Clay minerals have large surface areas that contribute to their high adsorption capacity. Pure clays were often used. However, their prices remain expensive. However, the natural clay minerals that are locally available can have economic and environmental benefits for textile wastewater treatment. The tested natural clays had given low removal yields. Therefore, we wanted to test particular rich organic matter clay for adsorbing azo dye, which is a very toxic molecule. In order to make the use of this clay type have a better efficiency for removal of this dye from the polluted waters, the optimal conditions had been specified. The results indicated that advised conditions were as follows: 5 min was the contact time of dye-clay; the better adsorbent masses were 0.25 g and 0.5 g per 100 ml solution for raw (ANb) and purified clays (ANp), respectively; the initial dye concentrations were 1 gL−1 for raw clay and 50 mgL−1 for purified clay; pH solution had any effect on the yield of dye removal only when raw clay was used; however, acid environment was advised when purified clay was the adsorbent and for the two tested clays about 20–30°C was the better solution temperature. X-Ray diffraction, Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) analysis confirmed that functional groups of clay adsorbed the dye. Langmuir maximum adsorption capacities of ANb and ANp were found to be 397 mgg−1 and 132.3 mgg−1 at pH 7 and 5, respectively. Raw and chemically activated samples gave similar results. Adsorption of ANb and ANp data showed better agreement with the pseudo-second-order kinetic model. Thermodynamic parameters of the two adsorbents confirmed that the adsorption was endothermic (ΔH > 0) and spontaneous (ΔG0 < 0). Energy level was high when purified clay was used; however, it was significantly lower when the adsorbent was raw clay. Therefore, it was likely that adsorption by carbonates and organic matter involved small energy amounts. Comparing between these and other previous results, Jebel Louka natural clay type is better recommended for MR removal from textile wastewater, since the removal yield was about 98%. Hence, this tested clay type could provide an alternative low-cost material that could be used in treatment of the textile wastewater rich in MR and the obtained adsorption model and desorption tests provided a background for pilot and industrial scale applications.

Adsorption of cationic methyl green (MG) on nontreated (AB) and purified (AP) natural Sejnane clay type was studied in an equilibrium batch process. This work reported the application of kaolinite-rich heterogeneous clay for the removal of a cationic dye. Effects of contact time, initial dye concentration, mass adsorbent, pH, and temperature on the MG removal were checked. The adsorbent before and after adsorption processes was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and atomic adsorption spectrophotometer. Equilibrium data were mathematically modeled using the Freundlich, Langmuir, and intraparticle diffusion models. Kinetic of adsorption was determined by pseudo-first-order and pseudo-second-order models. The free energy (ΔG°), standard enthalpy (ΔH°), and standard entropy (ΔS°) were calculated. A fast increase in the equilibrium removal of the cationic dye was obtained at a pH ranging between 3 and 11 and moderate temperature. This rapid MG adsorption proved the efficiency of kaolinite clay in cationic dye removal. Decolorizing yields were 73.3% for AB and 99.8% for AP. Thus, the adsorption capacity of purified clay was clearly higher than of H2SO4 and thermic activated clays. The data more closely resembled a pseudo-second-order model process, and the clay had reasonable Freundlich adsorption capacity. Adsorption process was endothermic and spontaneous chemisorption. SEM analysis showed that the adsorbed MG had remarkably changed the morphology of raw and purified clay surface. The low desorption rates confirmed effectiveness of this type of material for the retention of methyl green molecules. Thus, tested clays have no environmental impact.