Characterization of Camphene- and Fenchol-Based Hydrophobic Eutectic Solvents and Their Application in Aldehyde Extraction

Abstract

Binary terpenoid-based eutectic systems consisting of the natural substances camphene (CA), fenchol (FE), thymol (TH), menthol (ME), dodecanoic acid (DA), and 1-dodecanol (DO) are synthesized and screened for their Solid–Liquid Equilibrium (SLE) and eutectic compositions. Out of nine eutectic systems, 13 solvent compositions at eutectic points and next to them, in addition to the reference solvent, TH:ME, are synthesized and applied for the solvent extraction of the aromatic aldehydes vanillin (VAN), syringaldehyde (SYR), and p-hydroxybenzaldehyde (HYD) from an acidic aqueous model solution. The extraction efficiency is determined from aldehyde concentrations measured by High-Performance Liquid Chromatography (HPLC), taking into consideration mutual solubility measured by Karl Fischer titration (KF) and a Total Organic Carbon-analysis (TOC). Physicochemical properties, such as the density, viscosity, and stability of the solvents, are evaluated and discussed. Additionally, 1H-NMR measurements are performed to verify hydrogen bonding present in some of the solvents. The results show that all synthesized eutectic systems have a strong hydrophobic character with a maximum water saturation of ≤2.21 vol.% and solvent losses of ≤0.12 vol.% per extraction step. The hydrophobic eutectic solvents based on CA exhibit lower viscosities, lower mutual solubility, and lower extraction efficiency for the aromatic aldehydes when compared with FE-based solvents. The highest extraction efficiencies for VAN (>95%) and for SYR (>93%) at an extraction efficiency of 92.61% for HYD are achieved by the reference solvent TH:ME (50:50 mol.%). With an extraction efficiency of 93.08%, HYD is most preferably extracted by the FE–DO-solvent (80:20 mol.%), where the extraction efficiencies for VAN and SYR reach their maximum at 93.37% and 90.75%, respectively. The drawbacks of the high viscosities of 34.741 mPas of the TH:ME solvent and 31.801 mPas of the FE–DO solvent can be overcome by the CA–TH solvent, which has a viscosity of 3.436 mPas, while exhibiting extraction efficiencies of 71.92% for HYD, >95% for VAN, and >93% for SYR, respectively.