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Abstract: In the present study a low-cost adsorbent has been prepared from citrus fruit
peel and investigation has been made to explore the possibility of this adsorbent for
removal of dye. Operating parameters for carbonization of citrus fruit peel have been
optimized by response surface methodology (RSM). A detailed kinetic study and
equilibrium study has been performed to examine the potentiality of charred citrus fruit
peel as an adsorbent for the removal of methylene blue from its aqueous solution.
Introduction
The adsorption process is one of the most efficient methods to remove dyes from
effluents. Commercial activated carbon is the preferred adsorbent for dye removal
because of its extended surface area, microporous structure and high adsorption capacity,
but its widespread use is restricted due to its high cost. This has led to search for cheaper
adsorbent.
In the present work, a low cost adsorbent was prepared from citrus fruit (grape fruit) peel.
Citrus fruit peel has no use after the extraction of juice from the fruit and is thus
inexpensive and readily available. In the present investigation, the citrus peel was
carbonized with activating agent for preparation of adsorbent suitable for dye removal.
Among the different types of activating agents used, ortho-phosphoric acid was selected
based on its performance evaluated by decolorizing power of prepared adsorbent. This
reduces the number of experiments. Response Surface Methodology (RSM) is widely
used for optimization of process parameters [1-3]. However, use of RSM for optimization
of process parameters in preparation of adsorbent from waste product is new approach.
Three parameters that have been optimized are weight ratio of charcoal to activating
agent, temperature of carbonization and time of carbonization. Decolorizing power was
chosen as response for selection of best adsorbent and the best sample has been
designated as Charred Citrus Fruit Peel (CCFP). Different physical properties like bulk
density, solid density, moisture content and ash content of CCFP have been determined.
Kinetic study and equilibrium study for removal of dye have been performed using
CCFP.
Characterization of CCFP
The physical properties of the selected adsorbent (CCFP) were determined following
standard procedure using the undersize of 90microns [4]. The physical properties
estimated include bulk density, solid density, moisture content, ash content and
decolorizing power.
Kinetic Study
A stock solution of Methylene Blue was prepared by dissolving definite amount of
Methylene Blue (AR grade, MERCK) in distilled water. Various concentrations of
Methylene Blue solution were prepared from the stock solution by diluting it with
suitable amount of distilled water. The concentration of residual methylene blue in
solution was analyzed spectrophotometrically using UV-Visible Spectrophotometer (UV
2300, TECHCOM) at 660 nm. For kinetic study, the dye solution of specific
concentration was contacted with selected adsorbent in a batch contactor. The liquid
samples were taken at a particular interval and analyzed. The process parameters like
initial concentration of dye (25 – 100 ppm), weight of adsorbent (0.25 g – 1 g) and size of
adsorbent (-180+90micron to -300+250 micron) were varied in a prescribed manner.
Equilibrium Study
For equilibrium study 100ml stock methylene blue solution was prepared and diluted to
obtain 10ppm, 20ppm, 40ppm, 60ppm, 80ppm and 100ppm methylene blue solution in
conical flasks. 0.5g of charcoal was added to each flask and the lid was closed and they
were shaken overnight in a BOD incubator at constant temperature of 370C. Finally the
solutions were centrifuged and the clear liquid was analyzed spectrophotometrically by
UV Visible spectrophotometer at 660nm.
Based on results obtained using ANOVA, it was found that weight ratio and time of
carbonization have significant effect on decolorizing power. On the other hand quadratic
effects of weight ratio, carbonization temperature and carbonization time have significant
effect on docolorizing power. The interaction effects of weight ratio and carbonization
temperature, weight ratio and carbonization time and carbonization temperature and
carbonization time were considered significant. The conjugate effect of temperature and
weight ratio is shown in Fig. 1. According to the software the optimized conditions
obtained when weight ratio, temperature of carbonization and time of carbonization are 3,
5250C and 0.75 hr respectively.
Fig.1. Conjugate effect of temperature (0C) and weight ratio upon decolorizing power
Characterization of CCFP
CCFP has been characterized in terms of solid density, bulk density, moisture content,
ash content and values obtained are 1065 kg/m3, 2673.33 kg/m3, 12.94 % and 6.60%
respectively.
Kinetic Study
The kinetic results are evaluated by three different models which are
i) Morris-Weber model: qt = K d t 1 / 2
kt
ii) Lagergren first-order kinetic model: log( qe − qt ) = log q e − .
2.303
t 1 t
iii) Pseudo-second-order model (PSOM): = 2
+
qt k 2 q e q e
Among these three models, pseudo-second-order model (PSOM) fits more accurately
with the kinetic data obtained for various initial concentration of methylene blue ( 25-100
mg/l), amount of adsorbent (-300 - -250) and size (0.25-1.0g). This model assumes that
the sorption process is of pseudo-second-order and the rate limiting step is of
chemisorption nature. These are shown in Figures 2-4.
7
6
25 PPM
5
t/qt (min.g/mg)
50 PPM
4
75 PPM
3
2 100 PPM
0
-20 0 20 40 60 80
-1
t (min)
Fig. 2. Kinetics of adsorption of methylene blue with different initial concentration
fitted to Pseudo-Second-Order Model
Equilibrium Study
The equilibrium data have been fitted to Langmuir adsorption isotherm model and
Freundlich adsorption isotherm model. The experimental data are fitted more
satisfactorily with the Freundlich adsorption isotherm. The values of constants of
Freundlich adsorption isotherm are K F = 73 .7225 and n = 1.2288 .
5
1 gm
t/qt (min.g/mg)
4
.75 gm
3 .5 gm
2 .25 gm
0
0 20 40 60 80
t (min)
Nomenclature
q t = Adsorbate uptake at time t. (mg/g).
q e = Amount of sorbate adsorbed per unit gram of adsorbent at equilibrium. (mg/g)
K d = Rate constant of intraparticle transport. (mg g-1 h-1/2)
k = Overall rate constant. (h-1)
k 2 = Pseudo-second-order rate constant of sorption. (g mg-1 h-1)
t = Time. (h)
References
[1] Sahu, J. N., Acharya, J., Meikap, B. C., “Response Surface Modeling and
Optimization of Chromium(VI) Removal from Aquous Solution using Tamarind Wood
Activated Carbon in Batch Process.”, J. Hazard. Mater., (2009).
[2] Ravikumar, Krishnan, K., S., Ramalingam, S., Balu, K., “Optimization of Process
Variables by the Application of Response Surface Methodology for Dye Removal using
A Novel Adsorbent.”, Dyes. Pigments., 72, pp. 66-74 (2007).
[3] Kalil, S. J., Maugeri, F., Rodrigues, M. I., “Response Surface Analysis and
Simulation as A Tool for Bioprocess Design and Optimization.”, Process. Biochem., 35,
pp. 539-550 (2000).
[4] Dutta, S., Basu, J. K., Ghar, R. N., Sep. Purif. Technol., 21, pp. 227-235 (2001).