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Water is an important component for existence of all living beings. Since the beginning of
civilization, mankind flourished around the sources of water. With the skyrocketing growth in
population, climatic changes and industrialization, availability of fresh water on earth is declining
continuously, on the other hand demand is enlarging. After industrialization our water sources
such as oceans, rivers started squeezing in quality, due to anthropogenic activities which have
led to degradation of environment. Survival of living beings is threatened and earth’s support
system is endangered due to Pollution. Worldwide leading cause of diseases and deaths is due to
water pollution.
Water is contaminated by numerous inorganic and organic substances such as industrial wastes,
fertilizers, toxic chemicals, metals, dyes and its byproducts. Dyes are organic compounds used
as colouring material in various industries mainly textiles. Dyes transmit colour to water and a
small fraction is easily recognizable, which is aesthetically unacceptable. Due to complex
structure, dyes are difficult to degrade. Abundant production of dyes have undesirable
environmental effects. Despite the adverse effects caused by dyes to the environment, they are
continuously being discharged in water bodies thus disturbing the water cycle. The condition can
further intensify without strict remedial action. Thus, prioritizing wastewater treatment is
essential to avert crippling water problems. Today world is becoming more eco sensitive which
has given new impetus to waste water treatment. Researchers are in constant search of technically
feasible and economically viable methods for removing dyes and its toxic effects from the
environment. There are different methods that are used for the removal of dyes from wastewater
amongst them adsorption has been found to be more advantageous and effective method.
Adsorption is easy, reliable and versatile method for the removal of dyes. Over the past few
years, trend of using ecofriendly, low cost adsorbent has increased.
Focus of this study is on the adsorptive removal of two anionic dyes: Acid Yellow-36(AY-36)
and Direct Blue-86 (DB-86) from aqueous solution using low cost activated carbon as adsorbent.
So for present study, an agricultural waste, peanut shell was used as raw material for
manufacturing peanut shell activated carbon (PnsAC) using H3PO4 as chemical activator. The
pyrolysis is carried out under nitrogen environment at a ramp of 10 oC min-1 upto a temperature
of 650 oC for 2 hr activation time.
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To test the efficacy of PnsAC different characterization studies were performed. Thermal
stability was analyzed using TGA technique. Surface morphology was studied by SEM images
and elemental analysis was carried out using energy-dispersive X-ray spectroscopy (EDS).
Variation in surface functional groups were interpreted by Fourier Transform Infrared
spectroscopy (FTIR). Zero point charge for PnsAC was 2.3.
Investigations were done for studying the adsorption potential of PnsAC for the removal of
anionic dye AY-36. Batch experiments were conducted to study the effects of pH (2 – 11),
adsorbent dose (2 – 6 g L-1), and initial AY-36 concentration (100 – 250 mg L-1). The optimized
condition obtained by varying the variables were obtained at temperature 35 oC, initial dye
concentration 200 mg L-1, pH 2, PnsAC dose 4 g L-1 and equilibrium time 150 minutes. 98 %
removal of AY-36 was achieved at optimized conditions. Equilibrium adsorption isotherms,
kinetics, and thermodynamics were investigated. The experimental data were analyzed using
different isotherm models: Langmuir, Freundlich, Redlich–Peterson, Sip, and Toth. The kinetics
of adsorptive removal of dyes was studied with Pseudo first order, Pseudo second order and intraparticle
diffusion model. Equilibrium study revealed that Freundlich isotherm model described
best the experimental data. The kinetics of dye adsorption was found to confirm Pseudo second
order kinetics with a correlation coefficient value of 0.999. Kinetic study results indicated that
the chemisorption likely dominated the adsorption of AY-36 on peanut shell activated carbon
(PnsAC). Thermodynamic study revealed that the adsorption process was feasible, endothermic
and spontaneous.
Another dye DB-86 was adsorbed using PnsAC. Adsorbent dose of PnsAC was investigated
through batch experiments at various initial pH and DB-86 concentration, to obtain maximum
adsorption. This study showed that 78.6 % removal was obtained for 10 g L-1 PnsAC dose in 150
minutes (equilibrium time) at pH 2, while temperature was maintained at 35 oC. Kinetic,
equilibrium, and thermodynamic studies were carried out to validate the results from
experiments. Kinetic study confirms that the adsorption phenomena follow the Pseudo second
order rate equation. Isotherm study reveals that Freundlich, Redlich–Peterson, Sip, Radke–
Prausnitz, Koble-Corrigan, and Fritz–Schlunder isotherm models well explained the
experimental equilibrium data. Thermodynamic study showed a negative value of ΔG° which
advocated that the process of adsorption was spontaneous. Positive values of ΔH° and ΔS°
signified the endothermic and increased disorderness in the adsorption of DB-86, respectively.
Further, for effective adsorption, PnsAC was modified with alginate and used for the removal of
DB-86 dye. The alginate encapsulated activated carbon (PnsAC-alginate), prepared from waste
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peanut shell was used as an adsorbent. Alginate encapsulation was done by pouring homogenous
mixture of sodium alginate and PnsAC into the bath of 1 % calcium chloride solution. The effects
of temperature, equilibrium time, adsorbent dose, dye concentration and solution pH on the
adsorption of DB-86 onto PnsAC-alginate were studied. To the best of our knowledge, no attempt
have so far been made for optimization purpose using response surface methodology (RSM) in
the adsorptive removal of DB-86. Central composite design coupled with RSM was used to
optimize the adsorption feed conditions in order to achieve maximum dye removal efficiency.
The statistical analysis revealed that for maximum dye removal efficiency, the optimal conditions
were adsorbent dose of 24.65 g L-1, DB-86 dye concentration of 125.5 mg L-1 and pH of 3.1.
Under optimized conditions, experimental dye removal efficiency (98.4 ± 0.1%) agreed closely
with the predicted results, thus indicating the suitability of RSM in optimizing the feed
conditions. SEM, EDS, TEM, XRD, BET and FTIR analyses showed the surface morphology of
the adsorbents and confirmed the adsorption of DB-86 onto PnsAC-alginate. Crystalline behavior
of PnsAC-alginate were analyzed using X-Ray diffraction (XRD). Zero point charge for PnsACalginate
was 7.8. The experimental results also showed that the dye removal efficiency was
increased by 7 % compared to that with peanut shell activated carbon (PnsAC) as an adsorbent.
The adsorption kinetics of DB-86 was well described by Pseudo second order kinetic model with
intra-particle and film diffusion mechanisms. Langmuir isotherm model provided the best fit to
the adsorption equilibrium data, obtaining maximum dye adsorption capacity of 21.6 ± 0.9 mg
g-1. Estimation of thermodynamic parameters revealed that the adsorption process was feasible
and was spontaneous and endothermic in nature. The present study has demonstrated that the use
of positively charged PnsAC-alginate as an adsorbent is a cost effective and suitable alternative
for the removal of anionic DB-86 dye from aqueous solutions.
From above study we can conclude that, low cost adsorbents PnsAC and PnsAC-alginate can be
commercially converted into efficient adsorbents for the removal of AY-36 and DB-86 dyes from
aqueous solutions by adsorption. |
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