The role of kaolin and kaolin/ZnO nanoadsorbents in adsorption studies for tannery wastewater treatment

In the present study, comparative studies of kaolin and kaolin/ZnO nanocomposites for the adsorption of Cr(VI), Fe(III), COD, BOD, and chloride from tannery wastewater were investigated. ZnO nanoparticles and kaolin/ZnO nanocomposites were prepared by sol-gel followed by wet-impregnation methods. The prepared adsorbents were characterized using different analytical tools such as X-ray diffraction, Fourier transforms infrared, high-resolution transmission electron microscopy, energy dispersive spectroscopy, selective area electron diffraction and Brunauer Emmett-Teller (BET) and X-ray Photoelectron Spectroscopy (XPS). The HRSEM/EDS/XPS analysis confirmed successful immobilization of clay structural network on the lattice layers of zincite hexagonal structure of ZnO nanoparticles. BET measurement showed an increase in the surface area of kaolin/ZnO nanocomposites (31.8 m²/g) when compared to kaolin (17 m²/g). Batch adsorption studies were carried out by varying the parameters such as contact time, adsorbent dosage and temperature. The maximum removal of Cr(VI) (100%), Fe(III) (98%), COD (95%), BOD (94%) and Chloride (78%) was obtained at 15 min by kaolin/ZnO composites. While 78% Cr(VI), 91% Fe(III), 91% COD, 89% BOD and 73% Chloride were removed by kaolin under the same conditions. The kaolin/ZnO nanocomposites exhibited better adsorption performance than kaolin due to higher surface area of the former than the latter. It was found that the Jovanovic isotherm model fitted the adsorption experimental data most with the highest correlation (R² > 0.99) for both nanoadsorbents and indicate the occurrence of adsorption on monolayer and heterogeneous surfaces. The mechanism for the adsorption of metal ions in tannery wastewater onto the nano-adsorbents was examined using Weber Morris intra-particle diffusion model and Boyd plot which showed that the adsorption process was both intra-particle and film diffusion controlled. The thermodynamic parameters such as enthalpy change showed that that adsorption of metal ions and other parameters was feasible, spontaneous and endothermic. The ZnO/clay nanocomposites exhibited excellent recyclable and re-useable properties even after six repeated applications and can, therefore, be applied in wastewater treatment for removal of heavy metals and other physicochemical parameters.