IJSTE - International Journal of Science Technology & Engineering | Volume 2 | Issue 11 | May 2016

ISSN (online): 2349-784X

Column Studies for Removal of Toxic Ni(II) Ions

from Aqueous Solution by Esterified (Tectona
Grandis) Saw Dust
Dr. Jatinder Singh
Assistant Professor
Department of Chemistry
G.N.C Budhlada 151502

Bikramjit Singh
Associate Professor
Department of Chemistry
G.N.C. Budhlada 151502
Abstract

Heavy metals are highly toxic and non-biodegradable and their accumulation in the living tissues can cause various diseases and
disorders. Hence there is a need to remove these metal ions from the wastewaters from industries before discharging into the
environment. In the present paper removal of Ni(II) by esterified (Tectona grandis) saw dust by sequential bed and vertical columns
have been investigated. Column studies have been carried out at optimum pH and particle size and the effect of flow rate and metal
ion concentration have been investigated using sequential bed as well as vertical columns. Thomas model and Yoon-Nelson model
were used to evaluate model parameters and predict the adsorption performance and capacity in a fixed-bed column. The bed
capacity qo for sequential column is more than a vertical column at a flow rate of 1.2 l/hr and influent concentration of 200 mg/l.
It is found that breakthrough time for sequential column is more than vertical column.
Keywords: Adsorption, Esterified Saw Dust, Column Studies, Thomas model, Yoon-Nelson Model
________________________________________________________________________________________________________
I.

INTRODUCTION

The indiscriminate disposal of toxic metals into wastewaters by industrial activities is considered as the main cause and major
source of worldwide concern in the last few decades. Nickel contamination is mainly due to industries related to electroplating,
battery, mining and metallurgy of nickel, aircraft industries, pigments, and ceramic industries. The permissible level of nickel in
drinking water is 0.5 mg/L [1].
Chemical modification of agricultural by-product could enhance their natural capacity for the uptake of metal ions [2]. Corn
stalk treated with acrylonitrle [3], corncob treated with citric acid [4], rice husk treated with nitric acid and potassium carbonate
[5], bagasse treated with sulfuric acid [6], polyacrylamide grafted rice (Oryza sativa) husk and (Tectona grandis) saw dust [7],
thiolated cassava fiber, cassava bark waste and rice husk [8-10], esterified coir pith, rice husk, lemon and saw dust [11-14], have
been used.
Batch adsorption tests provide information on adsorption equilibrium characteristics and adsorption kinetics. However, batch
operations are not economical in practice and data on continuous flow fixed bed column operations are essential for industrial
adsorber design. The objective of the present study is to study the adsorption potential of esterification of sawdust with succinic
anhydride followed by activation with sodium bicarbonate has been investigated for Ni(II) ions by sequential bed and vertical
column in order to investigate the feasibility for its use in small scale industries.
II. MATERIAL AND METHODOLOGY
Preparation Of Adsorbents:
The saw dust of (Tectona Grandis) was procured from saw mill of Sangrur, Punjab, India. These were crushed, sieved, washed
with distilled water and dried at - 800C. The particles retained on 212-micron mesh size were used for the experiment.
Preparation Of Esterified Saw Dust:
Esterification [11] was carried out by stirring 7.5 g of rice husk with 7.5 g of succinic anhydride in 100 ml of N,N-dimethyl
formamide (DMF) at 80oC for two hours in the presence of a catalyst, triethylamine (0.1 eqv.). Esterified saw dust was treated with
1N NaHCO3 solution (50 ml, 1h, 20oC), washed with distilled water (50 ml) and dried for 12 h at 105 oC.
Preparation Of Metal Ion Solution:
The stock solution of the metal ions was obtained by dissolving the required amount of metal sulphate (Merck, A.R.grade) in
distilled water to get solution having concentration 300 mg/L of Ni +2 ions. Different concentrations were prepared by making
suitable dilutions.

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Column Studies for Removal of Toxic Ni(II) Ions from Aqueous Solution by Esterified (Tectona Grandis) Saw Dust
(IJSTE/ Volume 2 / Issue 11 / 123)

Characterization Of Adsorbent:
FTIR Analysis:
The samples were prepared by mixing 1mg of each material with 100mg of spectroscopy grade KBr. The FTIR spectra were
recorded using Nicolet Impact 410 equipment with detector at 4cm1 resolution from 500 to 4000cm 1 and 32 scans per sample.
Acid Value:
Esterified saw dust (150 mg) was mixed with 5 ml of 0.1 N H 2SO4 in 50 ml of distilled water and titrated [14] using 0.1 N NaOH
with phenolphthalein as indicator. Acid value for esterified saw dust was found to be 2.88 meq/g.
Saponification Value:
Esterified saw dust (300mg) was put into a 100 ml flask equipped with a reflux condenser in 20 ml of 0.5 N KOH in methyl alcohol.
The flask was heated at 650C for 1 hr and then 25 ml of 0.5 N H2SO4 was added, followed after 1hr by 50 ml of distilled water.
Titration was carried out with 0.1 N KOH using phenolphthalein as indicator [14]. Saponification value for esterified saw dust was
found to be 10.1meq/g.
Column Adsorption Studies:
Sequential Bed Column:

Fig. 1: Experimental Setup for sequential bed adsorption column

The sequential bed column was constructed by connecting glass tubes to contain the adsorbent (Fig.1) without using other materials
that could affect the adsorbate speed. The use of feed pumps was also avoided by taking into account the flow under gravity. The
first tube, filled with solid adsorbent, received the influent (controlled by a valve) which flowed through the second tube and so
on. The flow rate was controlled in such a way that contact time in the column is in the range of 2 to 3 h (hours). At the end of the
column a container was collecting the treated solution.
Vertical Column:
A 4 cm diameter and 60 cm height vertical column containing the adsorbent was set up (Fig.2). The down flow mode has been
used and the flow through the column was maintained using a rotameter to measure the flow.

Fig. 2: Experimental setup for Vertical column study

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Column Studies for Removal of Toxic Ni(II) Ions from Aqueous Solution by Esterified (Tectona Grandis) Saw Dust
(IJSTE/ Volume 2 / Issue 11 / 123)

The adsorbent was packed up to a depth of 40 cm in the column and the storage tank filled with metal ion solutions. Samples of
the effluent of the column were withdrawn at regular intervals and analysed for metal ion concentrations. The amount of Ni 2+ ion
concentration was determined titrimetrically by the standard method using EDTA solution [15]. Each set of experiments was
carried out in duplicate in order to check the reproducibility of the results and values were found to differ by +2%, which is well
within the experimental error.
III. RESULTS AND TABLES
Fourier Transform Infrared Spectroscopy (Ftir) Analysis:
In the FTIR spectrum of esterified saw, the most changes occurring on the adsorbent after adsorption of nickel are reflected in the
bands 3386.7 cm-1 which may be assigned to complexation of nickel ions with the ionized OH group of free hydroxyl groups
and bonded OH bands of carboxylic acids. The changes in peaks observed between 1728.9 cm-1, are indicative of stretching
vibration of CO bonds due to non-ionic carboxyl groups (COOH, COOCH3) and may be assigned to hydrogen bonding between
carboxylic acids or their esters and nickel [16] which confer their ability to exchange ions.

Fig. 3: FTIR Spectrum of esterified saw dust

Column Studies:
Effect of Influent Metal Ion Concentration:

Fig. 4: Breakthrough curves for adsorption of Ni(II) on saw dust at flow rate 1.2 l/hr, pH 6 on particle size 212 micron in sequential column at
different metal ion concentration

The shape of breakthrough curve are important characteristics for determining the operation and dynamic response of an adsorption
column. Column studies were carried out on saw dust at influent concentration 200,250 and 300 mg/l, pH 6, flow rate 1.2 l/h on
212 micron particle size in sequential column and vertical column respectively. The desired breakthrough point for influent
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Column Studies for Removal of Toxic Ni(II) Ions from Aqueous Solution by Esterified (Tectona Grandis) Saw Dust
(IJSTE/ Volume 2 / Issue 11 / 123)

concentrations was determined to be 0.5 Ct/C0. As seen in Fig. 4 & 5, the breakthrough point for saw dust occurred at 162 & 135 min for
concentration 200 mg/l, 112 & 80 min for concentration 250 mg/l and 62 & 58 min for concentration 300mg/l in sequential & vertical
column respectively. The results also show that the shape of the breakthrough curve is saturated earlier at a higher influent concentration
because the front of the adsorption zone quickly reached the top of the column. In contrast, lower influent concentration and longer
contact time, resulted in a shallow adsorption zone [17].
1.02
0.92

Ct/Co

0.82
200 m g/l

0.72

250 m g/l

0.62

300 m g/l

0.52
0.42
0.32
10

110

210

310

410

Time(min)

Fig. 5: Breakthrough curves for adsorption of Ni(II) on saw dust at flow rate 1.2 l/hr, pH 6 on particle size 212 micron in a vertical column at
different metal ion concentration

Effect of Flow Rate:

Column studies were carried out on saw dust at the flow rates of 1.2, 1.5 and 1.8 l/hr, at 200 mg/l influent concentration on 212
micron particle size in sequential column and vertical column respectively.\
0.95
0.85

Ct/Co

0.75
1.2 l/hr

0.65

1.5 l/hr

0.55

1.8 l/hr

0.45
0.35
0.25
10

110

210

310

410

Time(min)

Fig. 6: Breakthrough curves for adsorption of Ni(II) on saw dust at influent metal ion concentration 200 mg/l, pH 6 on particle size 212 micron
in sequential column at different flow rates

1
0.9

Ct/Co

0.8
1.2 l/hr

0.7

1.5 l/hr

0.6

1.8 l/hr

0.5
0.4
0.3
10

110

210

310

410

Time(min)

Fig. 7: Breakthrough curves for adsorption of Ni(II) on saw dust at influent metal ion concentration 200 mg/l, pH 6 on particle size 212 micron
in a vertical column at different flow rates

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Column Studies for Removal of Toxic Ni(II) Ions from Aqueous Solution by Esterified (Tectona Grandis) Saw Dust
(IJSTE/ Volume 2 / Issue 11 / 123)

As seen in Fig. 6 & 7, the breakthrough point for saw dust occurred at 162 & 135 min for flow rate 1.2 l/h, 110 & 90 min for
flow rate 1.5 l/h, and 70 & 60 min for flow rate 1.8 l/h in sequential & vertical column respectively. The breakthrough curve
became steeper and the breakthrough times were decreased and removal efficiency increases with decreasing flow rate. This can
be explained by the fact that at lower flow rates, the residence time of the adsorbate in the column would increase and metal ions
have more time to diffuse into the pores of adsorbent through intra particle diffusion, resulting in higher adsorption [18].
Column studies were further carried out on esterified saw dust at optimum influent concentration 200 mg/l, pH 6, flow rate 1.2
l/h on 212 micron particle size in sequential column and vertical column respectively. As seen in Fig. 8, the breakthrough point for
esterified saw dust occurred at 260 & 200 min in sequential & vertical column respectively. However, it has also been shown that
Thomas and YoonNelson models can sometimes provide a better description of the adsorption kinetics. So in this study, an
attempt has been made to find out their applicability describing the column performance study.
0.82
0.72

Ct/Co

0.62
Vertical column

0.52

Sequential column

0.42
0.32
0.22
0

100

200

300

400

Time (min)
Fig. 8: Breakthrough curves for adsorption of Ni(II) on esterified saw dust at flow rate 1.2l/h, influent metal ion concentration 200 mg/l, pH 6
on particle size 212 micron in sequential and vertical column

Modeling Of Breakthrough Curves:

Thomas model:
The Thomas model is one of the most general and widely used methods in column performance theory. The linear form of the
model is given as:
Co

M
1 k TH q o
kTH Co t
ln
Q
Ce

Where KTH is Thomas rate constant (L min-1mg-1); qo the maximum solid - phase concentration of the solute (mg g-1), Q the flow
rate (L min-1). The kinetic coefficient KTH and the adsorption capacity of the bed qo can be determined from a plot of ln(Co/Ct-1)
against time at a given flow rate [19]. The Thomas model gave a good fit of the experimental data, at the flow rates examined, with
high correlation coefficients of greater than 0.982. The values of KTH are found to be 11.8 10-5, 7.4 10-5 and values of qo are
found to be 986.0, 640.0 for sequential and vertical column respectively. These values showed that bed capacity qo for sequential
column is more than a vertical column at a flow rate of 1.2 l/hr and influent concentration of 200 mg/l.
Yoon and Nelson Model:
Yoon and Nelson model is based on the assumption that the rate of decrease in the probability of adsorption for each adsorption
molecule is proportional to the probability of adsorbate adsorption and the probability of adsorbate breakthrough on the adsorbent.
The Yoon and Nelson equation is expressed as;
C
ln t C t = KYNt - KYN
Co

where KYN is the rate constant (l mg-1); the time required for 50% adsorbate breakthrough (min); is the breakthrough time
(min). The kinetic coefficient KYN and can be determined from a plot of [(lnCt/Co-Ct)] against time t at a given adsorption
conditions [20]. This plot will result in a straight line with slope K YN and intercept KYN. The values KYN are found to be 0.028,
0.018 and values of are found to be 280.0, 196.0 for sequential and vertical column respectively. It is found that breakthrough
time for sequential column is more than vertical column.

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Column Studies for Removal of Toxic Ni(II) Ions from Aqueous Solution by Esterified (Tectona Grandis) Saw Dust
(IJSTE/ Volume 2 / Issue 11 / 123)

IV. CONCLUSION
Studies suggest that an esterified form of saw dust (Tectona Grandis) can be effectively used as adsorbent for removal of Ni(II)
ions from aqueous medium. The Thomas model gave a good fit of the experimental data. The values of KTH and bed capacity qo
for sequential column is more than a vertical column at a flow rate of 1.2 l/hr and influent concentration of 200 mg/l. It is found
that breakthrough time for sequential column is more than vertical column. Thus, the use of chemically modified agricultural
based adsorbents may contribute to the sustainability of the surrounding environment. These adsorbents offer a lot of promising
benefits for commercial purpose in the future for wastewater treatment due to their local availability, technical feasibility and cost
effectiveness. Since the experimental set-up for a sequential bed adsorption column is extremely simple and involves less capital
cost, it can find wide applications in small-scale industries, especially in developing countries.
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