Accepted Manuscript

Studies on adsorption behavior of an industrial waste for removal of chromium from

aqueous solution

H. Panda, N. Tiadi, M. Mohanty, C.R. Mohanty

PII: S1026-9185(16)30092-0
DOI: 10.1016/j.sajce.2017.05.002
Reference: SAJCE 31

To appear in: South African Journal of Chemical Engineering

Received Date: 26 December 2016

Revised Date: 7 May 2017
Accepted Date: 11 May 2017

Please cite this article as: Panda, H., Tiadi, N., Mohanty, M., Mohanty, C.R., Studies on adsorption
behavior of an industrial waste for removal of chromium from aqueous solution, South African Journal of
Chemical Engineering (2017), doi: 10.1016/j.sajce.2017.05.002.

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 ACCEPTED MANUSCRIPT

Studies on adsorption behavior of an industrial waste for removal of chromium from aqueous
solution

1. H. Panda

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Dept. of Civil Engineering, Veer Surendra Sai University of Technology Odisha, Burla-768018
Burla-768018
Email: [email protected]

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2. N. Tiadi
Dept. of Civil Engineering, Veer Surendra Sai University of Technology Odisha, Burla-768018

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Enail;[email protected]
3. M. Mohanty

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Dept. of Electrical and Electronics Engineering, IIIT Bhubaneswar-751013.
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Email: [email protected]

4. C. R. Mohanty
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Dept. of Civil Engineering, Veer Surendra Sai University of Technology Odisha,, Burla-768018
Email- [email protected]
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Studies on adsorption behavior of an industrial waste for removal of chromium from aqueous
solution
Running Title: Adsorption of Cr (VI) by industrial waste from aqueous solution

ABSTRACT

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An investigation on the adsorption characteristics of an industrial waste (Dolochar) for removal
of Cr (VI) from aqueous solutions was studied varying various parameters such as contact time,

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adsorbent dose, adsorbate concentration, pH. The study was conducted varying contact time,
adsorbent dose, adsorbate concentration, pH from 0 to 70 minutes, 10 to 25 g/l, 10 to 50 mg/l and
2 to 7.5 respectively. The results of this study showed that adsorption of chromium by dolochar

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reached to equilibrium after 60 min and after that a little change of chromium removal efficiency
was observed. Maximum chromium removal (≈ 95 %) was obtained at pH of 2 for adsorbent and
adsorbate dose of 20 g/l and 10 mg/l respectively. The obtained results showed that the adsorption

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of chromium (VI) follows Langmuir isotherm equation with a correlation coefficient equal to
0.997. In addition, the kinetics of the adsorption process follows the pseudo second-order kinetics
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model with a rate constant value of 0.821 min-1. Further, the potential of dolochar for the removal
of heavy metal was evaluated in a fixed-bed column at bed depth of 2.5 cm with initial
concentration of 10 mg/l. The breakthourh time and exhaust time were found to be 19.5 hrs and
90 hrs respectively. Total volume of water treated during the exhaust time was 23 liters. The
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results indicate that this industrial waste can be employed as a low cost alternative to commercial
adsorbents for removal of chromium (VI) from water and wastewater.
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Keywords: Adsorption; Dolochar; Chromium (VI); Isotherms; Column study; Breakthrough curve
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1. Introduction

The presence of metal ions in the environment is of major concern due to their toxicity to many life
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forms. Unlike organic pollutants, the majority of which are susceptible to biological degradation, metal
ions do not degrade into harmless end-products. The metals of most immediate concern are Cr, Mn, Fe,
Zn, and Cd which are widely distributed in materials which make up the earth's surface (Dean et al.,
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1972). Among these heavy metals, chromium occurs in higher concentration in the wastes from
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electroplating, paints, dyes, chrome tanning, paper industries, etc. This metal is very toxic. Over exposure
to high concentration of chromium can result in epigastric pain, nausea, vomiting, severe diarrhoea and
haemorrhage (Huang and Wu, 1977). Maximum contaminant level of chromium for the drinking water is
0.05 mg/L. Over the years, various conventional treatment methods such as chemical precipitation, ion
exchange, electrolytic recovery, membrane separation, floatation and adsorption have been used to

* Corresponding author. E-mail addresses: [email protected] (C. R. Mohanty).

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remove chromium from wastewater. Removal of chromium has also been investigated using
phytoextraction, reverse osmosis, adsorption, precipitation, ion-exchange, membrane and biological
processes (Sule and Ingle, 1996, Chiarle et al., 2000, Cengeloglu, 2003, Zhao, 2003, Pehlivan and
Arslan, 2006, Das and Mishara, 2010). These conventional methods are not suitable for the removal of
metals when it is present at low concentrations. Thus, to reduce the heavy metal ion concentration to an

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environmentally acceptable level, a cost-effective and efficient separation method is to be developed. Of
all the various water treatment techniques, adsorption is generally preferred for the removal of heavy
metal ions due to its high efficiency, easy handling, availability of different adsorbents and cost

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effectiveness (Kimbrough et al., 1999, Lin and Juang, 2002, Bhattacharya et al., 2006).
The uses of activated carbon as adsorbent in adsorption process are very popular for removal of metal

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ion from waste water, but are quite expensive and the regeneration of the carbon is not always possible
(Lalvani et al., 1998). A considerable research work has been done in the search of inexpensive

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adsorbents especially developed from various industrial waste materials i.e. fly ash (Pollard et al., 1992,
Ferraiolo et al., 1990), metal hydroxides (Namasi-vayam and Ranganathan, 1998), blast furnace slag
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(Dimitrova and Mehandgiev, 1998), biomass (Chang et al., 1997), peanut hull (Periasamy and Namasi-
vayam, 1994), bagasse pith (Aly and Daifullah,1998), carbonaceous material (Srivastava et al., 1989,
1997, Srivastava and Tyagi, 1995), bagasse fly ash (Dubey and Gopal, 2007), etc. In continuation it was
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decided to undertake a study to assess the potential of a sponge iron industry waste material such as
dolochar, as an adsorbent for the removal of Cr (VI) from aqueous solution. As far as our knowledge
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goes this is the first time when dolochar is used for Cr (VI) removal from synthetic sample.
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2. Materials and methods

This study was accomplished in environmental engineering laboratory, department of civil
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engineering, Veer Surendra Sai University of Technology Odisha in 2015-16. The details of materials and
methods of the study are discussed as below:
2.1 Reagents
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The entire reagents used were of A. R. grade. Stock solutions of the metal ions were prepared by
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dissolving K2Cr2O7) in doubly distilled water. All aqueous solutions were prepared in double distilled
water. The distilled water was examined for Cr (VI) concentration.

2.2 Apparatus and instruments

All the apparatus used were soaked in concentrated HNO3 for 12 h and then washed initially with tap
water and then with distilled water. Then the apparatus were dried in hot air oven. A digital pH meter
(Orion make) was used for all pH measurements. A high precision electrical balance was used for
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weighing. All absorbance measurements were carried out with a spectrophotometer (Thermo Spectronic
UV) equipped with 1-cm quartz cells. A mechanical shaker was used for shaking purpose. Gilson
micropipette with disposable tips was used to add sample.
2.3 Preparation and characterization of adsorbent
Dolochar sample was collected from one of the sponge iron plants of Odisha, India. The raw material

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did not cost anything. The adsorbent was made ready by the following procedure: first the dolochar
particles was washed in tap water and dried under the Sun for 2-3 days. Then it was crushed and dried.
The dolochar particles of 75µ were then washed thoroughly with tap water, and finally it was washed

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with distilled water and dried in hot-air oven at 100 ◦C for overnight. This as-prepared particle was used
for Cr (VI) adsorption. The specific surface area and pore volume of the dolochar particles was found

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out from the BET analysis. These values were 15.365 m2/g and 0.013 cm3/g respectively.
2.4 Analysis of chromium (VI) ions

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The concentration of residual chromium (VI) ions in the effluent was read spectrophotometrically by
using diphenyl carbazide as the complexing agent. One milliliter of a 0.2% (w/v) of diphenyl carbazide
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solution prepared in 95% ethyl alcohol and 1 mL of 1/5 H2SO4 solution was added to the sample (1 mL)
containing less than 100 mg/ L of chromium(VI) ions and diluted to 100 mL with double-distilled water.
The absorbance of the purple colored solution was read at 540 nm after 10 min(Dutta and Ghosh, 2013,
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Acharya et al., 2009a, Acharya et al., 2009b , Panda et al., 2011).

2.5 Batch sorption experiments
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Adsorption studies were mainly carried out by batch technique to obtain rate and equilibrium data.
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The effects of various parameters on the rate of adsorption process were observed by varying contact
time, t (5, 10, 15, 20, 30, 40, 50, 60, and 70 min), initial concentration of chromium ion, Co (10, 20, 30,
and 50 mg/L), adsorbent concentration, W (5, 10, 15, 20 and 25 g/L) and initial pH of solution (2, 3, 4.5,
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6, and 7.5). The experiments were performed in a thermal shaker at controlled temperature (30±1ºC)
using 250 ml Erlenmeyer flasks containing 100 ml of different chromium (VI) concentrations.
Continuous mixing was provided during the experimental period with a constant agitation speed for better
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mass transfer with high interfacial area of contact. The remaining concentration of chromium in each
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sample after adsorption was determined by spectrophotometer after filtering the adsorbent with Whatmen
filter paper to make it dolochar free. The pH of the final solution was measured at the end of the
experiment. The pH of the solution was adjusted to the required value by adding either dilute H2SO4 or
NaOH solutions. The batch process was used so that there is no need for volume correction. The
chromium (VI) concentration retained in the adsorbent phase was calculated according to
qe = (Ci − Ce) V (1)
W
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where Ci and Ce are the initial and equilibrium concentrations (mg/L) of chromium (VI) solution,
respectively, V is the volume (L), and W is the weight (g) of the adsorbent.
To increase the accuracy of the data, each experiment was repeated 3 times. Adsorption isotherm
studies were carried out with different adsorbent doses ranging from 5 to 25 g/L while maintaining the
initial chromium concentration at 50 mg/L.

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3. Results and discussion
3.1 Effect of contact time on adsorption efficiency

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Contact time is one of the effective factors in batch adsorption process. In this stage, all of the
parameters except contact time, including temperature (30 °C), adsorbent dose (20 g/L), pH (2), initial

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chromium concentration (10 to 50 mg/L) and agitation speed (150 rpm), were kept constant. The effect of
contact time on chromium adsorption efficiency showed in Fig. 1. As it is shown, adsorption rate initially

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increased rapidly, and the optimal removal efficiency was reached within about 1 h for any initial
concentration. The uptake of metal ion occurred in two stages i.e. an initial rapid uptake followed by
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subsequent slow uptake. The adsorption process appeared to proceed rapidly when the numbers of
available sites are much larger than the number of metal species to be adsorbed. The required contact time
increased with increase metal adsorbed. The adsorption capacities increased from 58 to 92, 42 to 70, 30 to
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62 and 23 to 48% for chromium concentration of 10, 20, 30, 50 mg/l respectively. There was no
significant change in equilibrium concentration after 1 h, the adsorption phase reached to equilibrium.
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Therefore, the contact time is decided 60 min for all experiments.

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3.2 Effect of Adsorbent dose on adsorption efficiency

At this stage, the experiments were done under the conditions described at previous stage with
constant pH of 2 and variable adsorbent dose (5, 10, 15, 20 and 25 g/L). The effect of adsorbent dose on
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the adsorption of chromium by dolochar was presented in Fig. 2. As illustrated in Fig. 2, chromium
removal efficiency increased with increase in adsorbent dose, since contact surface of adsorbent particles
increased. Increase in the adsorbent dosage enhanced the availability of more active sites for the
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adsorption, thus making easier penetration of metal ions to the adsorption sites. The adsorption capacities
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for chromium (VI) increased from 62 to 100, 60 to 90, 57 to 88 and 53 to 81% for 10, 20, 30, 50 mg/l
initial feed concentration respectively. A maximum removal of 100% was observed at adsorbent dosage
of 25 g/l at pH 2 for initial chromium (VI) concentration of 10mg/L. Adsorption for any adsorbent dose
beyond 20 mg/l gave more or less the same uptake. Therefore, the use of 20g/l adsorbent dose is justified
for economical purposes.
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3.3 Effect of adsorbate concentration on adsorption efficiency
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Initial concentration is one of the effective factors on adsorption efficiency. The experiments were
done with variable initial chromium concentration ( 5, 8,10, 12 and 15 mg/L) and constant temperature
(30 °C),pH (2), agitation speed (150 rpm), contact time (1 h) and adsorbent dose varying from 10 to 30
g/L). The experimental results of the effect of initial chromium concentration on removal efficiency were
presented in Fig. 3. As Fig. 3 is shown, chromium removal efficiency decreased with the increase in

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initial chromium concentration. In case of low chromium concentrations, the ratio of the initial number of
moles of chromium ions to the available surface area of adsorbent is large and subsequently the fractional
adsorption becomes independent of initial concentration. However, at higher concentrations, the available

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sites of adsorption become fewer, and hence the percentage removal of metal ions which depends upon
the initial concentration, decreases (Yu et al., 2003).

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3.4 Effect of pH on chromium adsorption

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The pH of the aqueous solution is clearly an important parameter that controlled the adsorption
process. The experiments of this stage were done under the conditions of constant temperature (30 °C),
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agitation speed (150 rpm), contact time (1 h), adsorbent dose (20 g/L) and initial chromium concentration
(10, 30, 50 mg/L). pH of solution was changed and the chromium removal was investigated. The
experimental results of this stage are presented in Fig. 4. As it is shown, the optimum pH of solution was
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observed at pH of 2 and by increasing pH, a drastic decrease in adsorption percentage was observed. This
might be due to the weakening of electrostatic force of attraction between the oppositely charged
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adsorbate and adsorbent that ultimately lead to the reduction in sorption capacity (Baral et al., 2006).
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Adsorption of hexavalent chromium varies as a function of pH with H2CrO4, HCrO4-, Cr2O72-and CrO42-
ions appear as dominant species. At pH of 2, HCrO4- is the dominant species. The surface charge of
dolochar is positive at low pH, and this may promote the binding of the negatively charged HCrO4- ions.
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The HCrO4– species are most easily exchanged with OH- ions at active surfaces of adsorbent under acidic
conditions (Argun et al., 2006).
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4. Adsorption isotherms
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Several models have been used to describe the experimental data of adsorption isotherms. The
Freundlich and Langmuir models are the most frequently employed models. In the present work both
models were used. The Freundlich isotherm model explains about the adsorption process wherein a
heterogeneous adsorbent surface involves in the multilayer distribution of the adsorbate with interaction
amongst adsorbed molecules (Maji et al., 2008 , Baraka et al., 2012,Diwevdi et al., 2008, Sing et al.,

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2008). The relation between the metal uptake capacity qe (mg/g) of adsorbent and the residual metal ion
concentration Ce (mg/l) at equilibrium is given by
ln qe = ln k + (2)

where the intercept ln k is a measure of adsorbent capacity, and the slope 1/n is the adsorption intensity. k
is related to temperature and the chemical or physical characteristics of adsorbents, where as “n” is an

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indicator of the change of intensity of adsorption process and also a measure of the deviation from
linearity of the adsorption. A higher value of n (n > 1) indicates favorable adsorption, whereas n < 1

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represents poor adsorption characteristics (Yang et al., 2013). The value of n = 3.66 suggests favorable
adsorption. The situation n > 1 is most common and may be due to a distribution of surface sites or any

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factor that cause a decrease in adsorbent-adsorbate interaction with increasing surface density. The
isotherm data fit the Freundlich model (R2 = 0.987).
The Langmuir isotherm suggests monolayer adsorption on a homogeneous surface with a finite number

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of adsorption sites and without any interaction between the adsorbed molecules (Acharya et al., 2009a,
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Acharya et al., 2009b).The Langmuir equation relates solid phase adsorbate concentration (qe), the uptake,
to the equilibrium liquid concentration (Ce) as follows:
qe = ( ) (3)
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where KL and b are the Langmuir constants, representing the maximum adsorption capacity for the solid
phase loading and the energy constant related to the heat of adsorption, respectively. It can be seen from
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Fig. 5 that the isotherm data fits the Langmuir equation well (R2 = 0.999).
The outcome values of parameters k, n, KL, b, R2 for all the experiments with pH of solution equal to 2
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for maximum removal of chromium (VI) are presented in Table 1.

Langmuir equation can also be used to calculate a dimensionless equilibrium parameter, RL also known
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as the separation factor and can be expressed as:

RL = 1/ (1+bC0) (4)
where, C0 is the initial concentration of chromium (mg/l).
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RL = 1 represents linear adsorption, while RL= 0 stands for the irreversible adsorption process. RL< 1 is
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for favorable adsorption, while RL> 1 represents unfavorable adsorption. In this case, the value of RL was
found to be 0.975, suggesting that the adsorption process was less than 1 but it was nearly equal to 1 so it
was linear adsorption.

5. Adsorption kinetic

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In order to define the adsorption kinetics of heavy metal ions, the kinetics parameters for the
adsorption process were studied for contact times ranging from 0 to 70 min by monitoring the removal
percentage of the Cr(VI). The data were then regressed against the Lagergren equation (Eq. 5), which
represents a first order kinetics equation and against a pseudo-second-order kinetics equation (Eq. 6).

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5.1 Pseudo-first-order model
Lagergren proposed a pseudo-first-order kinetic model. The integral form of the model is

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Log (qe-q) = log qe - t (5)

where q is the amount of chromium (VI) sorbed (mg/g) at time t (min), qe is the amount of chromium (VI)

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sorbed at equilibrium (mg/g), and Kad is the equilibrium rate constant of pseudo first-order adsorption
(min-1). This model was successfully applied to describe many adsorption systems.
5.2 Pseudo-second-order model

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The adsorption kinetics may also be described by a pseudo-second-order reaction. The linearized-
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integral form of the model is

= + (6)
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where K2 is the pseudo-second-order rate constant of adsorption(min−1) .

The applicability of the above model can be examined by each linear plot of (t/q) versus t and is
presented in Fig. 6. To quantify the applicability of each model, the correlation coefficient, R2, was
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calculated from these plots. The linearity of these plots indicates the applicability of the two models.
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However, the correlation coefficients, R2, showed that the pseudo-second-order model, an indication of a
chemisorptions mechanism, fits better the experimental data (R2 > 0.998) than the pseudo-first-order
model (R2 is in the range of 0.981-0.989) so the kinetics of adsorption is found to better fit to pseudo-
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second-order reaction.
The outcome values of parameters qe, Kad, K2, and R2 for all the experiments with pH of solution equal
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to 2 for maximum removal of chromium (VI) are presented in Table 2.

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6. Fixed bed studies

The fixed bed column study for the removal of Cr (VI) from wastewater by dolochar was conducted
by using a column of 4.5 cm diameter and 55 cm length. The column was packed with dolochar between
two supporting layers of pre-equilibrated glass wool. The schematic diagram of column study is shown in
Fig. 7. The column experiments were conducted with distilled water spiked with 10 mg/l metal solutions

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for dolochar with particle size 75 micron having a bulk density of 1.203 g/cm3, at bed depth of 2.5 cm and
maintaining a constant flow rate of 10 ml/min (~ 2.10 m3/m2/h) for Cr(VI).

The studies were conducted at the room temperature of 30 ± 2ºC. The breakthrough point was
considered when the ratio of effluent to influent concentration (C/C0) reaches at 0.1. The breakthrough

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plots for ratio of effluent to influent concentration in the column versus time at bed depths 2.5 cm are
shown in Fig. 8 for Cr (VI). It was observed that the time to achieve breakthrough was increased with the
increase of bed depths. The breakthrough and exhaust time were found to be 19.5 and 90 hrs respectively.

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Treated water volume within beak through and exhaust time were 5.3 and 23 litrs respectively. The
percentage of the total column saturated at breakthrough was found to be 95.68%.

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7. Conclusion

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Removal of chromium (VI) from waste water is possible using several abundantly available low-cost
adsorbents. The present investigation shows that the dolochar is an effective adsorbent for the removal of
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chromium (VI) from aqueous solutions. Dolochar was found to be effective, as the removal of Cr (VI)
reached 100% at normal temperature. It was also observed that the process of adsorption is strongly
affected by the experimental parameters such as adsorbent dose, adsorbate concentration, pH, and time.
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Among all of the selected parameters, pH of solution was the most effective on chromium removal. The
adsorption efficiency shall be affected in presence of other heavy metals as other metal ions shall compete
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with chromate ions. The affinity of the ions for the sorbent depends on ionic radius, electronegetivity and
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hydrolysis constants of ions. Although the removal of chromate ions in presence of other has not been
studied, this is suggested for future scope of work for other researchers.
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Table 1 Adsorption isotherms models parameter at pH 2 for chromium (VI) removal

Isotherm type Isotherm constants R2
Freundlich model k (l/g) 1/n 0.987
0.389 0.273

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Langmuir model KL (mg/g) b (l/g)
0.999
0.904 0.512

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Table 2 Kinetics models parameter at pH 2 for chromium (VI) removal
Kinetics order Parameter R2

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Pseudo-first-order qe (mg/g) Kad (min−1) (0.981-0.989)
model (0.194-0.893) 0.05
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Pseudo-second-order qe (mg/g) K2 (min−1)
model (0.477-1.300) (0.562-0.140) >0.998
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1
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90

PT
80

70

RI
60
Adsorption (%)

SC
50

40

U
30
AN
20 Symbol Initial feed conc.
( 10 mg/l)
( 20 mg/l)
10
M

( 30 mg/l)
( 50 mg/l)
0
0 10 20 30 40 50 60 70 80
D

Time (min)
TE

Fig. 1: Effect of contact time on Cr(VI) adsorption efficiency (initial concentration 10, 20, 30, 50mg/l,
EP

pH 2, speed 150rpm, temp 30ºC, particle size 75micron, adsorbent dose 20g/l)
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105
Symbol Initial feed conc.
100 % ( 10 mg/l)
% ( 20 mg/l)
% ( 30 mg/l)

PT
95
% ( 50 mg/l)
90

RI
85
Adsorption(%)

80

SC
75

70

U
65
AN
60

55
M

50
5 10 15 20 25
Adsorbent dosages, g/l
D

.
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Fig. 2: Effect of adsorbent dose on Cr(VI) adsorption efficiency (contact time 60 min, initial
concentration 10, 20, 30, 50mg/l, pH 2, speed 150rpm, temp 30ºC, particle size 75micron)
C EP
AC
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100

PT
95

90

RI
85
Adsorption (%)

SC
80

75

70

U
AN
65 Symbol Adsorbent dosages
(10 g/l)
M

(20 g/l)
60
(30 g/l)
4 6 8 10 12 14 16
D

Adsorbate, mg/l
TE

Fig. 3: Effect of adsorbate conc. on Cr(VI) adsorption efficiency (contact time 60 min, adsorbent dose
10, 20, 30 g/L, pH 2, speed 150rpm, temp 30ºC, particle size 75micron)
C EP
AC

3
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100

90

PT
80

RI
70
Adsorption (%)

SC
60

50

U
AN
40

Symbol Initial Cr(VI) conc.

30 (10 mg/l)
(30 mg/l)
M

(50 mg/l)
20
2 3 4 5 6 7 8
D

pH
TE

Fig.4: Effect of pH on Cr(VI) adsorption efficiency (contact time 60 min, initial concentration 10, 30,
50mg/L, speed 150rpm, temp 30ºC, particle size 75micron, adsorbent dose 20g/l)
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2.2

Initial concentration 50 mg/l

PT
2.0

RI
1.8

SC
1.6
1/qe

U
1.4
AN
1.2
M

1.0
0.0 0.1 0.2 0.3 0.4 0.5
D

1/Ce
TE

Fig. 5: Langmuir adsorption isotherm

EP
C
AC

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160
Symbol Initial feed conc.
(10 mg/l)

PT
140 (20 mg/l)
(30 mg/l)
(50 mg/l)
120

RI
100

SC
t/q

80

U
60 AN
40

20
M

0
0 10 20 30 40 50 60 70 80
D

Time (min)
TE

Fig. 6: Kinetics of Cr (VI) removal according to the pseudo-second-order model at initial feed concentration of 10,
20, 30, 50mg/l.
C EP
AC

6
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PT
RI
U SC
AN
M

Fig. 7: Schematic diagram of fixed bed column experimental set up

D
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CEP
AC

7
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RI
U SC
AN
Fig. 8: Breakthrough curve for Cr(VI) removal of C0 = 10 mg/l
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EP
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Highlights
1. An investigation on the adsorption characteristics of an industrial waste (Dolochar) for
removal of Cr (VI) from aqueous solutions was studied.

2. Maximum chromium removal (≈ 95 %) was obtained at pH of 2 with adsorbent and adsorbate

dose of 20g/l and 5 mg/l respectively

PT
3. The results indicate that this industrial waste can be employed as a low cost alternative to
commercial adsorbents for removal of chromium (VI) from water and wastewater.

RI
U SC
AN
M
D
TE
C EP
AC