Modeling and Optimization of Phenolic Compound Adsorption from Olive Wastewater Using XAD-4 Resin, Activated Carbon, and Chitosan Biosorbent

Abstract

This study proposes a circular economy strategy to recover phenolic compounds by valorizing shrimp shell waste into a chitosan biosorbent (CH-B). Its adsorption efficiency was evaluated compared to commercial activated carbon (AC) and synthetic XAD-4 resin. Kinetic analysis revealed that while both pseudo-first-order (PFO) and pseudo-second-order (PSO) models exhibited high correlations (R2 ≥ 0.96), both CH-B and XAD-4 resin were best described by the PFO model. This aligns with diffusion-controlled processes consistent with the porous and physical nature of these adsorbents. In contrast, AC followed the PSO model. Isotherm modeling indicated that CH-B and AC fit the Temkin model, reflecting heterogeneous surfaces, whereas XAD-4 followed the Langmuir model (monolayer adsorption). Notably, CH-B exhibited a maximum adsorption capacity (qm) of 229.2 mg/g, significantly outperforming XAD-4 (104.8 mg/g) and AC (90.2 mg/g). Thermodynamic and kinetic modeling confirmed that the adsorption mechanism was governed by a combination of electrostatic interactions, π–π stacking, and hydrogen bonding between the hydroxyl/amine groups of chitosan and phenolic compounds. Optimization using Box–Behnken design for CH-B showed optimal acidic pH and moderate temperature but non-significant effect of CH-B dose in the experimental domain. Optimisation results showed unexpected high removal efficiency at low CH-B dosages. A tentative explanation may be adsorbent aggre-gation, which needs to be confirmed by further experimental evidence.