Journal of Environmental Chemical Engineering 3 (2015) 1827–1836

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Journal of Environmental Chemical Engineering

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

Estimation of packed-bed parameters and prediction of breakthrough

curves for adsorptive removal of 2,4-dichlorophenoxyacetic acid using
rice husk ash
Sunil K. Deokara , Sachin A. Mandavganea,*
a
Department of Chemical Engineering, VNIT, South Ambazari Road, Nagpur 440010, India

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

Article history: In this paper, we studied the physicochemical characteristics of rice husk ash (RHA). Our results show
Received 30 December 2014 higher surface area, smaller silica-to-carbon ratio, and consequently higher batch adsorption capacity for
Accepted 15 May 2015 bigger RHA particles. Packed-bed performance of bigger particles (0.500–0.354 mm) was investigated for
Available online 30 June 2015
influent concentration (50–400 mg/L), flow rate (1–10 mL/min), and bed height (7–13 cm). The maximal
removal (53.86%) was achieved for an influent concentration of 50 mg/L, flow rate of 7 mL/min, and bed
Keywords: height of 9 cm. For minimal removal (34.60%), the corresponding parameters were 100 mg/L, 7 mL/min,
2,4-D
and 7 cm. Various mathematical models, including bed depth service time, Bohart–Adams, Wolborska,
Breakthrough capacity
Continuous study
Thomas, Clark, Yoon–Nelson, and deactivation kinetic, are applied to experimental data for breakthrough
Deactivation kinetic model curve prediction and to determine the optimal bed parameters. According to the bed depth service time
Packed-bed model model, 10% and 90% breakthrough capacities were determined to be 2628.10 and 7400.03 mg/L,
Rice husk ash respectively. The deactivation kinetic model for the solid–liquid adsorption system is found to best
elucidate the packed-bed data. Packed-bed adsorption capacity (mg/m2) for RHA is 2.7 times higher than
synthetic activated carbon.
ã 2015 Elsevier Ltd. All rights reserved.

Introduction
Spraying of pesticides in the open environment is a common
agricultural practice. These sprayed pesticides accumulate in the
soil or enter into water bodies (e.g., lakes, rivers) through run-off,
which has a hazardous effect on the health of both animals and
humans [1]. The presence of 2,4-dichlorophenoxyacetic acid (2,4-
D), one of the herbicides used to control broad leaf weed species, is
reported in groundwater and surface water [2]. Among the several
methods reported for the removal of pesticides from water,
adsorption has been found to be superior in terms of cost,
operation flexibility, and insensitivity toward contaminants [3,4].
Effective removal of 2,4-D from water has been achieved using
various adsorbents such as commercially available granular
activated carbon and activated carbon derived from date stones,
banana stalk, oil palm frond, and corncob [3,5–8]. The potential
adsorption capacity of several other adsorbents, such as industrial
wastes [1], modified silica gel [9], clay minerals [10,11], layered
* Corresponding author. Fax: +91 712 2223969.
E-mail addresses: sam@che.vnit.ac.in (S.K. Deokar), mandavgane1@gmail.com
(S.A. Mandavgane).
double hydroxide [12–14], had also been reported for the batch
removal of 2,4-D. In general, batch adsorption is performed to
investigate the maximal adsorbent capacity and kinetics of the
adsorption process [15]. Adsorption in packed column is commer-
cially worthwhile because the continuous contact between
adsorbate and adsorbent allows for efficient utilization of the
adsorbent, thereby enhancing the treatment of the effluent. In
addition, this method allows for parallel regeneration of the
adsorbent. To our knowledge, there is only one study on packed-
bed removal of 2,4-D in which activated carbon prepared from oil
palm fronds was used as the adsorbent [7].
In this paper, we investigated the packed-bed removal of 2,4-D
using RHA. Because the fluctuation of flow rate due to the wide
particle-size distribution leads to erroneous evaluation of packed
bed, batch adsorption experiments were performed to identify the
suitable particle size. Based on these results, RHA particles
measuring 0.500–0.354 mm having larger surface area and
capacity were selected. The column parameters are determined
and various packed-bed models are applied to experimental data.
The deactivation kinetic model, originally derived for gas–solid
adsorption, was applied for the first time to solid–liquid
adsorption, and it showed the best fit to the experimental data.

http://dx.doi.org/10.1016/j.jece.2015.06.025
2213-3437/ ã 2015 Elsevier Ltd. All rights reserved.
1828 S.K. Deokar, S.A. Mandavgane / Journal of Environmental Chemical Engineering 3 (2015) 1827–1836

difference between the initial and equilibrium concentrations of

Nomenclature
the adsorbate.

C0 influent concentration (mg/L) Packed-bed adsorption

C effluent concentration (mg/L)
t service time of column (min) A glass column (30 cm height, 1.2 cm internal diameter) with
N0 sorption capacity (mg/L) four outlets, with three outlets 3 cm apart and one at 9 cm from the
U0 linear flow velocity (cm/min) bottom to collect effluent, was fabricated for continuous adsorp-
Z bed height (cm) tion of 2,4-D. A preweighed quantity of RHA according to the bed
KBD and KAB adsorption rate constant [L/(mg min)] height was packed between two supporting layers of glass wool as
KT Thomas rate constant [L/(mg min)] shown in Fig. 1S. The glass wool prevents the flow of the adsorbent
q0 Thomas model adsorption capacity (mg/g) along with the effluent. Before performing the actual experiments,
QW and N0/r Wolborska adsorption capacity (mg/g), r (g/ double-distilled water was pumped upward through the bed to
cm3) remove trapped air using a peristaltic pump (model-PP201V;
m mass of adsorbent in column (g) Electro Lab), and the column was kept idle for 24 h. The samples
Q volumetric flow rate (mL/min) were collected periodically from the outlets at constant influent
b kinetic coefficient of external mass transfer rate. The effluent concentration Ct (mg/L) was measured using the
(min1) UV/VIS spectrophotometer. The column was operated at a constant
KYN Yoon–Nelson model kinetic constant (min1) temperature (30
2  C) and solution pH 3.5. Table 1 presents the
t0.5 time required for 50% adsorbate breakthrough details on the experimental conditions. The breakthrough (BT)
(min) curve (Ct/C0 vs time), with breakthrough (tb or t0.1) and saturation
n Freundlich constant (ts) points assumed at Ct/C0 = 0.10 and Ct/C0 = 0.97, respectively, was
r Clark model constant (min1) plotted for each experiment.
A Clark model constant
k0 Initial sorption rate constant [mL/(g min)] Estimation of packed-bed parameters
kd Deactivation rate constant (min1)
The dynamic performance of packed-bed adsorption depends
on experimental conditions that significantly affect the mass-
transfer resistance and thereby the adsorption parameters. The
following parameters were evaluated from the BT curves: bed
Materials and methods capacity, mass-transfer zone, bed utilization, adsorbent usage rate,
and volume of solution treated. Applying mass balance equation
Adsorbent across the column and assuming area under the BT curve is
proportional to capacity, as described by Geankoplis et al. [16] and
RHA was obtained from Yash Agro Energy Ltd. (Nagpur, India). Sotelo et al. [17], the breakthrough (Qb, mg/g) and saturation (Qs,
The raw RHA particles were segregated into five different particle mg/g) capacities were calculated using the following equations:
size ranges (0.500–0.354 mm, 0.354–0.251 mm, 0.251–0.152 mm,
0.152–0.089 mm, and less than 0.089 mm) by sieving them through Ztb  
C0 Q Ct
the following BSS meshes: 30–44, 44–60, 60–100, 100–170, and Qb ¼ 1 dt (1)
m C0
less than 170. The BET surface area of each particle size range was 0

measured using the Micromeritics ASAP 2010 apparatus. The

compositions of carbon, hydrogen, and nitrogen were determined
with an Elemental Analyzer (vario MACRO cube, Elementar, Hanau, Zts  
C0 Q Ct
Germany). The XRF analysis was performed using PW 2403 Qs ¼ 1 dt (2)
m C0
(PANalytical). 0

where tb (min) and ts (min) are the breakthrough and saturation

Adsorbate
Analytical-grade 2,4-D was purchased from Sigma–Aldrich and
the desired concentration of 2,4-D was prepared by dissolving it in
double-distilled water. The molecular formula and the molar mass
of 2,4-D are C8H6Cl2O3 and 221.04 g/mol, respectively.
times, respectively, and m (g) is the mass of the adsorbent. The
mass-transfer zone (MTZ, cm) [17], which refers to the length of
bed that participated in adsorption and advances through the bed
Table 1
Experimental conditions.

Expt. No. Influent concentration Flow rate Bed height

C0 (mg/L) Q (mL/min) Z (cm)
Batch adsorption
E1 50 7 9
E2 100 7 9
In a preliminary study, glass vials containing 25 mL 2,4-D E3 200 7 9
solution (100 mg/L) and a fixed dose of RHA of different particle E4 400 7 9
size fractions were shaken in a constant-temperature water bath E5 100 1 9
E6 100 3 9
for infinite time (approximately 24 h). Then, the mixture was
E7 100 7 9
filtered, and its equilibrium concentration was determined on a E8 100 10 9
UV/VIS spectrophotometer (Shimadzu, U.V. 1800, Japan) at lmax = E9 100 7 7
283 nm using 1-mL cuvettes (Sterna). The percentage removal for E10 100 7 9
each particle-size fraction was determined by calculating the E11 100 7 11
E12 100 7 13
 S.K. Deokar, S.A. Mandavgane / Journal of Environmental Chemical Engineering 3 (2015) 1827–1836 1829

from start to end, was calculated as follows: experimental and predicted tb was determined by
   
Q t t
MTZ ¼ Z 1  b (3) e ¼ 100 bexpt bpred (7)
Qs tbexpt:
where Z is the overall bed height (cm). In the MTZ, the bed
saturation varies from 100% to 0%, and the adsorbate concentration
varies from inlet concentration to zero (influent solution). The Results and discussion
fraction of bed utilization (FBU) was determined from MTZ. The
contact between adsorbate and adsorbent expressed as empty bed Characterization of adsorbent
contact time (EBCT) or residence time influences the volume of
influent treated and the nature of BT curve. The following The physicochemical characteristics of the five different
equations were used to determine EBCT and adsorbent usage rate particle-size fractions of RHA shown in Table 2 reveal that the
(Ur) [18]: BET surface area increases significantly with particle size, which is
V C AC Z in contrast to those reported in the literature [19,20]. In general, it
EBCT ¼ ¼ (4) is observed that the BET surface area increases with a decrease in
Q Q
the particle size of adsorbent. In this investigation, however, the
increasing trend of silica-to-carbon ratio with decreasing particle
m VCr size and pore shape (pore volume/pore diameter) is attributed to
Ur ¼ ¼ (5) the increase in BET surface area with particle size. In addition to the
V b V C Nb
probability of nonporous fines predominantly ending up as smaller
where VC (m3) and Vb (m3) are volume of adsorbent in the bed and
particle-size fractions, blocking of pores (mesopores/macropores)
volume of the solution treated at breakthrough, respectively; AC
by submicrometer-scale particles may be plausible reasons for the
(m2) is the cross-sectional area of the column; r (g/cm3) is
lesser BET surface area of smaller particles [21]. The pore volume
apparent density of adsorbent; and Nb is the number of bed
and diameter measurements confirm the existence of deeper and
volumes of solution needed to achieve adsorption breakthrough.
wider pores on the surface of bigger and smaller particles,
respectively.
Packed-bed modeling
Batch adsorption
The packed-bed models are formulated based on fundamental
transport equations that include solid–liquid material balance and
Batch adsorption results indicated higher removal of 2,4-D onto
adsorption rate. The adsorption rate more often depends on the
bigger particles owing to their greater surface area than smaller
adsorption mechanism, which involves a rate-limiting step (either
particles. Tsai et al. [21] have reported similar results for paraquat
diffusion or mass transfer) and the reaction between adsorbent
adsorption on activated clay. In our study, the percentage removal
and adsorbate. In the sequence of model development, at the final
shown in Fig. 1 is inversely proportional to the silica-to-carbon
step, the equation of the best-fit isotherm obtained from the batch
ratio as 2,4-D (anionic) is repelled by negatively charged silica.
study is used. The equations derived to model the packed-bed
Besides higher silica content, decrease in carbon content is also
system are in differential form and require complex numerical
methods to solve. In addition, the possibility of a numerical
solution not describing a packed-bed system cannot be ignored. It
has to be noted that the numerical solution of a particular packed-
bed model is not applicable for others as it is derived based on
adsorption rate and mechanism. Considering these facts, simple
packed-bed models (given in Table 1S) were developed to predict
dynamic performance of RHA bed for 2,4-D adsorption. Literature
sources indicate that all models except the deactivation kinetic
model were extensively used in various studies of solid–liquid
packed-bed adsorption. The error between predicted and experi-
mental (Ct/C0) values was calculated using Marquardt’s percent
standard deviation (MPSD) [18].
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
u 0    12
u Ct
 Ct
u 1 X
B C0 expt: C 0 pred: C
MPSD ¼ 100u t @   A (6)
NP Ct
C 0 expt:

where N is number of experimental measurements and P is

number of parameters. The percentage deviation between Fig. 1. Batch adsorption of 2,4-D on different particle size fractions of RHA.

Table 2
Physicochemical characteristics of RHA with different particle sizes.

Particle size Weight% BET surface area (m2/g) Pore volume (cm3/g) Pore diameter (nm) Silica-to-carbon ratio Hydrogen% Nitrogen%
(mm)
0.500–0.354 14.00 92.08 0.0144 9.37 6.02 1.266 0.73
0.354–0.251 15.00 44.37 0.0092 10.35 14.76 0.384 0.82
0.251–0.152 19.50 26.25 0.0061 12.00 23.61 0.617 0.46
0.152–0.089 20.00 17.92 0.0045 13.81 28.58 0.320 0.56
< 0.089 31.50 13.65 0.0037 16.15 31.83 0.290 0.51
1830 S.K. Deokar, S.A. Mandavgane / Journal of Environmental Chemical Engineering 3 (2015) 1827–1836

Table 3
Packed-bed parameters for adsorption of 2,4-D on RHA.

Expt. No. EBCT tb expt ts Vs Nb Ur Qb Qs MTZ FBU % Removal

(min) (min) (min) (mL) (g/mL) (mg/g) (mg/g) (cm)
E1 1.45 24.13 73.86 517.02 10.74 0.024 2.06 3.48 3.67 0.59 53.86
E2 1.45 12.50 55.14 385.98 5.60 0.046 2.12 4.25 4.51 0.50 44.21
E3 1.45 7.80 37.34 261.38 3.53 0.073 2.63 5.40 4.62 0.49 41.70
E4 1.45 4.00 22.92 160.44 1.80 0.143 2.68 5.93 4.93 0.45 36.85
E5 10.17 133.75 390.78 390.78 8.59 0.030 3.24 5.13 3.32 0.63 52.47
E6 3.39 38.50 155.08 465.24 7.36 0.035 2.80 5.03 3.99 0.56 47.86
E7 1.45 12.50 55.14 385.98 5.60 0.046 2.12 4.25 4.52 0.50 44.21
E8 1.02 4.50 25.00 250.00 2.90 0.089 1.08 2.34 4.85 0.46 37.42
E9 1.13 5.80 38.84 271.88 3.48 0.074 1.31 3.06 4.00 0.56 34.60
E10 1.45 12.50 55.14 385.98 5.60 0.046 2.12 4.25 4.51 0.50 44.21
E11 1.78 21.00 100.36 702.52 7.58 0.034 2.86 5.61 5.39 0.40 40.08
E12 2.10 31.26 135.78 950.49 9.54 0.027 3.57 6.79 6.16 0.32 42.89

responsible for reduction in 2,4-D removal onto smaller particles.

Therefore, particles measuring 0.500–0.354 mm were selected for 1.0
packed-bed adsorption of 2,4-D.
0.8
Packed-bed parameters

The packed-bed parameters presented in Table 3 show that 0.6

Ct/C0
EBCT is inversely proportional to flow rate and directly propor-
tional to bed height at constant adsorbent dosage and flow rate,
0.4 1 mL/min.
respectively. The adsorbent usage rate, that is, the mass of
adsorbent saturated with adsorbate per volume of solution treated, 3 mL/min.
is reduced with increase in EBCT. At the breakthrough point, 0.2 7 mL/min.
adsorbent capacity (Qb) is more than half of the saturation capacity
10 mL/min.
(Qs) for lowest concentration and flow rate, and for highest
0.0
absorbent loading. The maximum and minimum bed utilization 0 75 150 225 300 375
can be observed for the lowest flow rate and the highest influent
t (min)
concentration, respectively.
Fig. 3. Breakthrough curve at different flow rates (C0: 100 mg/L; Z: 9 cm).
Effect of influent concentration
similar effect for continuous removal of Drimarine red HF-3D dye
When the influent concentration is increased at Q and Z on peanut husk. Tailing of breakthrough curve is attributed to the
(constants), the saturation of column occurs early because of domination of intraparticle diffusion over the mass-transfer
limited adsorption sites. This leads to a reduction in tb and ts values, process [23]. In general, changes in influent concentration do
generating steeper BT curve (Fig. 2) at higher concentrations. In not affect the MTZ significantly [24]; however, in this study, MTZ is
addition, the surface coverage of adsorbent at higher concen- distinctly increased due to increased bed capacity.
trations enhances the activation energy that makes further
adsorption difficult. However, bed capacities (Qb and Qs) are Effect of flow rate
improved due to greater driving force induced by larger
concentration gradient between the liquid and solid phases for The increase in flow rate from 1 to 10 mL/min corresponds to
higher influent concentration. Nausheen et al. [22] reported a changes in the residence time, tR, from 10.17 to 1.02 min, of
adsorbate in the bed, which results in decline of tb and ts as well as
1.0

1.0
0.8

0.8
0.6
Ct/C0

0.6
Ct/C0

0.4 50 mg/L
0.4 7 cm
100 mg/L
9 cm
0.2 200 mg/L
0.2 11 cm
400 mg/L
13 cm
0.0
0 20 40 60 80 100 0.0
t (min) 0 40 80 120 160
t (min)
Fig. 2. Breakthrough curve at different influent concentrations (Q: 7 mL/min; Z:
9 cm). Fig. 4. Breakthrough curve at different bed heights (C0: 100 mg/L; Q: 7 mL/min).
 S.K. Deokar, S.A. Mandavgane / Journal of Environmental Chemical Engineering 3 (2015) 1827–1836 1831

100 Effect of bed height

10% Breakthrough
When the bed height (i.e., dosage) of adsorbent is increased, the
R² = 0.983
80 50% Breakthrough adsorption capacity, which is a function of surface area and thereby
Break through time t (min)

90% Breakthrough binding site, is also increased. Tailing of breakthrough curve in

60
40
20
0
6 7 8 9 10
Bed height Z (cm)
Fig. 5. BDST plot for different bed heights (C0: 100 mg/L; Q: 7 mL/min).
Qb and Qs. The lower flow rate offers adequate time for 2,4-D
molecules to penetrate into RHA pores, resulting in progressive
breakthrough curves as shown in Fig. 3. The length of MTZ is
increased and FBU is decreased (Table 3) due to increase in mass-
transfer rate with flow rate. Similar behavior of MTZ with respect
to variable flow rate has also been described by Han et al. [25] and
Sadaf et al. [26]. The decrease in capacity (Qb or Qs) and percentage
removal for higher flow rate can be attributed to insufficient
contact time between adsorbate and adsorbent due to early
discharge of 2,4-D molecules (adsorbate) from the RHA bed before
equilibrium is achieved. Sadaf et al. [26] also observed the
reduction in bed capacity and shortened breakthrough time at
higher flow rates for continuous removal of direct yellow 50 [27].
Fig. 4 represents the increased intraparticle diffusion due to
increase in EBCT with increase in bed height. Consequently, a
R² = 0.991
greater volume of pesticide is removed (Table 3). Fig. 4 shows the
increase in ts values for higher Z values, which expands MTZ. With
the expansion of MTZ, there is worse utilization of bed. By contrast,
the narrow MTZ for the lowest bed height suggests efficient
utilization of adsorbent, which would facilitate easy regeneration
R² = 0.991
of adsorbent from an energy point of view. However, the
breakthrough time is less for lower bed height due to axial
11 12 13 dispersion, which controls the mass-transfer mechanism [28]. This
is indicative of insufficient time for diffusion of 2,4-D molecules
into RHA. Therefore, the beds of increased height may be
recommended for better column performance.
The effect of any one of the three factors (C0,Q, and Z), keeping
other two factors constant, influences the nature of BT curve.
Treating Q and Z as constant, the BT curve tends to become steeper
at higher C0 and flatter at lower C0. A similar shape of BT curve is
observed for higher and lower values of Q at constant C0 and Z. By
contrast, the shape of BT curve changes from flatter to steeper
when the bed height is reduced and keeping the two factors
constant. The tb and ts values for the steeper BT curve are smaller
than those for the flatter BT curve.
Application of packed-bed models
Bed depth service time model
The BDST model is based on surface reaction theory and
provides information about efficiency of column operating under
constant conditions. This model can be used to obtain desired

Table 4
Packed-bed parameters for adsorption of 2,4-D on RHA by different models considered.

Expt. Bohart–Adams model Wolborska model Thomas model

No. KAB N0 tb pred(min) Є MPSD b (min1) QW tb pred Є MPSD KT q0 tb pred Є MPSD

[L/(mg min)] (mg/L) (mg/g) (min) [L/(mg min)] (mg/g) (min)
E1 2.40 x 103 1505.98 24.58 1.86 23.87 3.61 5.84 24.56 1.78 23.88 2.42 x 103 3.58 22.76 5.68 21.09
E2 1.80 x 103 1809.59 3.5 8 22.13 3.26 7.02 3.52 8.16 22.13 1.47 x 103 4.44 10.42 16.64 39.55
E3 1.35 x 103 2318.45 8.32 6.67 23.67 3.13 9 8.32 6.67 23.67 1.19 x 103 5.82 7.4 15.13 22.41
E4 1.25 x 103 2459.86 4.33 8.25 44.64 3.07 9.55 4.32 8 44.64 9.60 x 104 6.18 3.11 22.25 30.08
E5 2.40 x 104 2250.1 132.99 0.57 17.76 0.54 8.73 132.97 0.58 17.76 2.40 x 104 5.44 126.05 5.76 13.01
E6 8.10 x 104 2020.84 40.1 4.16 26.05 1.64 7.84 40.16 4.31 26.06 5.80 x 104 5.34 33.32 13.45 43.66
E7 1.80 x 103 1809.59 13.5 8 22.13 3.26 7.02 13.52 8.16 22.13 1.47 x 103 4.44 10.42 16.64 39.55
E8 5.34 x 103 852.798 4.36 3.11 27.69 4.55 3.3 4.36 3.11 27.69 3.10 x 103 2.54 3.07 31.78 64.11
E9 2.80 x 103 1277.68 6.22 7.24 35.13 3.58 4.96 6.23 7.41 35.14 2.60 x 103 3.24 5.43 6.38 31.49
E10 1.80 x 103 1809.59 13.51 8.08 22.13 3.26 7.02 13.52 8.16 22.14 1.47 x 103 4.44 10.42 16.64 39.55
E11 1.13 x 10-3 2329.03 20.99 0.05 24.19 2.63 9.04 20.98 0.1 24.19 7.90 x 104 5.97 14.83 29.38 43.82
E12 8.70 x 10-4 2825.22 32.84 5.07 30.66 2.46 10.96 32.87 -5.16 30.66 6.90 x 104 7.07 28.76 25.99 49.66

Expt. Clark model Yoon–Nelson model Deactivation kinetic model

No A r (min1) tb pred Є MPSD KYN t0.5 expt t0.5 pred Є MPSD k0 kd tb pred Є MPSD
(min) (min1) (min) (min) [mL/(g min)] (min1) (min)
E1 548.95 0.138 29.79 23.45 33.86 0.121 40.1 40.9 2 25.17 6.114 0.098 24.33 0.83 11.64
E2 130.71 0.167 16.02 28.18 46.62 0.147 23.3 25.17 8.03 39.47 5.419 0.145 12.97 3.76 9.62
E3 182.55 0.271 11.11 42.39 28.34 0.238 15 16.13 7.53 22.39 5.508 0.231 8.45 8.33 15.89
E4 89.21 0.435 5.27 31.83 34.02 0.384 8.15 8.72 6.99 30.25 5.331 0.419 4.32 8 15.6
E5 807.55 0.028 160.6 20.08 19.1 0.024 195.87 217.47 11 12.98 0.954 0.021 133.9 0.11 26.31
E6 220.08 0.066 48.44 25.81 49.12 0.058 62 71.21 14.85 43.62 2.516 0.058 38.06 1.14 13.92
E7 130.71 0.167 16.02 28.18 46.62 0.147 23.3 25.17 8.03 39.47 5.419 0.145 12.97 3.76 9.62
E8 68.99 0.353 5.77 28.22 70.38 0.31 7.6 9.34 22.89 64.38 6.773 0.356 3.68 18.22 16.96
E9 124.84 0.299 8.8 51.64 48.7 0.26 12.45 13.87 11.41 41.75 6.313 0.237 5.5 5.17 16.15
E10 130.71 0.167 16.02 28.18 46.62 0.147 23.3 25.17 8.03 39.47 5.419 0.145 12.97 3.76 9.62
E11 82.43 0.089 24.88 18.5 48.13 0.079 36.12 41.77 15.64 44.04 4.185 0.088 19.76 5.9 14.25
E12 227.92 0.078 41.43 32.56 55.4 0.069 53.05 59.42 12.01 49.47 3.606 0.061 30.68 1.84 23
1832 S.K. Deokar, S.A. Mandavgane / Journal of Environmental Chemical Engineering 3 (2015) 1827–1836
breakthrough curves [29]. A plot of bed height (Z) against time for
10%, 50%, and 90% breakthrough at constant Q and C0 based on the
BDST model is shown in Fig. 5. The coefficient of determination (R2)
indicates the best-fit BDST model for up to 50% breakthrough;
however, significant intraparticle diffusion in the latter part of the
BT curve for higher Z delays the 90% breakthrough, which results in
lower R2. According to the BDST model, adsorption of 2,4-D on a
chosen particle size of RHA is governed by complex mechanisms
involving more than one rate-controlling step, which can be seen
in Fig. 5, where the 50% breakthrough line (Fig. 5) did not pass
through origin [18]. From the straight-line equation, the N0 and KBD
values for 10% breakthrough are calculated as 2628.10 mg/L and
Fig. 6. Experimental and predicted breakthrough curves using the Bohart–Adams
and Wolborska models at varied (a) influent concentrations, (b) flow rates, and (c)
bed heights.
3.43  104 L/mg min, respectively. The corresponding values for
90% breakthrough are 7400.03 mg/L and 8.86  104 L/mg min.
Further, at constant Z (9 cm), predicted tb at 34.38 and 1.94 min is
investigated for 50 and 10 mL/min, respectively, as discussed by
Han et al. [25]. The minimum bed height required to attain 10 mg/L
Ct is determined as 5.84 cm at 7 mL/min, as described by Maiti et al.
[30].
Bohart–Adams model and Wolborska model
According to the Bohart–Adams model, the adsorption process
is continuous and stability of process is not achieved instan-
taneously [31,32]. The Wolborska model is based on mass-transfer
Fig. 7. Experimental and predicted breakthrough curves using the Thomas model at
varied (a) influent concentrations, (b) flow rates, and (c) bed heights.
 S.K. Deokar, S.A. Mandavgane / Journal of Environmental Chemical Engineering 3 (2015) 1827–1836 1833

equations dealing with diffusion mechanism [17]. Parameters for
the Bohart–Adams and Wolborska models are determined for the
range 0.01 < (Ct/C0) < 0.60, and these are listed in Table 4. It can be
seen that the value of N0 or QW is directly proportional to C0 and Z
and inversely proportional to Q. The increase in flow rate increases
turbulence, which leads to a reduction in the film boundary layer
surrounding the RHA particles. Consequently, KAB or b increases
[33]. The breakthrough times, tb, predicted by both models are
comparable with experimental values. The predicted and experi-
mental BT curves shown in Fig. 6 are closer and their close
approximation is confirmed by MPSD in Table 4. The fitting of
models with experimental data confirms the control of external
mass transfer in the initial part of breakthrough curves.
Deactivation kinetic model
Deactivation kinetic model, primarily developed for gas–solid
adsorption, involves a single activity term to denote the combined
effect of factors such as pore structure, active surface area, and
activity per unit area of solid reactant. Assuming the effect of
aforementioned factors in solid–liquid adsorption, this model is
applied in this study in the 0.01 < (Ct/C0) < 0.97 range and rate
constants are determined.
As can be seen in Table 4, when C0 or Q is increased at a fixed
adsorbent dosage, the number of molecules adsorbed on the active
sites is more, and therefore, deactivation rate constant (kd)
increases. However, kd is reduced for greater Z due to increase
in number of active sites at constant C0 and Q. The change in the

Thomas model
The solid-phase concentration of the solute is calculated by
applying the Thomas model to experimental data in the 0.01 < (Ct/
C0) < 0.97 range. Results presented in Table 4 indicate the increase
in Thomas model adsorption capacity (q0) with increase in C0 and Z
due to increase in concentration gradient and number of
adsorption sites, respectively. The value of q0 also increases with
increase in EBCT, which decreases Q. A similar change in q0 with
change in C0, Q, and Z is previously reported for the removal of
direct yellow 50 dye by Sadaf et al [27]. Values of MPSD at lower C0,
Q, and Z values indicate the absence of limitations to external and
internal diffusions of 2,4-D on the adsorbent surface. Fig. 7 shows a
comparison between experimental and predicted breakthrough
curves using the Thomas model. The deviation between experi-
mental results and results predicted by the Thomas model may be
due to the fact that this model is based on second-order reaction
kinetics, whereas the adsorption is governed by both chemical
reaction kinetics and interphase mass transfer [33].

Clark model
The Clark model applied in the 0.01 < (Ct/C0) < 0.97 region
provides information about the augmented mass transfer rate (r)
with increase in C0 (Table 4). The molecular diffusion path is
reduced in water blanket surrounding adsorbent, which results in
higher r with increase in Q. However, the value of r is reduced for
greater Z owing to the increase in adsorption sites as a result of
higher adsorbent loading. The behavior of r for the Clark model is
similar to the adsorption of phosphate [34,35]; however, this
model appears inappropriate for the present system, as can be
deduced from the poor values of standard deviations (Є and MPSD)
presented in Table 4. By contrast, the Thomas model better
describes the present system. Literature reports indicate that a
combination of Freundlich isotherm (in batch, Fig. 2S) and Clark
model (in column study) best explains the experimental results
[36]. From our study, it can be concluded that a combination of
Langmuir isotherm (in batch, Fig. 3S) and Thomas model (in
column study) best explains the experimental results because both
assume monolayer adsorption. Fig. 8.

Yoon–Nelson model
The Yoon–Nelson model is applied in the 0.01 < (Ct/
C0) < 0.97 range to predict the 50% breakthrough time and the
obtained results are reported in Table 4. The intraparticle diffusion
after 50% column saturation forms nonsymmetrical BT curves
(Fig. 9), indicating delay in saturation time. This results in higher
predicted 50% breakthrough time than that obtained in the
experiments. The parameter KYN in Table 4 is a function of C0, Q,
and Z and is inversely proportional to breakthrough time. The
increase in C0 and Q results in an increase in the driving force for
mass transfer, which directly affects KYN. The higher value of Z
offers longer path for molecules to travel through the bed, resulting Fig. 8. Experimental and predicted breakthrough curves using the Clark model at
in reduced KYN values. varied (a) influent concentrations, (b) flow rates, and (c) bed heights.
1834 S.K. Deokar, S.A. Mandavgane / Journal of Environmental Chemical Engineering 3 (2015) 1827–1836

Fig. 10. Experimental and predicted breakthrough curves using the deactivation
kinetic model at varied (a) influent concentrations, (b) flow rates, and (c) bed
heights.
Fig. 9. Experimental and predicted breakthrough curves using the Yoon–Nelson
model at varied (a) influent concentrations, (b) flow rates, and (c) bed heights.
the Bohart–Adams and Wolborska models are in closer agreement
than that predicted by the Thomas and Clark models, provided the
initial adsorption rate is more significant for variables Q and Z than former two models are applied to the initial part of BT curves.
C0 due to simultaneous change in effluent concentration and Therefore, the Bohart–Adams and Wolborska models provide
weight–time factor (B = m/Q). In comparison with other models, BT better fit to explain the initial part of breakthrough curves. The
curves predicted by the deactivation kinetic model are in better experimental t0.5 value and that predicted by the Yoon–Nelson
agreement with experimental curves as shown in Fig. 10. model are similar, but the MPSD range is large. The experimental tb
value and that predicted by the deactivation kinetic model are
Comparison of models almost the same for all experiments. Comparatively, lower values
and shorter variation range of MPSD for the deactivation kinetic
The R2 value close to unity indicates satisfactory fitting of BDST model present close approximation of experimental and predicted
model up to 50% breakthrough, after which MTZ becomes values. Thus, the deactivation kinetic model is found to be better to
nonuniform. The experimental tb value and that predicted by explain packed-bed adsorption of 2,4-D on RHA than other models.
 S.K. Deokar, S.A. Mandavgane / Journal of Environmental Chemical Engineering 3 (2015) 1827–1836
Though the best fit is deactivation kinetic model but since capacity
cannot be calculated using it, next best fit model is Thomas model
and the capacity based on it is 7.07 mg/g. The adsorption capacities
obtained by various models are comparable however BDST model
though does not fit best gives maximum capacity.
Adsorption capacity: RHA versus activated carbon for packed-bed 2,4-
D removal
The adsorption capacity of activated carbon (predicted by the
Thomas model) with surface area of 1237.13 (m2/g) [7,37] and that
of the present adsorbent (RHA) for 2,4-D are 0.03 and 0.08 mg/m2,
respectively. Thus, a square meter of RHA has 2.67 times higher
adsorption potential than activated carbon. In addition, an
activated carbon column requires 5–10 h for saturation, whereas
an RHA column takes comparatively less time. Therefore, from a
cost and capacity point of view, RHA is a better adsorbent for 2,4-D
removal in a packed bed.
Conclusions
In batch adsorption of 2,4-D using RHA, it is observed that
bigger particles have higher removal potential due to higher
surface area and lower silica-to-carbon ratio, compared with
smaller particles. Packed-bed removal of 2,4-D using bigger
particles is efficient as demonstrated in this study. The difference
in saturation capacities is more than that of corresponding
breakthrough capacities, which confirms the stability of column
after breakthrough.
Among the various packed-bed models applied, from the BDST
model, the following are concluded: (i) more than one rate-
controlling step is involved in the adsorption of 2,4-D and (ii) MTZ
does not move with constant length. According to the Adams–
Bohart and Wolborska models, the kinetics in the early stages of
adsorption is dominated by external mass transfer. The Thomas
model is more suitable than Clark model because removal of 2,4-D
involves monolayer adsorption. Because the deactivation kinetic
model provides the best agreement between experimental and
predicted data over the entire BT curve, it is considered suitable for
describing the solid–liquid adsorption system without the need for
evaluating the structural properties of the adsorbent.
Acknowledgments
The authors are thankful to the Science and Engineering
Research Board, India, for providing a research grant (grant No. SB/
S3/CE/077/2013) to undertake this work. Sophisticated characteri-
zation facilities provided by IBM, Nagpur and CSMCRI, Bhavnagar
(India) are acknowledged. The authors thank Dr Sayaji Mehtre,
Scientist BARC, Mumbai, for his assistance in characterization
studies. Guidance by Dr B D Kulkarni is thankfully acknowledged.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jece.2015.06.025
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