Enhanced removal of bisphenol A using pine-fruit shell-derived hydrochars: Adsorption mechanisms and reusability

We synthesized NaOH-activated hydrochars via hydrothermal carbonization (HTC) of Brazilian pine fruit shells at HTC residence times of 24, 48, and 72 h. The hydrochars were used as adsorbents to remove bisphenol A (BPA) from aqueous solutions. The surface area of the samples can reach up to 2220 m² g^-1, and the maximum adsorption of BPA onto the surfaces was achieved at a pH of 7.0 (708 mg g^-1). Adsorption occurred mainly via monolayer formation with a low retention time of the adsorbate (τ) on the surfaces, indicating that the BPA molecules reached the already occupied active sites and returned after undergoing heat exchange (τ > 0). Adsorption is an endothermic spontaneous process that results in a balance between entropic and enthalpic contributions. In such a reaction, ΔG°< 0, even with ΔH°> 0, the process occurs with an important increase in the entropy. The desorption was more efficient with ethanol and methanol than with HCl, NaOH, and NaCl owing to the dipole-dipole forces between the adsorbate and the alcohols. Additionally, the low desorption efficiency using acid, base, and salts can be attributed to competitive effects between the desorption agents and the active sites of the adsorbents.