RESUMEN
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.
RESUMEN
Carboxylic acids can be isolated from fermentation broths using reactive liquid-liquid extraction, offering an alternative to the environmentally harmful state-of-the-art process of precipitating calcium lactate. To enhance the sustainability of liquid-liquid extraction processes, greener solvents, such as natural deep eutectic solvents, are investigated. However, fermentation broths often exhibit pH values unsuitable for carboxylic acid extraction, which can be adjusted using mineral acids, though mineral acids may be co-extracted. In this study, we systematically examine the co-extraction of hydrochloric, nitric, sulfuric, and phosphoric acid during extraction and back-extraction of lactic acid. The solvent phase consisted of tri-n-octylamine, trioctylphosphine oxide, or tributyl phosphate diluted in a thymol-menthol deep eutectic solvent. The back-extraction was conducted using a diluent swing with p-cymene as the antisolvent and water as the receiving phase. Tri-n-octylamine showed the highest efficiency for lactic acid (up to 29.8%) but also the highest co-extraction of mineral acids (up to 50.9%). In contrast, trioctylphosphine oxide exhibited a lower but more selective lactic acid extraction (5.94%) with low mineral acids co-extraction (0.135%). Overall, the highest co-extraction was observed for phosphoric acid and the lowest for nitric acid. In conclusion, the selected solvent phase composition and mineral acid influence the co-extraction and, thus, final product purity. The successful application of the natural deep eutectic solvent as the modifier enhances the sustainability of liquid-liquid extraction processes.
RESUMEN
In kraft pulping, large quantities of biomass degradation products dissolved in the black liquor are incinerated for power generation and chemical recovery. The black liquor is, however, a promising feedstock for carboxylic acids and lignin. Efficient fractionation of black liquor can be used to isolate these compounds and recycle the pulping chemicals. The present work discusses the fractionation of industrial black liquor by a sequence of nanofiltration and bipolar membrane electrodialysis units. Nanofiltration led to retention of the majority of lignin in the retentate and to a significant concentration increase in low-molecular-weight carboxylic acids, such as formic, acetic, glycolic and lactic acids, in the permeate. Subsequent treatment with bipolar membrane electrodialysis showed the potential for simultaneous recovery of acids in the acid compartment and the pulping chemical NaOH in the base compartment. The residual lignin was completely retained by the used membranes. Diffusion of acids to the base compartment and the low current density, however, limited the yield of acids and the current efficiency. In experiments with a black liquor model solution under optimized conditions, NaOH and acid recoveries of 68-72% were achieved.