the center of the particles and the con- the appearance of the breakpoint time. The breakpoint time is
tinuity condition on the external surface of the adsorbent bed are usually defined as the time of adsorption when the effluent con-
expressed by Eqs. (14) and (15), respectively: centration from the column was about 1–5% of the influent con-
centration. The total quantity of adsorbed Cr(VI) (qt, mg) in the
@c
¼ 0; r ¼ 0; t > 0 ð14Þ column for a given inlet Cr(VI) concentration and flow rate was cal-
@r
culated from Eq. (20):
@c Z t¼ttotal
kf ðC b  C e Þ ¼ Dp eP ; r ¼ ap ; t > 0 ð15Þ QAc Q
@r qt ¼ ¼ C ad dt ð20Þ
1000 1000 t¼0

The area under the breakthrough curve (Ac) was obtained by

3.2. Solid diffusion
plotting the adsorbed concentration (Cad, mg L1) versus time (t,
min). Total amount of Cr(VI) sent to column (mt) was calculated
The mass balance equation for the intra-particle solute trans-
from Eq. (21):
port due to the solid diffusion mechanism is given by Eq. (16):
  C b0 Qt t
@qp Ds @ @qp mt ¼ ð21Þ
¼ 2 r2 ð16Þ 1000
@t r @r @r
where tt is the time equivalent to total capacity of the column
The symmetry condition at the center of the particles and the con- which is defined by Eq. (22):
tinuity condition on the external surface of the adsorbent bed are
qt
expressed by Eqs. (17) and (18), respectively: tt ¼ tf ð22Þ
mt
@qp
¼ 0; r ¼ 0; t > 0 ð17Þ Total percentage removal of Cr(VI) was calculated from Eq. (23):
@r
qt
Total percentage removal of CrðVIÞðSÞ ¼  100 ð23Þ
@qp mt
kf ðC b  C e Þ ¼ Ds qP ; r ¼ ap ; t > 0 ð18Þ
@r The empty bed residence time (EBRT) is the time required for
the liquid to fill the empty column. The EBRT is given by Eq. (24):
3.3. Adsorption isotherm
Bed volume
EBRT ¼ ð24Þ
Volumetric flow rate of the liquid
The adsorption isotherm for the present system of Cr(VI) re-
moval using sawdust was found to be favorable and non-linear, The adsorbent exhaustion rate (Ra) is the mass of adsorbent used
is well described by Langmuir isotherm (Langmuir, 1918), and is (W) per volume of liquid treated at breakthrough point which is gi-
given by Eq. (19): ven by Eq. (25):
qe bC e Adsorbent exhaustion rate ðRa Þ
h¼ ¼ ð19Þ
qm 1 þ bC e mass of adsorbent in column
¼ ð25Þ
volume treated at breakthrough
4. Solution algorithm The fraction of unused bed-length was calculated from Eq. (26):
tb
Since the non-linear adsorption equilibrium was considered, y¼1 ð26Þ
the preceding set of partial differential equations (Eqs. (1)–(19)) tt
was solved numerically by reduction to a set of algebraic equations Various parameters such as tt, tf, tb, qt, mt, S, EBRT, Ra and y were
using the Explicit Finite Difference technique. Finite difference evaluated for the Cr(VI) removal using sawdust in the fixed-bed
technique has been successfully applied to solve such type of par- adsorption column for different operating conditions and reported
tial differential equations in other studies by the authors group in Table 1. The effect of column parameters such as flow rate, mass
(Babu and Gupta, 2005). An algorithm to solve these coupled equa- of adsorbent and the inlet Cr(VI) concentration on the performance
tions was developed and implemented into a computer program of the breakthrough curves were investigated.
using MATLAB (v.6.1) software.
5.1.1. Effect of flow rate
5. Results and discussion Flow rate of wastewater stream is an important parameter for
the design of an adsorption column. Studies were conducted at dif-
The performance of sawdust as an adsorbent was investigated ferent values of flow rates varied from 10 to 20 mL min1 while the
in a batch system and reported in previous study (Gupta and Babu, mass of adsorbent and the inlet Cr(VI) concentration were kept
2009). The adsorbent capacity of sawdust for Cr(VI) removal was constant at 25 g and 50 mg L1, respectively at a pH value of 1.
also compared with other low-cost adsorbent and found to be a The effect of flow rate on the breakthrough curve is shown in
promising alternative for removal of Cr(VI) from aqueous solutions. Fig. 2. As can be seen from the breakthrough curves, higher break-
point time of the process was achieved at a lower flow rate. As the
5.1. Continuous adsorption experiments flow rate increases, breakthrough time was obtained earlier. This
can be explained by the fact that at a low value of EBRT, the diffu-
Fixed-bed adsorption studies were conducted to evaluate the sion process that controls the adsorption becomes slow, and hence,
dynamic behavior of Cr(VI) removal onto the sawdust. The most the adsorbent need more time to bind with the metals efficiently.
important criterion in the design of fixed-bed adsorption systems The breakthrough times obtained are 630, 440 and 240 min for the
is the prediction of fixed-bed column breakthrough curves or the flow rate values of 10, 15 and 20 mL min1, respectively. The total
 S. Gupta, B.V. Babu / Bioresource Technology 100 (2009) 5633–5640 5637

Table 1
Different parameters for the Cr(VI) removal using sawdust in a fixed-bed adsorption column for different operating conditions.

S. no. Cb0 (mg L1) W (g) Q (mL min1) tt (min) tf (min) tb (min) qt (mg) mt (mg) S (%) EBRT (s) Ra (g L1) y (–)
1 50 25 10 1080 1450 630 540 725 74.5 20 3.9 0.42
2 50 25 15 860 1240 440 645 930 69.4 13.3 3.8 0.48
3 50 25 20 660 990 240 660 990 66.6 10 5.2 0.63
4 50 30 10 1260 1690 850 630 845 74.6 24 3.5 0.31
5 50 15 10 660 1110 310 330 555 59.4 12 4.8 0.53
6 75 25 10 940 1470 420 705 1102 63.9 20 5.9 0.55
7 100 25 10 740 1330 280 740 1330 55.6 20 8.9 0.62

time, corresponding to the stoichiometric capacity of the column,
was found to be decreasing from 1080 to 660 min with an increase
in the flow rate from 10 to 20 mL min1 as given in Table 1. The to-
tal percentage removal of Cr(VI) for the fixed-bed adsorption col-
umn was found to decrease from 74.5% to 66.6% with an increase
in the flow rate from 10 to 20 mL min1 (Table 1). The fraction of
unused bed-length at breakthrough point shows an increasing
trend (0.42–0.63) with an increase in the flow rate (10–
20 mL min1). Fig. 1 shows that as the flow rate increases, the
breakthrough curve becomes steeper.
The decrease in the breakthrough time with an increase in the
flow rate may be due to a fixed saturation capacity of the bed based
on the same driving force giving rise to a shorter time for satura-
tion at higher flow rates. The probable reason for the increase in
the steepness of breakthrough curve and the decrease in the re-
moval efficiency (74.5–66.6%) with increase in the flow rate (10–
20 mL min1) is that, when the residence time of Cr(VI) in the col-
umn is not long enough for the adsorption equilibrium to be
reached at that flow rate, the Cr(VI) solution leaves the column be-
fore equilibrium occurs. And hence the contact time for Cr(VI)
using sawdust was very short at higher flow rates, which caused
a reduction in the removal efficiency (Table 1). Another reason
for the faster saturation of the adsorbent bed at higher flow rates
could be that with an increase in the flow rate, mixing increases
and the thickness of the liquid film surrounding the adsorbent par-
ticle decreases, thus reducing the film transfer resistance and
hence an increase in the mass transfer rate.
5.1.2. Effect of mass of adsorbent
The breakpoint time also depends on the mass of adsorbent
(bed-length) used in the fixed-bed adsorption column. The effect
of the mass of adsorbent was studied for 15, 25 and 30 g for saw-
dust while maintaining the constant flow rate and the initial Cr(VI)
concentration as 10 mL min1 and 50 mg L1, respectively at a pH
value of 1. Fig. 3 shows the performance of breakthrough curves
at different values of mass of adsorbent. It is evident from Fig. 3
that as the mass of adsorbent increases, the obtained value of
breakthrough time increases. The breakthrough times were ob-
tained as 310, 630 and 850 min for 15, 25 and 30 g of sawdust,
respectively. The total time, corresponding to the stoichiometric
capacity of the column, shows an increasing trend (660–
1260 min) with an increase in the mass of adsorbent (15–30 g) (Ta-
ble 1). The removal efficiency of Cr(VI) for the fixed-bed adsorption
column increased from 59.4% to 74.6% with an increase in the mass
of adsorbent from 15 to 30 g (Table 1). The fraction of unused bed-
length at the breakthrough point was found to decrease in the
range of 0.53–0.31 for the sawdust amount of 15–30 g (Table 1).
The rate of adsorbent exhaustion was decreased from 4.8 to
3.5 g L1 with an increase in the mass of sawdust from 15 to 30 g.
Fig. 3 shows that with an increase in the amount of adsorbent,
the capacity of the adsorption column to adsorb Cr(VI) increases
which results in a delay to obtain the breakpoint time. This may
be due to the increase in the adsorbent surface area with increase
in the adsorbent amount which provides more binding sites for the
adsorption. For smaller bed-length, the rate of adsorbent exhaus-
tion was higher which shows a faster exhaustion of the fixed-bed.
5.1.3. Effect of initial Cr(VI) concentration
A change in the initial Cr(VI) concentration has a significant
influence on the characteristics of the breakthrough curve. The
adsorption performance of sawdust was tested by varying the inlet
Cr(VI) concentration from 50 to 100 mg L1. The breakthrough
curves for sawdust obtained at different initial Cr(VI) concentra-
tions are shown in Fig. 4. As the initial Cr(VI) concentration was

1.0 1.0
0.9 0.9
0.8 0.8
0.7 0.7
0.6 0.6
Cb/Cbo

0.5 0.5
Cb/Cbo

0.4 0.4
0.3 0.3
-1
0.2 Q = 10 mL min 0.2
-1 Mass = 15 g
Q = 15 mL min
0.1 -1 0.1 Mass = 25 g
Q = 20 mL min Mass = 30 g
0.0 0.0
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000 1200 1400 1600 1800
Time (min) Time (min)
Fig. 2. Effect of flow rate on breakthrough curve for Cr(VI) removal using sawdust Fig. 3. Effect of mass of adsorbent on breakthrough curve for Cr(VI) removal using
(Cb0 = 50 mg L1 and W = 25 g). sawdust (Cb0 = 50 mg L1 and Q = 10 mL min1).
5638 S. Gupta, B.V. Babu / Bioresource Technology 100 (2009) 5633–5640

1.0 The ionic state of the functional group on the sawdust surface
depends on the pHzpc (zero point of charge) value of adsorbent.
0.9
The value of pHzpc of sawdust was obtained as 6.0, and below this
0.8 pH value, the surface charge of the sawdust is positive (Suksabye
et al., 2007). In the present study, the pH of the initial Cr(VI) solu-
0.7
tion was maintained as 1 which was less than the value of pHzpc.
0.6 This indicates that the active sites of sawdust are positively
charged. Within the solution pH range of 1.0–3.0, chromium ions
0.5
Cb/Cbo

can exist in the form of HCrO4. At lower solution pH value of 1,

0.4 the increase in Cr(VI) adsorption is due to the electrostatic attrac-
tion between positively charged groups of sawdust surface and the
0.3
HCrO4.
-1
0.2 Cb0 = 50 mg L
-1
Cb0 = 75 mg L 5.3. Mathematical modeling and simulation
0.1 -1
Cb0 = 100 mg L
0.0 In the present work, the linear velocity variation along the col-
0 200 400 600 800 1000 1200 1400 1600 umn height is considered in the mathematical model for fixed-bed
Time (min) adsorption column. The proposed mathematical model is simu-
lated and validated using the parametric values reported by Bautis-
Fig. 4. Effect of initial Cr(VI) concentration on breakthrough curve for Cr(VI)
ta et al. (2003) (Table 2). The present model is also compared with
removal using sawdust (W = 25 g and Q = 10 mL min1).
the experimental data reported by Bautista et al. (2003) with the
predicted results obtained using the present model and the model
proposed by Bautista et al. (2003) as shown in Fig. 5. The obtained
increased from 50 to 100 mg L1, the break point time decreased value of standard deviation (s.d.) indicates that the present model
from 630 to 280 min. The total time for adsorption, corresponding (s.d. = 0.113) shows an improvement over the previous model
to the stoichiometric capacity of the column, was found to be de- (s.d. = 0.139) given by Bautista et al. (2003). The incorporation of
creased from 1080 to 740 min with an increase in the initial Cr(VI) velocity variation along the bed results in a better steepness of
concentration from 50 to 100 mg L1 (Table 1). The total percent- the breakthrough curve as stated by Ruthven (1984) and Ma
age removal of Cr(VI) for the fixed-bed adsorption column was de- et al. (1996). This establishes the fact that the effect of velocity var-
creased from 74.5% to 55.6% with an increase in the initial Cr(VI) iation on breakthrough curve is significant.
concentration (Table 1). The fraction of unused bed-length at The comparison of experimental results and the model predic-
breakthrough point was obtained in the range of 0.42–0.62 for tions (pore diffusion and solid diffusion models) for Cr(VI) adsorp-
50–100 mg L1 of the initial Cr(VI) concentration (Table 1). The tion using sawdust is shown in Fig. 6. Model parameter values for
rate of adsorbent exhaustion was increased from 3.9 to 8.9 g L1 simulation in the present study are listed in Table 2. The shape of
with an increase in the initial Cr(VI) concentration from 50 to the breakthrough curves obtained using the pore diffusion and so-
100 mg L1. lid diffusion models were found to be almost similar for Cr(VI) re-
The increase in the initial Cr(VI) concentration led to reach bed moval. This indicates the suitability of both the models for Cr(VI)
saturation earlier and the breakthrough time was quickly obtained removal using sawdust. Suitability of both the models is also con-
due to the relatively slower transport because of a decrease in dif- firmed by the values of standard deviation obtained in the range of
fusion coefficient and the decreased mass transfer coefficient at 0.063–0.105 for pore diffusion and 0.036–0.13 for solid diffusion
low Cr(VI) concentration (Ruthven, 1984). Binding sites, quickly for different operating conditions (Table 3). In case of pore diffu-
filled at higher initial concentration, result in a decrease in the sion, Cr(VI) ions are adsorbed outside the surface of the adsorbent
breakthrough time. It is observed that the adsorbent gets saturated as well as inside the pores of the adsorbent. Moreover, for solid dif-
faster at higher concentrations of adsorbate due to the higher rate
of adsorbent exhaustion at higher Cr(VI) concentration. For a low
initial Cr(VI) concentration, breakthrough occurs very late and Table 2
the surface of the adsorbents is saturated with Cr(VI) at a relatively Model parameters values used for simulation.
longer time. This fact is probably associated with the availability of
Parameter Values Values
adsorption sites around or inside the adsorbent particles that are (Bautista et al., 2003) (present study)
able to capture the Cr(VI) at a lesser retention time.
e, Bed porosity (–) 0.58 0.4
ep, Particle porosity (–) 0.53 0.3
5.2. Mechanism of Cr(VI) adsorption qp, Particle density (kg m3) 1970 1200
qb, Bed densitya (kg m3) 900 125
In adsorption, atoms, ions or molecules of an adsorbate diffuse ql, Liquid densitya (kg m3) 1000 1000
DL, Axial dispersion coefficienta 5.9  1010 4.31  109
to the surface of the solid adsorbent, where they either chemically
(m2 s1)
bond with the solid surface or are physically held with weak inter- qm, Maximum adsorption capacity 45.4 41.9
molecular forces. The electrostatic, chemisorptive and functional (mg g1)
group interactions define the affinity of an adsorbent for a specific b, Langmuir isotherm constant 0.84 0.43
(mL mg1)
adsorbate. The metallic ions uptake on sawdust mainly depends on
Dp, Pore diffusivity (m2 s1) 2.5  10 11
6.62  109
(1) the metal ions concentration, and (2) the adsorption and reduc- Ds, Solid diffusion coefficient – 8.60  1013
tion phenomena that simultaneously take place on the sawdust (m2 s1)
surface. These phenomena are strongly related to the solution kf, External mass transfer 1.5  106 2.5  105
pH. The solution pH plays a major role in the adsorption of Cr(VI) coefficient (m s1)
D, Bed diameter (m) 0.016 0.015
and it can be related to the type and ionic state of the functional
a
group present on the adsorbent surface (Babu and Gupta, Assumed values based on the usual ranges reported in the literature (Malkoc
2008a,b; Gupta and Babu, 2009). et al., 2006; Ruthven, 1984).
 S. Gupta, B.V. Babu / Bioresource Technology 100 (2009) 5633–5640 5639

1.0 and solid diffusion models are similar. It can be observed from
Fig. 6 that the experimental data for Cr(VI) adsorption using saw-
0.9
dust fit well with the models during the initial time period of
0.8 adsorption, but not so in the latter part of adsorption as reflected
in the respective breakthrough curves. This may be due to the high
0.7
fraction of unutilized bed-length (0.31–0.62) which is responsible
0.6 for more flattening of the breakthrough curve at the latter stage
of adsorption (McCabe et al., 2007). Langmuir isotherm model is
Cb/Cbo

0.5
found to be better than the Freundlich isotherm model to describe
0.4 the equilibrium data for Cr(VI) adsorption on sawdust (Gupta and
Babu, 2009). Langmuir isotherm is considered as favorable iso-
0.3
therm, whereas the Freundlich isotherm is accepted as a strongly
0.2 favorable isotherm. The unused bed-length for favorable isotherm
With velocity variation (Present model)
is higher than the strongly favorable isotherm (McCabe et al.,
0.1 Without velocity variation (Bautista et al., 2003)
Experimental 2007).
0.0 After having seen the good agreement between model predicted
0 400 800 1200 1600 2000 2400 values and the experimental results, the proposed model is sub-
Time (sec) jected to parametric study. The adsorption column performance
is also affected by the other model parameters such as particle ra-
Fig. 5. Comparison between theoretical and experimental results obtained using
dius and external-film mass transfer coefficient. The obtained
proposed mathematical model (Cb0 = 1000 mg L1, Q = 1 mL min1 and W = 30 g).
breakthrough time was highly sensitive to the particle radius and
external-film mass transfer coefficient. The corresponding sensitiv-
ity values obtained were 2.638  104 min m1 and 3.125  103
1.0 min2 m1, respectively.

0.9
6. Conclusions
0.8
0.7 This study, on fixed-bed column adsorption using a low-cost
adsorbent (sawdust), showed that Cr(VI) removal is a strong func-
0.6 tion of the flow rate, the mass of adsorbent and the initial Cr(VI)
concentration. The obtained breakthrough curves are strong func-
Cb/Cbo

0.5
tions of the percentage removal, the adsorption exhaustion rate
0.4 and the fraction of unused bed-length. The proposed mathematical
0.3 model was successfully validated with the literature data and the
obtained experimental data of this study. The pore diffusion and
0.2 Pore diffusion solid diffusion models were found to be suitable for explaining
0.1 Solid diffusion the breakthrough behavior attained for Cr(VI) removal using
Experimental sawdust.
0.0
0 400 800 1200 1600 2000 2400
Acknowledgements
Time (min)
Fig. 6. Comparison of experimental and theoretical breakthrough curve for Cr(VI) Authors thank University Grants Commission (UGC), New Delhi,
removal using sawdust (Q = 10 mL min1, C0 = 50 mg L1 and W = 30 g). India for their financial support.

References

Table 3 Agency for Toxic Substances and Disease Registry (ATSDR), 1993. Toxicological
Standard deviation values for Cr(VI) adsorption on sawdust by fixed-bed adsorption Profile for Chromium. US Public Health Service, US Department of Health and
column on different operating conditions. Human Services, Altanta, GA.
Ahmad, W.A., Zakaria, Z.A., Razali, F., Samin, J., in press. Evaluation of the combined
S. Cb0 W Q Standard deviation (s.d.) Cr(VI) removal capacity of sawdust and sawdust-immobilized acinetobacter
no. (mg L1) (g) (mL min1) haemolyticus supplied with brown sugar. Water Air Soil Pollut., doi:10.1007/
Pore diffusion Solid diffusion
s11270-009-0037-5.
model model
APHA, 1985. Standard Methods for the Examination of Water and Wastewater, 16th
1 50 25 10 0.093 0.077 ed. APHA, AWWA, WPCF, Washington, DC.
2 50 25 15 0.066 0.097 Babu, B.V., Gupta, S., 2005. Modeling and simulation of fixed-bed adsorption
3 50 25 20 0.105 0.130 column: effect of velocity variation. J. Eng. Technol. 1, 60–66.
4 50 30 10 0.063 0.036 Babu, B.V., Gupta, S., 2008a. Adsorption of Cr(VI) using activated neem leaves as an
5 50 15 10 0.072 0.118 adsorbent: kinetic studies. Adsorption 14, 85–92.
6 75 25 10 0.071 0.106 Babu, B.V., Gupta, S., 2008b. Removal of Cr(VI) from wastewater using activated
tamarind seeds as an adsorbent. J. Environ. Eng. Sci. 7, 553–557.
7 100 25 10 0.099 0.118
Bautista, L.F., Martinez, M., Aracil, J., 2003. Adsorption of a-amylase in a fixed bed:
operating efficiency and kinetic modeling. AIChE 49, 2631–2641.
Contreras-Ramos, S.M., Alvarez-Bernal, D., Trujillo-Tapia, N., Dendooven, L., 2004.
Composting of tannery effluent with cow manure and wheat straw. Bioresour.
fusion, most of the Cr(VI) diffusion takes place at the outer surface Technol. 94, 223–228.
of the adsorbent. In the present study, the adsorbent used is saw- Gode, F., Moral, E., 2008. Column study on the adsorption of Cr(III) and Cr(VI) using
dust having a lesser bulk and particle density which signifies that Pumice, Yarıkkaya brown coal, Chelex-100 and Lewatit MP 62. Bioresour.
Technol. 99, 1981–1991.
the most of the surface of sawdust is available for adsorption. So Gode, F., Atalay, E.D., Pehlivan, E., 2008. Removal of Cr(VI) from aqueous solutions
the shape of the breakthrough curves obtained for pore diffusion using modified red pine sawdust. J. Hazard. Mater. 152, 1201–1207.
5640 S. Gupta, B.V. Babu / Bioresource Technology 100 (2009) 5633–5640
Gupta, S., Babu, B.V., 2009. Removal of toxic metal Cr(VI) from aqueous solutions
using sawdust as adsorbent: equilibrium, kinetics, and regeneration studies.
Chem. Eng. J. 150, 352–365.
Kumar, R., Bishnoi, N.R., Bishnoi, G.K., 2007. Biosorption of chromium (VI) from
aqueous solution and electroplating wastewater using fungal biomass. Chem.
Eng. J. 135, 202–208.
Langmuir, I., 1918. The adsorption of gases on plane surfaces of glass, mica and
platinum. J. Am. Chem. Soc. 40, 1361–1367.
Li, H., Liu, T., Li, Z., Deng, L., 2008. Low-cost supports used to immobilize fungi and
reliable technique for removal hexavalent chromium in wastewater. Bioresour.
Technol. 99, 2234–2241.
Liao, H.T., Shiau, C.Y., 2000. Analytical solution to an axial dispersion model for the
fixed-bed adsorber. AIChE 46, 1168–1176.
Ma, Z., Whitley, R.D., Wang, N.H.L., 1996. Pore and surface diffusion in
multicomponent adsorption and liquid chromatography systems. AIChE 42,
1244–1262.
Malkoc, E., Nuhoglu, Y., 2007. Potential of tea factory waste for chromium(VI)
removal from aqueous solutions: thermodynamic and kinetic studies. Sep.
Purif. Technol. 54, 291–298.
Malkoc, E., Nuhoglu, Y., Dundar, Y.M., 2006. Adsorption of chromium(VI) on
pomace—an olive oil industry waste: batch and column studies. J. Hazard.
Mater. B 138, 142–151.
McCabe, W.L., Smith, J.M., Harriott, P., 2007. Unit Operations of Chemical
Engineering, seventh ed. McGraw-Hill International Edition, USA.
Memon, S.Q., Bhanger, M.I., Khuhawar, M.Y., 2005. Preconcentration and separation
of Cr(III) and Cr(VI) using sawdust as a sorbent. Anal. Bioanal. Chem. 383, 619–
624.
Mungasavalli, D.P., Viraraghavan, T., Jin, Y.C., 2007. Biosorption of chromium from
aqueous solutions by pretreated Aspergillus niger: batch and column studies.
Colloids Surf. A 301, 214–223.
Namasivayam, C., Yamuna, R.T., 1995. Adsorption of chromium (VI) by a low-cost
adsorbent: biogas residual slurry. Chemosphere 30, 561–578.
Ruthven, D.M., 1984. Principles of Adsorption and Adsorption Processes. John Wiley
& Sons, New York.
Sankararamakrishnan, N., Dixit, A., Iyengar, L., Sanghi, R., 2006. Removal of
hexavalent chromium using a novel cross linked xanthated chitosan.
Bioresour. Technol. 97, 2377–2382.
Sarin, V., Singh, T.S., Pant, K.K., 2006. Thermodynamic and breakthrough column
studies for the selective sorption of chromium from industrial effluent on
activated eucalyptus bark. Bioresour. Technol. 97, 1986–1993.
Selvaraj, K., Manonmani, S., Pattabhi, S., 2003. Removal of hexavalent chromium
using distillery sludge. Bioresour. Technol. 89, 207–211.
Sotelo, J.L., Uguina, M.A., Delgado, J.A., Celemin, L.I., 2004. Adsorption of methyl
ethyl ketone and trichloroethane from aqueous solutions onto activated carbon
fixed-bed adsorbers. Sep. Purif. Technol. 37, 149–160.
Suksabye, P., Thiravetyan, P., Nakbanpote, W., Chayabutra, S., 2007. Chromium
removal from electroplating wastewater by coir pith. J. Hazard. Mater. 141,
637–644.
Yan, G., Viraraghavan, T., Chen, M., 2001. A new model for heavy metal removal in a
biosorption column. Adsorpt. Sci. Technol. 19, 25–43.
Yu, L.J., Shukla, S.S., Kenneth, L.D., Shukla, A., Margrave, J.L., 2003. Adsorption of
chromium from aqueous solutions by maple sawdust. J. Hazard. Mater. B 100,
53–63.