Efficient removal of tizanidine and tetracycline from water: A single and competitive sorption approach using carboxymethyl cellulose granulated iron-pillared clay

Abstract

This study deals with the development of a granulated Fe-pillared clay (Fe-PC) using carboxymethylcellulose (CMC) as a binder to present it as an innovative adsorbent for the individual and competitive adsorption of tetracycline (Tc) and tizanidine (Tz) from water. An optimum pH value of 7 was determined for both individual and multi-component adsorption. The optimal dosage of granulated Fe-PC was determined to be 1.5 g/L for Tz and 3 g/L for Tc, resulting in constant removal rates of 80 % for Tc and 90 % for Tz. Tizanidine showed a higher affinity for powdered or granulated Fe-PC compared to tetracycline, due to its smaller molecular size and increased amine functional groups. Consequently, Tz showed improved kinetic rates (initial pseudo-second order sorption rates of 170.79 and 25.62 mg/g.h for Tz and Tc, respectively) and equilibrium capacities (maximum monolayer adsorption capacity of granulated Fe-PC at room temperature over Tc and Tz, 54.89 mg/g and 66.40 mg/g). Granulation affected the kinetic rate for both adsorbates, albeit with a more pronounced effect for Tc. The adsorption of Tz was less sensitive to temperature changes, indicating a lower enthalpy change of adsorption (14.24 and 77.91 kJ/mol for Tz and Tc, respectively). HCl for Tc and NaCl for Tz were identified as optimal desorption eluents, confirming the involvement of cation exchange in Tz adsorption. Surface functional group analysis confirmed the proposed complexation mechanisms. Tz consistently showed a higher affinity for granular Fe-PC than Tc, especially at lower adsorbent dosages. This article provides a comprehensive insight into the characterization of the prepared adsorbents and their cyclic adsorption-desorption performance for Tc and Tz.