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While the specific recovery of valuable chemicals from waste streams represents an environmentally-friendly and potentially economically-relevant alternative to synthetic chemical productions, it remains a largely unmet challenge. This is partially explained by the complexity of designing sorption materials able to target one specific compound and able to function in complex matrices. In this work, a series of cyclodextrin-based polymers (CDPs) were designed to selectively extract phenolic compounds from a complex organic matrix that is olive oil mill wastewater (OMW). In order to endow these polymers with selective adsorption properties, several monomers and cross-linkers were screened and selected. The adsorption properties of the CDPs produced were first tested with selected phenolic compounds commonly found in OMW, namely syringic acid, p-coumaric acid, tyrosol and caffeic acid. The selected CDPs were subsequently tested for their ability to adsorb phenolic compounds directly from OMW, which is known to possess a high and complex organic content. It was demonstrated through high-performance liquid chromatography-mass spectroscopy analyses that efficient removal of phenolic compounds from OMW could be achieved but also that two compounds, namely tyrosol and hydroxytyrosol, could be selectively extracted from OMW.

BACKGROUND: Olive mill wastewaters (OMWs) represent a major environmental concern due to their high organic load and phytotoxic activity. The selective recovery of phenolic compounds (PCs) from OMW is promising, thanks to the antioxidant and antimicrobial properties of PCs. The goal of this work was to perform a life cycle assessment (LCA) and cost–benefit analysis (CBA) of a full-scale process of PC adsorption/desorption on resin Amberlite XAD16N. The industrial process was designed on the basis of laboratory tests aimed at performing a preliminary process optimization. RESULTS: Adsorption tests were conducted at different velocities in a 1.8-m column packed with XAD16N. The optimal superficial velocity and retention time (2.78 m h –1 and 0.56 h) allowed the attainment of satisfactory performances in terms of resin operating capacity (0.46), PC adsorption yield (0.92), PC mass fraction in the sorbed product (0.50 g PC /g VS ) and specific antioxidant activity (3–6 g ascorbic acid /g PC ). Six consecutive adsorption/desorption cycles, operated with the same resin load, resulted in stable process performances. The LCA indicated that the environmental impact of the process could be decreased markedly through the addition of an anaerobic digestion step for the production of irrigation-quality water and fertilizers from the dephenolized OMW. The PC market price required for the generation of a positive business case resulted relatively low (€1.7–13.5 kg PC–1 ). CONCLUSION: The results indicate that the proposed PC adsorption/desorption technology, if integrated with an anaerobic digestion step, represents a promising solution for the treatment and valorization of OMW, a major agro-industrial waste in Mediterranean countries.

A continuous-flow adsorption/desorption process for the recovery of phenolic compounds (PCs) from olive mill wastewaters (OMWs) was developed in a 0.53 m packed column, using a previously selected resin (Amberlite XAD16) and an actual OMW. The main goals of the study were (i) to evaluate the PC adsorption/desorption performances of XAD16 by means of adsorption isotherms and adsorption/desorption breakthrough tests, and (ii) to develop a reliable model of the process. A combination of centrifugation and microfiltration resulted necessary to attain a high suspended solid removal (98.5%) and thus avoid clogging of the packed bed. The quality of two packing procedures was evaluated by means of frontal analysis tests. XAD16 performed well in terms of both adsorption yield at 20% breakthrough (87–88%) and PC/COD selectivity (PC/COD adsorption constant = 7–9). The desorption solvent (acidified ethanol) was effectively regenerated by vacuum distillation. The adsorption breakthrough curves were successfully simulated with a 1-D convection/dispersion model with mass-transfer (R2 = 0.95–0.99; kLa = 0.8–2.5 · 10−3 1/s), whereas an equilibrium adsorption model with dispersion failed to predict the experimental data. In the perspective of a process scale-up, the simulation of the best-performing operational condition was used to evaluate the process performances for different column lengths (0.5–10 m). A precise and automated HPLC method for total PC measurement was developed and compared to the traditional Folin–Ciocalteu methodology. Further research is needed to optimize the desorption step, to scale up the process and to evaluate the long-term resin performances.

The goals of this work were (i) to compare two anion ion exchange resins (IRA958 Cl and IRA67) and a nonionic resin (XAD16) in terms of phenolic compounds adsorption capacity from olive mill wastewater and (ii) to compare the adsorption capacity of the best resin on columns of different length. The ion exchange resins performed worse than nonionic XAD16 in terms of resin utilization efficiency (20% versus 43%) and phenolic compounds/COD enrichment factor (1.0 versus 2.5). The addition of volatile fatty acids did not hinder phenolic compounds adsorption on either resin, suggesting a noncompetitive adsorption mechanism. A pH increase from 4.9 to 7.2 did not affect the result of this comparison. For the best performing resin (XAD16), an increase in column length from 0.5 to 1.8 m determined an increase in resin utilization efficiency (from 12% to 43%), resin productivity (from 3.4 to 7.6 gsorbed phenolics/kgresin), and phenolics/COD enrichment factor (from 1.2 to 2.5). An axial dispersion model with nonequilibrium adsorption accurately interpreted the phenolic compounds and COD experimental curves.