Humic Acid Recovery from Leachate Nanofiltration Concentrate Using Halloysite Nanotube-Coated Tubular Ceramic...

Landfill wastewater is a serious environmental problem and represents a high-concentration source of valuable organic compounds such as humic acids (HAs). The nanofiltration (NF) concentrate generated during treatment poses an even more significant environmental challenge, and the recovery of these substances is compatible with circular economy principles but requires innovative, pollution-resistant separation technologies. This study presents a novel hybrid approach for HA recovery by integrating naturally occurring clay minerals, such as halloysite nanotubes (HNTs), as a dynamic coating layer onto tube-shaped ceramic ultrafiltration membranes. The research was conducted in two stages: batch adsorption-desorption experiments followed by membrane integration. In the first stage, the batch adsorption studies showed that HA adsorption by HNTs followed the Freundlich isotherm model. The maximum HA adsorption capacity for HNTs increased with increasing initial concentration. In desorption studies, recovery rates of 74.6% were achieved with 1.5 N sodium hydroxide (NaOH) and 67.5% with 1.5 N potassium hydroxide (KOH). In membrane studies, the optimum HNT coating concentration was determined as 0.05 g/L. While an average removal efficiency of 85.3% was obtained in synthetic HA filtration, the desorption efficiency after regeneration was around 35-37%. In experiments with real NF concentrate, HA removal efficiencies ranged from 19 to 64% for concentrations of 5, 10, and 20 mg/L, with the highest desorption efficiency (59.3%) obtained in the 10 mg/L NF concentrate. The results reveal that the complex structure and competing components in the real wastewater matrix limit the removal and recovery performance compared to synthetic solutions.