Hydroxypropyl methylcellulose-sugarcane bagasse adsorbents for removal of 17α-ethinylestradiol from aqueous solution and freshwater

Abstract

Adsorbents made of hydroxypropyl methylcellulose (HPMC) and sugarcane bagasse (BG) microparticles were applied for the separation of 17α-ethinylestradiol (EE2) from aqueous solution in batch, and from aqueous solution and freshwater in fixed-bed columns. HPMC chains and BG microparticles were crosslinked by the esterification with citric acid. The adsorbents presented compression modulus values that increased from 208 ± 20 kPa (pure HPMC) to 917 ± 90 kPa, when the content of BG particles added to HPMC was 50 wt% (HPMC50BG). The porosity (~ 97%), specific surface area (1.16 ± 0.10 m²/g) and swelling degree (20 ± 1 g water/g) values were not affected by the addition of BG particles. The adsorption isotherms determined for EE2 on HPMC and on HPMC50BG fitted to the Langmuir and Freundlich models; the adsorption capacity of HPMC was slightly higher than that of composite HPMC50BG. Nevertheless, the addition of BG particles rendered outstanding mechanical reinforcement and dimensional stability to the adsorbents. The adsorption was driven by (i) hydrophobic interactions between EE2 methylene and aromatic groups and HPMC methyl groups, as evidenced by FTIR spectroscopy, and (ii) H bonds between HPMC and EE2 hydroxyl groups, as revealed by the adsorption enthalpy change (ΔH_ads) of - 45 kJ/mol. Column adsorption experiments of EE2 from aqueous solution on HPMC and HPMC50BG indicated adsorptive capacity (q₀) values of 8.06 mg/g and 4.07 mg/g, respectively. These values decreased considerably for the adsorption of EE2 from river water, probably due to the competition of EE2 with humic substances dissolved in natural water. The HPMC adsorbents could be recycled retaining up to 83% of the original efficiency.

Keywords: 17α-ethinylestradiol; Batch adsorption; Column adsorption; Freshwater; Hydroxypropyl methylcellulose; Sugarcane bagasse.