Removal of methylene blue dye using nano zerovalent iron, nanoclay and iron impregnated nanoclay – a comparative study

Abstract

There has been an increasing challenge from the emission of methylene blue (MB) dye-containing wastewater and its management methods in industry. The sorption process is one conventionally used method. In this study, nanoclay, nano zero valent iron (nZVI), and iron impregnated nanoclay were prepared and studied for the removal of MB dye in batch mode. The effects of operating parameters like pH, dye concentration, sorbent dosage, and contact time were investigated and optimized. The nZVI, nanoclay, and iron impregnated nanoclay sorbents showed zeta potentials of −32.1, −53.4, and −40.7 mV, respectively. All the nano adsorbents were crystalline. The nanoclay was characterized by an average surface area, pore volume and pore diameter of 43.49 m² g⁻¹, 0.104 cm³ g⁻¹ and 2.806 nm, respectively. nZVI showed a surface area of 47.125 m² g⁻¹, pore volume of 0.119 cm³ g⁻¹, and pore diameter of 3.291 nm. And iron impregnated nanoclay showed a surface area of 73.110 m² g⁻¹ with a pore volume of 15 cm³ g⁻¹ and a pore diameter size of 3.83 nm. A Langmuir EXT nitrogen gas adsorption isotherm (R² ∼ 0.99) was the best fit. The thermodynamics parameters, such as ΔG° (−12.64 to −0.63 kJ mol⁻¹), ΔH° (+0.1 to +62.15 kJ mol⁻¹) and ΔS° (+0.10 to +0.22 kJ mol⁻¹), confirmed that a spontaneous and endothermic adsorption process took place at a high rate of disorder. Iron impregnated nanoclay showed higher negative Gibbs free energy (−12.64 kJ mol⁻¹), higher enthalpy change (+62.5 kJ mol⁻¹) and entropy (+0.22 kJ mol⁻¹) and gave a better MB removal performance. In addition, the lower negative heat of enthalpy for all adsorptions proved the dominance of physisorption. The methylene blue adsorption isotherm on nZVI and nanoclay showed the best fit with the Freundlich isotherm model with correlation coefficients (R²) ∼0.98 and 0.99, respectively. Whereas the Langmuir adsorption isotherm was the best fit for iron impregnated nanoclay (R² ∼ 0.98). The adsorption activities of nZVI, nanoclay and iron impregnated nanoclay were fitted to a pseudo-second-order kinetic model with correlation coefficients (R²) of 0.999, 0.997 and 0.983, respectively. The optimal pH 7.0 (RE: 99.1 ± 0.73%), initial MB concentration 40 ppm (RE: 99.9 ± 0.03%), contact time 120 min (RE: 99.9 ± 0.9%), and adsorbent dose 80 (99.9 ± 0.03%) were obtained for iron impregnated nanoclay. The optimal operational parameters of nanoclay and nZVI, respectively, were pH 11.0 and 13.0, initial MB concentration 20 and 20 ppm, adsorbent dose 100 and 140 mg, and contact time 120 and 140 min. In general, iron impregnated nanoclay has shown promising cationic dye adsorbance for industrial applications; but a recyclability test is suggested before scale-up.