from 01.01.2007 to 01.01.2019
Lovely Professional University
from 01.01.2007 to 01.01.2021
Phagwara, India
Phagwara, India
Water is the most crucial thing to mankind and so its contamination by various agencies is posing a threat to the natural balance. So, in the present work, the efficiency of various adsorbents derived from plant waste, to remove different dyes from aqueous solution was evaluated. Parameters for study were contact time, concentration and pH. Various combinations of plant ashes were used for the study. It was found that adsorbent prepared from the combination of orange peels, pomegranate and banana peels ashes, exhibited good adsorption capacity for methylene blue, congo red and crystal violet. All these dyes were completely removed from the aqueous solution while methyl orange was not removed. Congo red was removed completely within 40 min of contact with the adsorbent while methyl orange took 3 hrs to be removed to the extent of 48% only. The adsorption coefficient of congo red was found to be 2.33 while value for methylene blue and crystal violet was 1 and 1.66 respectively. The characterization of adsorbent was done by Scanning Electron Microscopy and IR spectroscopy. SEM image revealed the surface of adsorbent to be made of differential pores. From the results it became evident that the low-cost adsorbent could be used as a replacement for costly traditional methods of removing colorants from water.
Textile water, orange peels, pomegranate peels, adsorption, congo red, SEM
INTRODUCTION
Water is one of the most imperative substances
on the Earth. About 75% of our body consists of
water. Water is used for such a wide variety of purposes
like drinking, washing, bathing, as well as in agriculture
and many others industries. According to World
Health Organization (WHO) data, about 85% of rural
population lacks potable drinking water. Currently, the
water contamination is serious problem. About 80%
of diseases in First world countries are associated with
stained drinking water. In Second world countries,
15 million infants die annually due to poor hygiene,
polluted drinking water, and malnutrition. Chemical
impurities such as heavy synthetic fertilisers, industrial
metals, dyes of textile industry, and poisonous minerals
can cause hazardous effect on human and animal life.
Since these particles are very small in size, they can
penetrate into the ground water [1].
Purification of water is a tedious process that
requires a number of stages [2]. Textile goods are the
necessary need of individuals, while textile industry
is of immense economic importance. There are 2324
textile industries that require using a number of dyes,
additional chemicals, and sizing materials [3]. Different
stages of technological processes of textile dyeing
industry produce huge volumes of waste water. The
waste water discharged from textile mill includes a large
amount of concentrated industrial dyes.
Generally, dye stuffs are complex aromatic
substances that are difficult to be removed. Methods
used for dye removal include flocculation, chemical
coagulation, chemical oxidation, photochemical
degradation, membrane filtration, adsorption, as well as
aerobic and anaerobic biological degradation. However,
waste after removing dyes reduces light diffusion,
affecting thus aquatic plants. In turn, it may be toxic to
some aquatic animals [4]. Moreover, these methods are
not cost effective and environmentally friendly. None
of them is effective in complete removal of dye from
wastewater [4]. Dyed water not only poses aesthetic
problem, but also causes serious ecological problems, for
example, it significantly impacts photosynthetic.
Modern studies show that adsorption with the help
of activated carbon is a very efficient method to remove
various organic compounds from the waste water [5].
Numerous researchers have searched alternative
23
Kaur Harpreet et al. Foods and Raw Materials, 2019, vol. 7, no. 2, pp. Х–Х
adsorbents deriving them from farming waste or natural
materials to remove dyes from wastewater. Some of
these alternatives are palm ash, orange peel ash, shale
oil ash, pomelo (Citrus grandis L.) peel, fat-free soya,
bottom ash, sunflower seed shells, mandarin peel, wheat
husk guava leaf powder, as well as steel and fertiliser
industries waste [6].
Enormous amounts of fruit peels are disposed, while
they might be used in the interest of the environment.
Agricultural wastes can be employed as a low-cost
adsorbent for removal of dyes, such as methylene blue,
crystal violet, methyl orange, and congo red, from
aqueous solution [6]. Orange peel consists of a large
amount of cellulose, hemi-cellulose, pectin, lignin,
and other low molecular weight compounds, together
with limestone. It can be used as an efficient and costeffective
bio-adsorbent for removing dyes metals and
organic pollutants from industrial wastewater [7–12].
Apart from the traditional methods, there are a number
of recent studies on bioremediation [16–22].
Consequently, the aim of the study was to determine
the effectiveness of the combination of plant ash in
removing congo red, crystal violet, methylene blue,
and methyl orange dyes from aqueous solution. The
parameters studied were contact time, dye concentration
and pH variation.
STUDY OBJECTS AND METHODS
Materials. Glassware and apparatus used: conical
flasks, a round bottom flask, a volumetric flask, funnel
measuring cylinders, beakers, pipettes, a condenser, a
soxhlet apparatus, an electronic weighing balance, an
oven, a muffle furnace, a magnetic stirrer pH meter, and
a UV-visible spectrometer.
Chemical used: AgNO3, ethanol, double distilled
water, methylene blue, congo red, crystal violet, and
methyl orange.
Plants used: orange peels, pomegranate peels, banana
peels, drumsticks, and pea pods.
Methods. To prepare peel extracts, peels of
pomegranate, orange, banana, and drumstick tree
obtained from local market or fruit stalls were cleaned
with distilled water twice to remove dust and watersoluble
impurities. After that, these were cut into small
pieces, and kept for 2 days for proper drying. The dried
material was powdered, and extraction was carried out
in a Soxhlet apparatus using methanol as solvent.
Activated charcoal was obtained by putting the dried
plant peels in the muffle furnace at 450–500°C and
keeping the samples to constant weight.
The stock solution with a concentration of
0.1 g/L was prepared for different dyes. The different
concentrations of the dye solutions were obtained from
the stock solution by dilution method. Methylene blue,
congo red, crystal violet, and methyl orange were used
as adsorbates.
Kinetics study was performed as follows. 0.6 g of
adsorbent was added into 250 mL conical flasks filled
with 100 mL of diluted solutions (25–200 mg/L). The
solutions were stirred constantly, and the concentration
of dye at maximum wavelength was measured using a
double beam UV-visible spectrometer. The capacity of
dye adsorbed at time t, Qt (mg/g), was calculated by the
given formula:
Qt = (A0–At) v/W (1)
where At is concentration at time t, A0 is the initial
concentration, v is volume of solution, and W is the
weight of adsorbent used [13].
To study the dependence of initial concentration of
dyes and contact time on the degree of removing dyes,
0.6g of each sample (orange, banana, and pomegranate
ash) was added to each 100 mL flask with various dyes
having different concentrations. The solution was stirred
on the magnetic stirrer at room temperature. The time
required for complete adsorption was determined.
RESULTS AND DISCUSSION
Different dyes, namely, methylene blue, congo red,
crystal violet, and methyl orange were taken to evaluate
the adsorption capacity of the adsorbent.
According to Figs. 1–4, the effectiveness of dye
removal increased with an increase in time. This might
be due to the better interaction between dye molecules
and those of activated charcoal. It was observed that the
initially dye removal occurred faster and followed first
order kinetics. This was proportional to the availability
of active sites, and an equilibrium between adsorption
and desorption was than established.
The absorbance of methylene blue at λmax (about
390 nm) decreased with increasing contact time (Fig. 1).
The complete absorbance of methylene blue with the
adsorbent took 60 min.
The variation of absorbance of crystal violet with
time was studied by a UV-visible spectroscopy (Fig. 2).
Crystal violet exhibited λmax at 390 nm. It was found that
the dye was completely removed after 30 min of contact
with adsorbent.
Figure 1 Absorbance of methylene blue at different contact
time
Fig 1: Absorbance of methylene blue at different contact time
0.00
0.04
0.08
0.12
200 300 400 500
Absorbance
Wavelength, nm
MB(0.01) 20 min 30 min
40 min 50 min 60 min
24
Kaur Harpreet et al. Foods and Raw Materials, 2019, vol. 7, no. 2, pp. Х–Х
Similarly, congo red was completely removed in
40 min of contact with the adsorbent (Fig. 3).
On the contrary, the adsorbent was not effective
for methyl orange removal (Fig. 4). Even two hours of
contact time was not enough to adsorb the dye. This
could be due to the fact that methyl orange does not have
any functionality that could make the Vander Waals’
interaction with the adsorbent.
The successful removal of various dyes by the
combination of plant ashes proved the efficacy of the
combination for bioremediation of textile water. As
seen from Figure 5, complete dye removal took 5 h. The
textile effluent water contained a large amount of heavy
metals and different kinds of dyes, so it took longer for
adsorbent to absorb the colourant.
Adsorption coefficient of activated charcoal for
different dyes at time t. Adsorption coefficient was
calculated as the amount of dye adsorbed with one
gram of the adsorbent (mg/g). Adsorption coefficient
was found to be different for each dye (Table 1) because
adsorption depended upon the compatibility of the
dye structure with the surface and the porosity of the
adsorbent. It was found that absorption capacity for
Figure 2 Absorbance of crystal violet at different contact time
Figure 3 Absorbance of congo red at different contact time
Figure 4 Absorbance of methyl orange at different contact
time
Figure 5 Absorbance of textile raw water at different time
of contact
Fig 1: Absorbance of methylene blue at different contact time
Fig 2: Absorbance of crystal violet at different contact time
Fig 3: Absorbance of Congo red at different contact time
0.00
0.04
0.08
0.12
200 300 400 500
Absorbance
Wavelength, nm
MB(0.01) 20 min 30 min
40 min 50 min 60 min
0.00
0.10
0.20
0.30
0 100 200 300 400 500 600
Absorbance
Wavelength, nm
0 min 15 min 20 min
30 min 35 min 40 min
Figure 6 Contact time of different dyes at dye concentration
of 0.015
-0.05
0.10
0.25
0.40
0.55
0 100 200 300 400 500
Absorbance
Wavelength, nm
0 min 10 min 40 min
80 min 120 min
0.0
0.5
1.0
1.5
2.0
400 Absorbance
0 hour 3.5 0
40
80
120
Crystal Violet Methylene Blue Congo Red Methy Orange
Time(min)
-0.05
0.10
0.25
0.40
0.55
0 100 200 300 400 500
Absorbance
Wavelength, nm
0 min 10 min 40 min
80 min 120 min
0.0
0.5
1.0
1.5
2.0
400 500 600 700 800
Absorbance
Wavelength, nm
0 hour 1 hour 2 hour 3 hour
3.5 hour 4.5 hour 5 hour
0
40
80
120
Crystal Violet Methylene Blue Congo Red Methy Orange
Time(min)
-0.05
0.10
0.25
0.40
0.55
0 100 200 300 400 500
Absorbance
Wavelength, nm
0 min 10 min 40 min
80 min 120 min
0.0
0.5
1.0
1.5
2.0
400 500 Absorbance
Wavelength, 0 hour 1 hour 3.5 hour 4.5 hour 0
40
80
120
Crystal Violet Methylene Blue Congo Red Methy Orange
Time(min)
Methyl methyl orange was significantly lower, whereas that for
congo red had maximum value at contact time of 30 min
(Fig. 6).
Percentage of dyes adsorbed with adsorbent. The
percentage of dye elimination indicated the efficiency
of adsorbent (Table 2). The results made it possible
to conclude that 100% of congo red was removed in
40 min, whereas the removal of only 48% of methyl
2.4
2
1.6
1.2
0.8
0.4
0
0 200 400 600
-0.05
0.10
0.25
0.40
0.55
0 100 200 300 400 500
Absorbance
Wavelength, nm
0 min 10 min 40 min
80 min 120 min
0.0
0.5
1.0
1.5
2.0
400 500 600 700 800
Absorbance
Wavelength, nm
0 hour 1 hour 2 hour 3 hour
3.5 hour 4.5 hour 5 hour
0
40
80
120
Crystal Violet Methylene Blue Congo Red Methy Orange
Time(min)
-0.05
0.10
0.25
0.40
0.55
0 100 200 300 400 500
Absorbance
Wavelength, nm
0 min 10 min 40 min
80 min 120 min
0.0
0.5
1.0
1.5
2.0
400 500 600 700 800
Absorbance
Wavelength, nm
0 hour 1 hour 2 hour 3 hour
3.5 hour 4.5 hour 5 hour
0
40
80
120
Crystal Violet Methylene Blue Congo Red Methy Orange
Time(min)
C.V 0.015 10 min 20 min
25 min 30 min
25
Kaur Harpreet et al. Foods and Raw Materials, 2019, vol. 7, no. 2, pp. Х–Х
orange took 120 min. In spite of the fact that both methyl
orange and congo red dyes have similar structure, the
percentage of their removal from the solution differs.
One of the causes for that could be the presence of
two primary amine groups in congo red, which could
contribute to binding of dye with adsorbent. Thus, the
structure of adsorbate played a crucial role in adsorption
efficacy. The efficiency of adsorption depended upon
the pore size of the adsorbent. The results of the study
confirmed that the structure of congo red dye was wellmatched
with the pore size of the adsorbent, which
allowed it to exhibit fairly efficient adsorption (Table 2).
pH of dyes after treatment. The change in pH of
different dye solutions was studied before and after the
treatment with adsorbent. As one can see from Table 3,
pH of the solution increased after the treatment. It could
be due to introduction of basic component from the
activated charcoal to the dye solution. Additional work
could be done to find out the reason for the same.
Characteristics of the adsorbent. The adsorbent
was analysed by Fourier transform infrared
spectroscopy (FTIR) and scanning electron microscopy
(SEM). The FTIR spectrum of the activated charcoal
Table 1 Adsorption coefficient of dyes at contact time of 30
min
Dye Structure of dyes Adsorption
coefficient,
mg/g
Congo
Red
2.33
Methylene
Blue
1.00
Crystal
Violet
N+
N
N
Cl
-
1.66
is shown in Figure 7. The various peaks were observed
due to different functional groups. The peak at about
2200 cm–1 could be due to the presence of sp hybridised
carbon. The peak at 1660 cm–1 corresponded to aromatic
C=C stretching. The peak value at 3166 cm–1 indicated
the presence of C-H group.
Surface morphology revealed the adsorbent had
porous structure. This could be due to the evaporation
of the chemical reagent throughout the carbonisation
process, leaving the vacant spaces on the surface of the
adsorbent. It is obvious from the SEM image (Fig. 8)
that the adsorbent is a mixture of activated charcoal
prepared from dissimilar plant material. The presence
of dissimilar plant materials in the adsorbent could be
accountable for elimination of broad range of dyes both
cationic and anionic.
Characteristics of the adsorbent after adsorption.
The FTIR analysis of adsorbent after reaction with dye
showed a number of additional peaks, perhaps due to the
functional groups present in the dye that was adsorbed
onto the adsorbent.
FTIR spectrometry demonstrated one additional
vibrational peak at 1386.61 cm–1, which can be due to
C-N stretching. The stretching vibration was observed at
872.88 cm–1 due to the presence of C-Cl bond. The C-S
stretching band was observed at 572 cm–1. Every new
peak definited that methylene blue was adsorbed on the
activated charcoal by assembling altered kinds of bonds.
Table 2 Percentage removal of dyes
Dye Concentration,
g/L
Time,
min
Dye
removal, %
Congo red 0.015 40 100
Methylene blue 0.015 120 100
Crystal violet 0.015 60 100
Methyl orange 0.0025 120 48
Table 3 pH of dye solutions before and after treatment with
adsorbent
Concentration
Congo red Crystal
violet
Methylene
blue
Methyl
orange
T1 T2 T1 T2 T1 T2 T1 T2
0.015 7.34 10.90 8.50 10.00 7.70 10.30 7.57 9.74
0.01 7.30 10.06 7.50 10.12 7.43 10.25 7.50 –
0.005 7.20 10.02 7.30 10.24 7.39 10.21 7.40 –
0.0025 7.12 9.85 7.10 10.27 7.20 9.74 7.25 –
SD = ± 0.05
T1 – before treatment; T2 – after treatment
Figure 7 Infrared spectra of activated charcoal
0.05
0.10
0.25
0.40
0.55
0 100 200 300 400 500
Wavelength, nm
0 min 10 min 40 min
80 min 120 min
0.0
0.5
1.0
1.5
2.0
400 500 600 700 800
Absorbance
Wavelength, nm
0 hour 1 hour 2 hour 3 hour
3.5 hour 4.5 hour 5 hour
0
40
80
120
Crystal Violet Methylene Blue Congo Red Methy Orange
26
Kaur Harpreet et al. Foods and Raw Materials, 2019, vol. 7, no. 2, pp. Х–Х
The FTIR analysis of activated charcoal after
adsorption of crystal violet revealed no additional peaks
(Fig. 10). One of the causes can be crystal violet inserted
in pores.
As for the FTIR spectra (Fig. 11) of activated
charcoal with adsorbed congo red dye, three additional
peaks were observed. Those were recorded at 3463,
2514, 1795, and 603 cm–1 that were due to N-H
stretching, O-H stretching of carboxylic acid, C=O
stretching, and C-C bending due to alkane, respectively.
The presence of these functional groups confirms the
adsorption of congo red dye on the activated charcoal.
Figure 9 Infrared spectra of activated charcoal after
adsorption of methylene blue
Figure 10 Infrared spectra of activated charcoal after
adsorption of crystal violet
Figure 11 Infrared Spectra of activated charcoal after
adsorption of congo red
CONCLUSION
The results of this study made it possible to conclude
that activated charcoal prepared from mixture of orange,
banana, and pomegranate peels by carbonisation method
had a great potential for removal of dyes from textile
wastewater. In the present work, this adsorbent was
tested on congo red, methylene blue, crystal violet, and
methyl orange dyes. Studies showed that this adsorbent
was effective in removing congo red, methylene blue,
and crystal violet dyes from aqueous solutions, while
it was not quite capable of removing methyl orange.
Surface chemistry of activated carbon played an
important role in dye adsorption. The type of the dye
adsorbed on the adsorbent also depended on its textural
min
0.0
0.5
1.0
1.5
2.0
400 500 600 700 800
Absorbance
Wavelength, nm
0 hour 1 hour 2 hour 3 hour
3.5 hour 4.5 hour 5 hour
Red Methy Orange
Fig-10: Infrared spectra of activated charcoal after adsorption of crystal violet
Fig.11: Infrared Spectra of activated charcoal after adsorption of congo red
0
Crystal Violet Methylene Blue Congo Red Methy Orange
Time(Figure 8 SEM image of the activated charcoal
27
Kaur Harpreet et al. Foods and Raw Materials, 2019, vol. 7, no. 2, pp. Х–Х
properties, such as porosity and surface area. The
adsorbent under study gave the best result for congo red
dye. Thus, the present research developed a low-coat and
environmentally friendly technology to remove dyes,
as an alternative to known expensive and damaging
methods.
1. Robert S. Africa south of the Sahara-A geographical interpretation. Second Edition. New York: Guilford Press; 2004. 477 p.
2. Farhaoui M, Derraz M. Review on Optimization of Drinking Water Treatment Process. Journal of Water Resource and Protection. 2016;8(8):777-786. DOI: https://doi.org/10.4236/jwarp.2016.88063.
3. Romero V, Vila V, de la Calle I, Lavilla I, Bendicho C. Turn-on fluorescent sensor for the detection of periodate anion following photochemical synthesis of nitrogen and sulphur co-doped carbon dots from vegetables. Sensors and Actuators, B: Chemical. 2019;280:290-297. DOI: https://doi.org/10.1016/j.snb.2018.10.064.
4. Kale RD, Kane PB. Colour removal using nanoparticles. Textile and clothing sustainability. 2016;2(4). DOI: https://doi.org/10.1186/s40689-016-0015-4.
5. Dixit A, Dixit S, Goswami CS. Process and plants for wastewater remediation: A review. Scientific Reviews and Chemical Communications. 2011;1(1):71-77.
6. Tan KA, Morad N, Teng TT, Norli I, Pannerselvam P. Removal of Cationic Dye by Magnetic Nanoparticle (Fe3O4) Impregnated onto Activated Maize Cob Powder and Kinetic Study of Dye Waste Adsorption. APCBEE Procedia. 2012;1:83-89. DOI: https://doi.org/10.1016/j.apcbee.2012.03.015.
7. Ranganathan K, Karunagaran K, Sharma DC. Recycling of wastewaters of textile dyeing industries using advanced treatment technology and cost analysis-Case studies. Resources, Conservation and Recycling. 2007;50(3):306-318. DOI: https://doi.org/10.1016/j.resconrec.2006.06.004.
8. Zhang L, Zhang Y, Tang Y, Li X, Zhang X, Li C. et al. Magnetic solid-phase extraction based on Fe3O4/graphene oxide nanoparticles for the determination of malachite green and crystal violet in environmental water samples by HPLC. International Journal of Environmental Analytical Chemistry. 2018;98(3):215-228. DOI: https://doi.org/10.1080/03067319.2018.1441837.
9. Dalavi DK, Suryawanshi SB, Kolekar GB, Patil SR. AIEE active SDS stabilized 2-naphthol nanoparticles as a novel fluorescent sensor for the selective recognition of crystal violet: application to environmental analysis. Analytical Methods. 2018;10(20):2360-2367. DOI: http://doi.org/10.1039/C8AY00328A.
10. Gautam S, Khan SH. Removal of methylene blue from waste water using banana peel as adsorbent. International journal of Science, Environment and Technology. 2016;5(5):3230-3236.
11. Bello OS, Bello LA, Adegoke KA. Adsorption of dyes using different types of sand: A review. South African Journal of Chemistry. 2013;66:117-129.
12. Akinola LK, Umar AM. Adsorption of crystal violet onto adsorbents derived from agricultural wastes: kinetic and equilibrium studies. Journal Applied Science Environment Management. 2015;19(2)279-288. DOI: https://doi.org/10.4314/jasem.v19i2.15.
13. Rafatullah M, Sulaiman O, Hashim R, Ahmad A. Adsorption of methylene blue on low-cost adsorbents: A review. Journal of Hazardous Material. 2010;117(1-3):70-80. DOI: https://doi.org/10.1016/j.jhazmat.2009.12.047.
14. Fba R, Akter M. Removal of dyes form textile wastewater by Adsorption using Shrimp shell. International Journal of Water Resources. 2016;6(3). DOI: https://doi.org/10.4172/2252-5211.1000244.
15. Ibrahim MB, Sulaiman MS, Sani S. Assessment of Adsorption Properties Of Neem Leaves Waste for the Removal of Congo Red and Methyl Orange. 3rd International Conference on Biological, Chemical & Environmental Sciences; 2015; Kuala Lumpur. Kuala Lumpur, 2015. pp. 85-89. DOI: http://doi.org/10.15242/IICBE.C0915067.
16. Beldean-Galea MS, Copaciu F-M, Coman M-V. Chromatographic Analysis of Textile Dyes. Journal of AOAC International. 2018;101(5):1353-1370. DOI: https://doi.org/10.5740/jaoacint.18-0066.
17. Pradel JS, Tong WG. Determination of malachite green, crystal violet, brilliant green and methylene blue by microcloud-point extraction and nonlinear laser wave-mixing detection interfaced to micellar capillary electrophoresis. Analytical Methods. 2017;9(45):6411-6419. DOI: https://doi.org/10.1039/c7ay01706e.
18. Foguel MV, Pedro NTB, Wong A, Khan S, Zanoni MVB, Sotomayor MDPT. Synthesis and evaluation of a molecularly imprinted polymer for selective adsorption and quantification of Acid Green 16 textile dye in water samples. Talanta. 2017;170:244-251. DOI: https://doi.org/10.1016/j.talanta.2017.04.013.
19. Tan L, Chen K, He R, Peng R, Huang C. Temperature sensitive molecularly imprinted microspheres for solidphase dispersion extraction of malachite green, crystal violet and their leuko metabolites. Microchimica Acta. 2016;183(11):2991-2999. DOI: https://doi.org/10.1007/s00604-016-1947-8.
20. De B, Karak N. A green and facile approach for the synthesis of water-soluble fluorescent carbon dots from banana juice. RSC Advances. 2013;3(22):8286-8290. DOI: https://doi.org/10.1039/c3ra00088e.
21. Shen C, Shen Y, Wen Y, Wang H, Liu W. Fast and highly efficient removal of dyes under alkaline conditions using magnetic chitosan-Fe (III) hydrogel. Water Research. 2011;45(16):5200-5210. DOI: https://doi.org/10.1016/j.watres.2011.07.018.
22. Pedraza A, Sicilia MD, Rubio S, Pérez-Bendito D. Assessment of the surfactant-dye binding degree method as an alternative to the methylene blue method for the determination of anionic surfactants in aqueous environmental samples. Analytica Chimica Acta. 2007;588(2):252-260. DOI: https://doi.org/10.1016/j.aca.2007.02.011.
