Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent...

Naphthenic acids (NA) are organic compounds commonly found in crude oil and produced water, known for their recalcitrance and toxicity. This study introduces a new adsorbent, a polymer derived from spent coffee grounds (SCGs), through a straightforward cross-linking method for removing cyclohexane carboxylic acid as representative NA. The adsorption kinetics followed a pseudo-second-order model for the data (0.007 g min^-1 mg^-1), while the equilibrium data fitted the Sips model ( $$ = 140.55 mg g^-1). The process's thermodynamics indicated that the target NA's adsorption was spontaneous and exothermic. The localized sterical and energetic aspects were investigated through statistical physical modeling, which corroborated that the adsorption occurred indeed in monolayer, as suggested by the Sips model, but revealed the contribution of two energies per site ( $$ ). The number of molecules adsorbed per site $$ ) was highly influenced by the temperature as $$ decreased with increasing temperature and $$ increased. These results were experimentally demonstrated within the pH range between 4 and 6, where both C₆H₁₁COO^-(aq.) and C₆H₁₁COOH(aq.) species coexisted and were adsorbed by different energy sites. The polymer produced was naturally porous and amorphous, with a low surface area of 20 to 30 m² g^-1 that presented more energetically accessible sites than other adsorbents with much higher surface areas. Thus, this study shows that the relation between surface area and high adsorption efficiency depends on the compatibility between the energetic states of the receptor sites, the speciation of the adsorbate molecules, and the temperature range studied.