Adsorption of methyl red on activated carbon derived from custard apple (Annona squamosa) fruit shell: Equilibrium isotherm and kinetic studies
Graphical abstract
Introduction
Colored effluents discharged from fabric, paint, paper, and leather industries are major source of aquatic pollution. The presence of dyes even in low concentration (< 1 mg/L) is highly visible and affects the photosynthesis of planktons. The removal of synthetic color stuff from effluents is often difficult due to their no-biodegradability and recalcitrant nature. Methyl red (MR) is a mono-azo anionic dye (C15H15N3O2, Mol. wt., 269.30 g/mol) soluble in ethanol, ether, glacial acetic acid and water. It is commonly used in textile and other industries. The dye is harmful as it may cause eyes, skin irritation, and digestive tract irritation, if inhaled [1]. In aerobic conditions, it is considered mutagenic to living organisms [2]. Various physico-chemical treatment methods including advanced oxidation [3], electrocoagulation/electrodialysis [4], [5], photo-catalysis [6], [7] and reverse osmosis/nanofiltration [8], [9] are rather expensive and limited in applicability. The decolorization of dye-containing wastewaters by adsorption is a superior technique in terms of its cost effectiveness, ease of operation, high efficiency, and reuse of material [10], [11]. Commercial activated carbon (AC) is an excellent adsorbent due to high surface area (500–2000 m2/g) and porous structure, but its high cost precludes its wider application for effluent treatment, so the need for alternative low cost activated carbons, which may be derived from cheap, easily obtainable, and biodegradable lignocellulosic wastes. The carbon activation is generally carried out by physical or chemical procedures. In physical activation procedure, a lignocellulosic waste precursor is carbonized under nitrogen atmosphere, and the resulting carbon is subjected to partial or controlled gasification at high temperature preferably with steam or carbon dioxide [12]. The steam or CO2 react with the carbon structure to evolve CO, CO2, H2 or CH4 gases, which are responsible for the formation of pores [12]. On the other hand, the chemical activation process involves impregnation of precursor with chemicals such as ZnCl2, FeCl3, AlCl3, Na2CO3 and K2CO3 [13], [14], [15], [16], [17], [18], [19], inorganic acids (H3PO4, H2SO4, and HNO3) [20], [21], [22], [23], [24] and bases (KOH, NaOH) [25], [26], [27], [28]. Chemical activation has proved to be better than physical activation process largely due to higher yield, increased surface area, shorter activation time, well controlled textural properties and better porosity of the activated carbon [29]. The use of ZnCl2 has declined owing to environmental issues with zinc disposal. H3PO4 is the most commonly used chemical agent for the synthesis of activated carbon due to the pyrolytic decomposition of the raw precursor and the formation of the crosslinked structure [30], and may be easily removed by washing with cold/hot water after the activation. Potassium carbonate, K2CO3 is considered a cleaner activating agent, which does not produce any deleterious reagent during the process.
Recently, activated carbons derived from various carbonaceous materials such as cocoa shell [31] coconut shell (H3PO4) [32], pineapple waste (ZnCl2) [33], sour cherry stones (ZnCl2) [34], coconut shell (KOH) [35], Cucumis sativus (H2SO4) [36], olive-waste cake (H3PO4) [37], Kenaf core fiber (H3PO4) [38], date stone (FeCl2/ZnCl2) [39], sugarcane bagasse (KOH) [40], and orange peel (K2CO3) [41], linseed deoiled cake (H3PO4) have been prepared by chemical activation for treatment of industrial wastewater [29].
The non-edible fruit shell of custard apple (Annona squamosa), which is an agro-waste material, can be gainfully utilized as precursor for activated carbon preparation. To the best of our knowledge, no studies on the removal of dyes from water using activated carbon prepared from custard apple fruit shell are reported. In this work, custard apple fruit shell (CAS) was utilized as a low cost precursor for activated carbon production using K2CO3 and H3PO4 as the activating agents. The adsorption efficiencies of the activated carbons prepared by K2CO3 (ACCO3) and H3PO4 (ACPO4) activation for effective removal of methyl red (MR) was evaluated. The experimental equilibrium and kinetic data were modeled using Langmuir, Freundlich, D-R and Temkin isotherm, and pseudo-first order, pseudo-second order, intra-particle and liquid film diffusion to estimate the adsorption process.
Section snippets
Raw material and chemicals
The outer shell of custard apple was acquired in the local market of Jamia Nagar, New Delhi. All chemicals used were of AR grade. Methyl red (MR; Loba Chemie, Mumbai, India), H3PO4, K2CO3, NaCl, NaOH and HCl (all Merck, India) were used as received. The stock MR solution (250 mg/L) was prepared in double distilled water, which was diluted to desire concentrations. The activated carbon (AC) was prepared in a programmable muffle furnace (Matrix Scientific, India) with N2 inlet. The
Characterization of adsorbent
The % yield and ash content was 24.2, 1.39 and 38.6, 1.02 for ACCO3 and ACPO4, respectively. The bulk density of ACCO3 was 0.685 and 0.619 g/cm3 for ACPO4. The BET surface area, pore volume and pore size was 431.3 m2/g, 0.053 cm3/g and 21.63 Ǻ for ACCO3 and 1065.0 m2/g, 0.269 cm3/g and 31.91 Ǻ for ACPO4 (Fig. 1). The pore sizes of activated carbon in the range of 20–50 Ǻ suggest the mesopore. Similar textural properties of activated carbon prepared from other lignocellulosic wastes such as grape seeds
Conclusions
Various adsorption parameters such as contact time, initial MR concentration, adsorbent dose, initial solution pH, and temperature for the removal of MR using ACCO3 and ACPO4were optimized. The adsorption data conformed well for Langmuir isotherm, which indicated that the adsorption sites on the surface of adsorbent are energetically homogeneous. The Langmuir adsorption capacity, Qm (mg/g) for ACPO4 (435.25 mg/g) was found to be higher than that for ACCO3 (226.90 mg/g). The kinetic data fitted
Acknowledgment
The authors would like to thank and acknowledge Dr. Sreedevi Upadhyayula (Associate Professor), Department of Chemical Engineering, Indian Institute of Technology Delhi, New Delhi - 110 016, India, for providing surface area analysis.
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2023, Results in EngineeringCitation Excerpt :Adsorption is recognized as the superior method for water purification due to its convenience, ease of operation, and simplicity of design [8,9] Various materials have been used as adsorbents to remove methyl red from the aquatic environment. These adsorbent materials include zeolite [10], silica [11], activated carbon [1,12], biomass [13] and char [14]. In particular char-based materials, various char have been prepared from multiple raw materials to remove methyl red from the water.