Modification of natural zeolite clinoptilolite and ITS application in the adsorption of herbicides
Henrique Straioto, Paula Valéria Viotti, Alexandre Amado de Moura, Alexandre Diório, Mara Heloísa Neves Olsen Scaliante, Wardleison Martins Moreira, Marcelo Fernandes Vieira, Rosângela Bergamasco
Abstract
The clinoptilolite natural zeolites (NZs) posses low herbicide adsorption capacity demanding acid-, alkali-, or salt chemical modifications that enhance its adsorption. However, this may affect the material structure and charge distribution. Alternatively, zeolites may be synthesized at a high cost and time-consuming process. Consequently, new methods, such as the hydrothermal method, for NZ modification needs to be studied. In this sense, a novel surface-modified zeolite (SMZ), using hexadecyltrimethylammonium bromide (CTAB), in acid media was produced by the hydrothermal method and applied for the adsorption of Atrazine (ATZ), Diuron (DIU) and 2,4-D. Commercial NZ and SMZ were characterized by SEM, XRD, TGA, FT-IR, AA spectroscopy, pHPZC, Zeta potential and N2-physisorption. The SMZ chosen for the adsorption experiments was the one with the highest modification yield and adsorption capacity obtained from a complete design of experiments (CTAB=0.74 ; D=12 Mesh; HCl=0.1 M; t=6 h and T=205 ºC). The adsorption experiments revealed that the SMZ adsorption capacity for the herbicide 2,4-D (qmax=9.02 mg/g) was greater than that obtained for ATZ (qmax=2.11 mg/g) and DIU (qmax=1.85 mg/g), which was explained by the presence of the hydroxyl group and by geometric characteristics of the 2,4-D. Adsorption models’ fitting showed that the adsorption of 2,4-D onto SMZ were best described by pseudo-second order kinetic (k2=0.005-0.006 g/mg.min; qe,exp=7.122-8.614 mg/g) and Langmuir isothermal model (KL=0.283-0.499 L/mg; qm=7.167-7.995 mg/g). These results indicate that the hydrothermal method is a viable alternative to enable the use of NZs for the adsorption of emerging contaminants from wastewater.