International Journal of Applied Environmental Sciences

ISSN 0973-6077 Volume 7, Number 2 (2012), pp. 149-154

© Research India Publications
http://www.ripublication.com/ijaes.htm

Response Surface Optimization for the Decolorization

of Crystal Violet Dye from Aqueous Solutions by
Waste Crab Shells

Narayana Saibaba K.V.1, *, P. King2, R. Gopinadh3

and D.K.N. Lakshmi4
1,2
Andhra University, Department of Chemical Engineering,
Environmental Pollution Control Engineering Laboratory,
Visakhapatnam-530003, Andhra Pradesh, India
E-mail: kvnsai@yaho.com
3
GITAM University, GIT, Department of Biotechnology,
Visakhapatnam-530453, Andhra Pradesh, India
E-mail: gopinaadh@yahoo.com
4
Andhra University, Department of Botany,
Environmental Pollution Control Engineering Laboratory,
Visakhapatnam-530003, Andhra Pradesh, India
E-mail: kvnsai@yaho.com
*Corresponding Author E-mail: kvnsai@yahoo.com

Abstract

A simple, economical, locally available, highly efficient and eco-friendly

adsorbent was studied as an ideal alternative to the current expensive method
of removing dyes from waste water. This study investigated the potential use
of carbon prepared from waste crab shells for removal of a basic dye, crystal
violet (C.V). The influence of various operational parameters such as
temperature, initial pH, contact time, adsorbent dosage and initial C.V
concentration of the solution were studied by a series of batch experiments.
Adsorption experiments indicated that the adsorption capacity was dependent
on operating variables and the process was strongly dependent on pH and
adsorbent dosage. The adsorption parameters were optimized by using
Response Surface Methodology (RSM). ANOVA analysis indicated that the
interaction between dye and adsorbent was significant. The results show that
carbon prepared from waste crab shells could be effective and economical for
removal of dyes from aqueous solutions.

Keywords: Dye removal, Charcoal, Crab, RSM, CCD.

150 Narayana Saibaba K.V. et al

Introduction
Dyes are synthetic chemical compounds with complex aromatic structures. They are
the first contaminants to be recognized visually by human eye. Color present in
effluent streams inhibits the sunlight penetration into the stream and reduces
photosynthetic activity in water streams and upsets aquatic life [1-3]. Hence, disposal
of dye effluents into the water streams causes damage to aquatic life as well as
humans by mutagenic and carcinogenic effects [4-6].
Biosorption process is one of the most efficient and competitive methods used for
dye removal because of its simplicity, high efficiency, and wide ranging availability
[5,7]. Numerous attempts have been made to develop highly effective, low cost and
locally available adsorbents [5,8]. But still there is a need to develop economical and
highly effective adsorbent to treat dye effluents. Hence, the present work is aimed to
develop a simple, cost effective and environmentally benign method for removal of
crystal violet from aqueous solution using carbon prepared from crab shell waste (CC)
as sorbent. The various experimental parameters affecting optimal adsorption were
also investigated in detail.

Materials and Methods

Materials: Crystal violet dye (mol. formula C25H30ClN3, mol. wt. 407.99, λmax =590
nm, make Fisher Scientific), Chemicals HCl and NaOH used in this study were
purchased from lotus enterprises, visakhapatnam, India. Deionized water was used to
prepare the dye solutions. All the glassware was washed thoroughly with deionized
water before use.

Preparation of biosorbent: The waste crab material was collected from nearby fish
market, fishing harbor, Visakhapatnam, Andhra Pradesh, India. The shells of the crab
were separated from the waste material and washed with deionized water till no color
was obtained in effluent water. Then it was dried in sunlight for overnight, crushed in
roll crusher and grounded in a ball mill for 20 minutes. The grounded material was
placed in a muffle furnace at 5000C for 3 hr and resulted activated carbon (CC) was
screened using a sieve shaker for 30 minutes then different sized particle mixtures
were collected separately from the sieve analysis and stored in a dessicator for further
use.

Experimental procedure: The stock solution of dye at desired concentration was

prepared by dissolving accurately weighed amount of CV dye in deionized water in
1000 ml volumetric flask. It was diluted to the required concentrations of dye (50 ppm
– 150 ppm) in 250 ml Erlenmeyer flasks by mixing with appropriate volumes of
deionized water. Dye solutions of 50 ml were taken in a 100 ml Erlenmeyer flasks and
required pH’s were maintained by using 0.1N HCl or 0.1N NaOH. Dye solutions were
contacted with the appropriate amounts of biosorbents and kept at 120 rpm in an
orbital shaker. The solutions pH was measured by using a pH meter. Dye
concentrations were determined by using UV-Vis Spectrophotometer at a wavelength
corresponding to the maximum absorbance of dye, λmax = 590 nm.
Response Surface Optimization for the Decolorization 151

Experimental Design and Data Analysis: A Central Composite Design [9] was used
to evaluate the effects of process parameters on dye removal efficiency. Temperature
(x1), pH (x2), time (x3), adsorbent dosage (x4) and initial dye concentration (x5) were
chosen as the independent variables. Percentage of dye removal (Y) from water was
selected as the dependent output variable. A half fraction factorial Central Composite
Design (CCD), with sixteen cube point runs, ten axial point runs and 6 replications at
the centre point leading to a total number of 32 experiments were employed for the
optimization of parameters for removal of CV dye from aqueous solution.

Results and Discussion

The CCD design matrix and the observed responses were given in table -1. All
experimental runs were conducted at two replicates and average values were shown in
table-1. The RSM analysis for the optimization of parameters shows that dye removal
percentage was a function of temperature, pH, time, adsorbent dosage and initial dye
concentration. The main effects of each of the parameter on dye removal efficiency
were determined and shown in figure -1. A plot of temperature versus percentage
removal of CV shows that the percentage removal of dye decreased with increased
temperature. This indicates the exothermic nature of the process. Similar temperature
effects were obtained with other adsorbents also [7].
It is clear from the figure -1 that percentage removal increased with increased pH
and reached maximum at pH of 12. Time course profile of figure-1shows that removal
efficiency increased with time up to 52.5 minutes thereafter dye removal rate
proceeds at slower rate till equilibrium is reached. This might be attributed that
increased time allowed the particles to reach equilibrium hence, removal efficiency
increased. These results are in accordance with the results obtained by other
researches on dye removal [8, 9].
The effect of biosorbent’s dose on removal of CV dye from solution was
significant as seen in figure-1. It was noticed that percentage removal of CV increased
significantly with increased adsorbent dosage up to 0.6 g. However, beyond the
dosage of 0.6 g changes in percentage removal of CV is marginal. The effect initial
dye concentration plot indicated that the effect of dye concentration on removal of
dye is modest. The removal efficiency increased slightly up to the concentration of
100 ppm after that removal efficiency again decreased. This might be due to the non
availability of active sites to the dye particles [10].
From the results of the experiments the following second order polynomial
equation (3) was developed to represent the percentage removal of CV dye.
Y1 = -16.2424 - 1.2618 X1 + 6.7045 X2 + 0.5786 X3 + 66.2191 X4
+ 0.6413 X5 - 0.0022 X12 - 0.2965 X22 - 0.0036 X32 - 27.6679 X42
- 0.0025 X52 + 0.0032 X1X2 - 0.0136 X1X3 - 0.6412 X1X4 + 0.0136 X1X5
+ 0.0402 X2X3 + 3.6056 X2X4 - 0.0277 X2X5 + 0.3915 X3X4
- 0.0015 X3X5 - 0.4502 X4X5 (1)

The predicted values of percentage removal using the above equation (1) were
given along with experimental data (Table-1). The proposed model suggests that the
152 Narayana Saibaba K.V. et al

adsorbent dose and pH had a strong effect; linear and quadratic terms had more
influence in comparison to the interaction term. The optimum combination of all
parameters for percentage removal of dye was predicted by using prediction profiler
of the software. The maximum removal efficiency was predicted to be 93% which
was obtained at a temperature of 200C, pH of 8.887, contact time of 72 min, adsorbent
dose of 0.68 g and initial dye concentration of 75 ppm (figure -2).

Table 1: CCD plan matrix in coded values and Responses

Run Order X1 X2 X3 X4 X5 % Removal of dye

Observed Predicted
1 0 0 0 0 0 62.326 62.145
2 -1 -1 1 -1 -1 48.867 49.049
3 -1 1 -1 -1 -1 63.243 62.481
4 -1 -1 -1 -1 1 51.526 51.807
5 0 0 0 0 0 62.326 62.145
6 0 0 0 -2 0 51.726 51.896
7 1 1 -1 1 -1 62.536 61.62
8 1 -1 -1 1 1 41.256 41.382
9 -1 -1 1 1 1 54.125 54.312
10 1 1 1 -1 -1 58.334 57.697
11 2 0 0 0 0 50.369 50.848
12 0 0 0 2 0 62.624 63.54
13 0 0 2 0 0 62.862 63.22
14 0 0 0 0 0 62.326 62.145
15 0 0 0 0 -2 54.748 55.673
16 -1 1 1 -1 1 70.248 69.77
17 -1 1 1 1 -1 92.369 91.513
18 -1 1 -1 1 1 65.686 64.928
19 0 0 0 0 2 55.824 55.985
20 0 0 0 0 0 62.326 62.145
21 1 1 1 1 1 68.125 67.492
22 -2 0 0 0 0 72.394 73.001
23 1 -1 -1 -1 -1 34.853 34.975
24 1 -1 1 1 -1 41.567 41.595
25 0 -2 0 0 0 35.125 33.965
26 -1 -1 -1 1 -1 50.867 50.77
27 1 1 -1 -1 1 58.435 57.896
28 0 0 0 0 0 62.326 62.145
29 1 -1 1 -1 1 42.958 43.363
30 0 0 0 0 0 62.326 62.145
31 0 2 0 0 0 73.254 75.501
32 0 0 -2 0 0 50.258 50.987
Response Surface Optimization for the Decolorization 153

Figure 1: Main effects plot for percentage removal of CV dye

Figure 2: Response surface optimization plots for percentage removal of CV dye

Conclusions
In this work, statistical methods were successfully applied for optimization of process
variables for the removal of CV dye from aqueous solutions. With the application of
Central Composite Design a high removal efficiency design was successfully
developed. Highly significant quadratic polynomials were also obtained. The results
clearly showed that the CV removal efficiency was highly influenced by initial pH
and adsorbent dosage. However the effects of temperature, contact time and dye
concentration were marginal.
154 Narayana Saibaba K.V. et al

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