South Asian Journal of Engineering and Technology Vol.2, No.24 (2016) 155–168
155
ISSN No: 2454-9614
Removal of Crystal Violet dye from water using Banana peel
charcoal and AMPS-g- Banana peel charcoal hydrogels: A
comparative study
I. Inigo Babu
1, S. Lokeshwaran
2, J. Sadish Kumar
2, K. Shyam Sundar
2,
Venkatesan Srinivasan1*
1Department of Chemistry, Adhiyamaan College of Engineering, Hosur, Tamilnadu. 635109. 2Department of Chemical Engineering, Adhiyamaan College of Engineering, Hosur, Tamilnadu. 635109.
Corresponding author: (Venkatesan Srinivasan)
E-mail:[email protected]
Received: 13/12/2015, Revised: 12/02/2016 and Accepted: 27/04/2016
Abstract
Removal of Crystal Violet dye has been reported by using Banana peel charcoal as the
adsorbent. A novel method of grafting this charcoal with poly(AMPS) hydrogels has been
successfully achieved. The efficiency of banana peel charcoal and AMPS-g-banana peel
charcoal hydrogels as an activated adsorbent in the removal of CV dyes has been studied and
their capacities are compared. Qmax, %R and the experimental conditions such as optimum
adsorbent dose, optimum pH and kinetic studies were reported. BET surface area of the
banana peel has been reported.
Key words: Banana peel, poly(AMPS-g-banana peel) hydrogel, Adsorbent, CV dye.
*Reviewed by Organizing committee of 4th National Conference On Emerging Trends and New Challenges in Biotechnology
1.INTRODUCTION Water is one of the vital necessities for survival of human beings. Wastewater
reclamation, re-use are vital to meet the water requirements for irrigation, industry and
domestic use due to increase in population. Commonly some of the dyes are toxic in nature.
Adsorption process has been found to be one of the best treatment methods for crystal violet
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(CV) removal. As the control of water pollution has become an increase in importance in
recent years. The use of physical/chemical treatments like reverse osmosis, coagulation are
not economically feasible. CV dye is synthetic organic compounds that provides bright and
lasting colour to other substance. There are various industries like paper industries, textile
industries like dye usage. The water discharge from dying processes exhibit a high BOD and
COD, visible pollutants high amount of dissolved solids. Effluents discharged from
industries are highly coloured and toxic to aquatic life. Particularly, CV dyes are
carcinogenetic in nature. Therefore, it’s must to treat CV dye effluent before being
discharged into the environment. Thus, there is a need to control an emission of dyes into
environment. The maximum permissible chemical oxygen demand (COD) limit is 4.0 mg/l
and biological oxygen demand (BOD) limit is 100-300 mg/l according to USPH standard.
Therefore, due to insufficient biodegradation techniques of dyes, this may be not right choice
for treating dyes in polluted water [1, 2]. Many of them do not operate at low concentration of
coloured compound in the effluent. Also, they are very expensive for treating wide range of
CV dye in water. Adsorption has received considerable attention for colour removal from
waste waters as it offers more economical and effective method [3].
2.MATERIALS AND METHOD
Banana peel charcoal preparation
Banana peels were collected from domestic waste and washed thoroughly to remove
dust using distilled water [refer fig.1], then dried in air-oven at 80˚C for 4 hours. The dried
carbon was grounded into powder of size 1-2 mm as shown in fig.2. Several washing steps
needed with shaking for one hour to remove the colour pigment by using deionised water.
Then, dried in oven for 2 hours at 60˚C [4, 5] as shown in fig.2b.
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Fig.1. banana peel Fig.2a.banana peel charcoal
Fig.2b.dried banana peel charcoal Fig.3. Poly (AMPS)-g-banana peel
charcoal
i) AMPS-g- banana peel charcoal hydrogels
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Poly (AMPS) hydrogels were synthesized by free radical copolymerization. 3.3300 g
of AMPS (99.0% Sigma Aldrich, Bangalore), 0.1500 g of MBA (99.8% Sigma Aldrich,
Bangalore) as a cross linker and 0.0400 g of KPS (98%, Merck, India) as a free radical
indicator, then 1 g of Banana peel charcoal and the ingredients were made into 5 ml solution,
using distilled water in a 5 ml measuring jar. Then, it is transferred into the 250 ml beaker
and kept in air-oven at 56˚C for 10 minutes. A black colored gel was formed as shown in
fig.3.
Point of zero charge studies (Pzc)
i) Banana peel charcoal
By the use of salt addition method [18, 24], Pzc studies were carried out,
independently assessed for Banana peel charcoal and poly(AMPS-g-banana peel charcoal)
hydrogels. In this method 0.3 g of each Banana peel charcoal was added to 50.0 ml of 0.1 M
NaNO3 in twenty 100 ml plastic beakers. The pH was adjusted using a pH meter to 2, 2.5, 3,
3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11 and 11.5 with 0.1 M HNO3 and 0.1
M NaOH as required in each beaker. These were then shaken for 48 hours in a revolving
water bath to reach equilibrium.
∆pH = pHii - pHi (1)
Where, pHi = initial pH of the solution; pHii = final pH of the solution. A graph of pHi
against ∆pH was plotted and Pzc was taken as the point where ∆pH = 0.
ii) AMPS-g-banana peel charcoal hydrogels
By the use of salt addition method [18, 24], Pzc studies were carried out,
independently for assembled forms Banana peel charcoal. The method was followed as in the
above section (i).
3.Results and discussion
Pzc studies
The values of Pzc were determined for assembled Banana peel charcoal and Poly
(AMPS)-g-banana peel charcoal. The results show the relatively high Pzc value signals the
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predominance of positively charged surface groups. With this, information users desiring
positive or negative surface charges to remove specific pollutants shall be able to adjust their
pH values accordingly. The pzc value of banana peel is 1.51.The pzc value of banana peel is
3.2.
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.510.0
-7
-6
-5
-4
-3
-2
-1
0
1
pHii-pHi
pHi
pHii-pHi
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.510.0
-5
-4
-3
-2
-1
0
1
2
pH
ii-p
Hi
pHi
Fig.4.Pzc studies of banana peel Fig.5.Pzc studies of AMPS -g- banana peel
hyrogel
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Surface area study
As it was obtained from N2 adsorption-desorption method that the BET surface area
of the Banana peel charcoal was found to be 120m2/g as shown in fig.6 and the
corresponding plot in the figure confirms the suitability of the same as the adsorbent.
Fig.6.surface area study
Adsorption study
All batch experiments were conducted using 40ml of aqueous solution containing
known CV concentration to which a weighed amount of banana peel or grafted banana peel
(1g) was added as shown in fig.7. The solution is stirred continuously at room temperature at
1-2 hrs. The sample was periodically taken out from each flask and filtered through a
Whatmann No. 1 filter paper before CV dye analysis as shown in fig 8&9. The adsorption
studies were performed in duplicate. The values were used to plot the graph. The adsorption
efficiency at a given contact time for the selected adsorbents were determined by the
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following equation.
%R =
x 100
Where, %R is percentage removal and are the concentrations of dye
before and after the adsorption process. For banana peel With 20 ppm of CV dye as the
minimum concentration, 99.5% of CV dye has been removed. 140 ppm as the maximum
concentration of CV dye, 95.2% of CV dye has been removed as shown in fig.10 & 11. For
AMPS-g-banana peel charcoal hydrogels with 20 ppm of CV dye as the minimum
concentration, 99.5% of CV dye has been removed. With 240 ppm as the maximum
concentration of CV dye, 90.2% of CV dye has been removed as shown in fig.12 & 13.
Fig.7.CV dye prepared in different concentrations Fig.8.CV dye using banana peel charcoal
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Fig.9. after adsorbtion of CV dye using Amps grafted banana peel Charcoal
Banana peel charcoal
0 20 40 60 80 100 120 140 160 180 200 220 240
95
96
97
98
99
100
% R
Conc (ppm)
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0 20 40 60 80 100 120 140 160 180 200 220 240
0
1
2
3
4
5
6
Q (
mg
/g)
Conc (ppm)
Fig.10.%removal of CV Dye Fig.11. Adsorbtion capacity of adsorbent
Amps-g- banana peel charcoal hydrogels
0 50 100 150 200 250 300 350 400
40
50
60
70
80
90
100
CONC
% (R)%R
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0 100 200 300 400 500
0
10
20
30
40
50
60
70
Conc(ppm)
QQ(mg/g)
Fig.12. %removal of CV dye Fig.13.Adsorbtion capacity of adsorbent
Effect of pH The pH of medium is one of the important parameters which affect the CV dye
adsorption. The removal of CV increases with increasing pH of solution at the initial stage
and it later finds rapid decrease. The same trend has been observed for both the adsorbents at
their corresponding optimized conditions of adsorbents dose and contact times [7]. In the
acidic medium, the surface of adsorbent is highly protonated and hence, more CV dye can be
attracted towards the surface due to electrostatic interaction.
For Banana peel The adsorption showed a maximum at pH = 1 to 2 and it shows that the dye is better
removed by banana peel in slightly acidic range, than the neutral or basic. The adsorption
dye was found to be decreased after the maximum. Therefore, the pH = 1 was chosen as the
optimum pH for the rest of adsorption process [refer fig.14]. The %R was better for the
banana peel.
For AMPS-g- banana peel charcoal hydrogels The adsorption showed a maximum at pH = 1 to 4 and it shows that the dye is better
removed by banana peel in slightly acidic range, than the neutral or basic. The adsorption
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dye was found to be decreased after the maximum. Therefore, the pH = 1.5 was chosen as the
optimum pH for the rest of adsorption process[refer fig.15]. The %R was better for the
banana peel.
1 2 3 4 5 6 7
40
50
60
70
80
90
100
pH
R
%R
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
40
50
60
70
80
90
100
pH
%R
Fig.14.Effect of pH on banana peel Fig.15.Effect of pH on Amps-g-banana peel
charcoal hyrogels.
Effect of time Depend upon the percentage uptake of the initial metal ions and contact time. The
data obtained from the adsorption of ions onto banana peel charcoal and grafted banana peel
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charcoal with AMPS hydrogels showed that the adsorption increased with increasing contact
time. Further increase in contact time had negligible effect on the amount of ions adsorbed [8,
9].
The subsequent experiments shows that the equilibrium time was maintained at 120
minutes, which was considered sufficient for the removal of different metal ions by Banana
peel charcoal and AMPS-g-banana peel charcoal.
For Banana peel charcoal By comparing, three different CV dye concentration (in ppm) with respect to time is
given below fig (Banana peel charcoal).At 50 ppm equilibrium reaches at 75 minutes, 99.5%
removal is achieved. At 70 ppm equilibrium reaches at 90 minutes, 99.01% removal is
achieved. At 100 ppm equilibrium reaches at 75 minutes, 98.7% removal is achieved as
shown in fig.16.
For AMPS-g- banana peel charcoal hydrogel By comparing, three different CV dye concentration (in ppm) with respect to time is
given below Poly AMPS-g- Banana peel hydrogel. At 100 ppm equilibrium reaches at 98
minutes, 99.05% removal is achieved. At 200 ppm equilibrium reaches at 115 minutes,
98.10% removal is achieved. At 300 ppm equilibrium reaches at 120 minutes, 97.7%
removal is achieved. By increasing the concentration there is decrease in the %removal due
to less contact time. By increase the contact time at high concentration improves the%
removal as shown in fig.17.
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-20 0 20 40 60 80 100 120 140
0
20
40
60
80
100
TIME(min)
(CV)50PPM
(CV)70PPM
(CV)100PPM
%R
-20 0 20 40 60 80 100 120 140
0
20
40
60
80
100
TIME(min)
(CV)100PPM
(CV)200PPM
(CV)300PPM
%R
Fig.16. Effect of Time on banana peel Fig.17.Effect of pH on Amps-g-banana peel charcoal
4.CONCLUSION
Removal of CV dye from aqueous solution was proved using low cost adsorbents.
Poly(AMPS-g-banana peel charcoal) hydrogels was more effective, and the removal
reached to the maximum of 99%. The optimum pH was found to be 1 and 1.5 for
respectively, banana peel charcoal and Poly(AMPS-g-banana peel charcoal). The
efficiency of banana peel charcoal was found improved from 6 mg/L to 365 mg/L. This
study proves the improvement of removal capacity of the banana peel charcoal after
having grafted with a polymer hydrogels.
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