Research Outputs
Triazolium‐based ionic liquids supported on alumina as catalysts to produce 5‐HMF from fructose
The dehydration of fructose to selectively produce 5‐HMF was catalytically developed in a new type of ionic liquids based on triazoles supported on alumina (Al2O3). The synthesis of triazoles by 1,3‐dipolar cycloaddition allows for creating a tailor‐made triazole, that was eventually used to design catalysts based on triazolium‐based ionic liquids. In this work, four catalysts based on triazolium‐ionic liquids supported on Al2O3 were synthesized to produce 5‐HMF from fructose in DMSO as the reaction solvent. According to their molecular structure, the catalysts were tagged as TR1/Al2O3, TR1‐HSO4/Al2O3, TR2/Al2O3, and TR2‐HSO4/Al2O3.
[Tf2N]-based ionic liquids for the selective liquid-liquid extraction of levulinic acid/formic acid: COSMO-RS screening and ternary LLE experimental data
The separation of Levulinic (LA) acid and Formic acid (FA) from aqueous streams represents an important and challenging separation in biorefineries, where ionic liquids (ILs) provide a sustainable environment for liquid-liquid extractions of these acids. In this work, a COSMO-RS screening of bis (trifluoromethylsulfonil)imide [Tf2N]− based IL was first conducted and then followed by experimental validation to search for the most suitable cation for this separation. After the screening, ternary liquid-liquid equilibrium experiments at 298.15K and the subsequent data correlation using the Non-Random Two Liquid model (NRTL) were performed for future industrial implementation. Results indicated that the phosphonium cations, especially the trihexylthetradecyl phosphonium cation [P66614]+, produced the highest selectivity rates among all the experimentally measured ILs.
A review towards selective cobalt recovery in solvent extraction: Potential of ionic liquids as diluents and extractants
Cobalt (Co) stands out as one of the most critical metals in contemporary use, particularly due to its increasing demand in technological products and especially in electromobility. Over the years, ionic liquids (ILs) have provided a green alternative to volatile organic solvents in hydrometallurgy due to their outstanding properties, such as the negligible vapor pressure and their increased selectivity provided in separation processes, which opens the possibility to ramp up the Co-production while maintaining sustainable mining processes. Thus, this review offers a complete comprehensive and critical summary of published works on the use of ILs in the hydrometallurgy of Co, starting from the leaching from a primary source by conventional methods and then, from the pregnant leach solution (PLS) focuses on the advantages and disadvantages of solvent extraction (SX) in different aqueous media (chlorinated, nitrated, and sulfated) in which ILs are used to separate selectively Co from a multi-metal mixture. In the following section, its recovery from the loaded organic phase by acid stripping is discussed. Finally, this review provides the challenges that ILs should overcome to be viable for large-scale industrial applications and the opportunities that exhibit for selective recovery of Co from PLS capitalizing.
Hydrophobic eutectic solvents for the selective solvent extraction of molybdenum (VI) and rhenium (VII) from a synthetic pregnant leach solution
In this work, a study on the selective solvent extraction (SX) of molybdenum (Mo) and rhenium (Re) from a synthetic pregnant leach solution (PLS) has been carried out using nine different hydrophobic eutectic solvents (HES). Experiments were carried out using pure HES to evaluate the selective extraction and the subsequent stripping of these metal ions; then, the best HES was dissolved in kerosene to study the SX stoichiometry. Results indicated that only TOPO-based and N8881-Cl-based HES did not form emulsions, third phases or precipitates. These HES achieved a selective extraction because these obtained almost a 100% extraction towards Mo and Re from the PLS and very low extractions for Copper (Cu) and Iron (Fe) in one equilibrium stage. The stripping experiments showed that 95% of Mo and 22% of Re were stripped out from the loaded TOPO-based HDES, respectively, opening the possibility for the selective stripping of the metal species for further purification. Finally, the extraction stoichiometry was proposed based on an experimental slope analysis and the measurement of cations and anions transferred into the aqueous phase in which HES acts as a neutral extractant in the complexation of the Mo and Re salts. These promising results suggest that HES could be attractive for more sustainable mining industry.
Ionic liquids for the selective solvent extraction of lithium from aqueous solutions: a theoretical selection using COSMO-RS
In this study, the theoretical design of ionic liquids (ILs) for predicting selective extraction of lithium from brines has been conducted using COSMO-RS. A theoretical model for the solvent extraction (SX) of the metal species present in brines was established considering extraction stoichiometry, the distribution of the extractants between aqueous and IL phases, and IL dissociation in the aqueous phase. Theoretical results were validated using experimental extraction percentages from previous works. Results indicate that, in general, the theoretical results for lithium extraction follow experimental trends, except from magnesium extraction. Finally, based on the model, an IL was proposed that was based on the phosphonium cation as the extractant, along with the phase modifier tributylphosphate (TBP) in an organic diluent in order to improve selectivity for lithium ex- traction over sodium. These results provide an insight for the application of ILs in lithium processing, avoiding the long purification times reported in the conventional process.
Rhenium(VII) extraction from sulfuric aqueous solutions using ionic liquids as diluent and extractant: Insights on the extraction stoichiometry and process parameters
Background: Rhenium(Re) is a highly valuable metal recovered from molybdenite leach liquors by solvent extraction (SX) using toxic organic solvents. This work proposes an extracting phase free of volatile organics composed by the ionic liquid (IL) trioctylmethylammonium benzoate [TOMA][BA] as the extractant, due to its ability to extract Re(VII), and the IL 1‐octyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide [omim][Tf2N] as the diluent, due to its high hydrophobicity where the extraction stoichiometry and process parameters such as the initial pH, the extractant concentration in the diluent and stripping using ammonium hydroxide () and sodium hydroxide () were assessed. Results: This extracting phase yielded high extraction percentages: 95% with only 3% (v/v) of [TOMA][BA] in [omim][Tf2N]. A detailed study of the SX stoichiometry was carried out through slope analysis, showing that the SX occurs in two steps: first, the extraction of acid; then, the extraction of the metal ion via anion exchange with the transfer of IL‐diluent anion to the aqueous phase. Additionally, the extracting phase was tested in a synthetic molybdenite leached pregnant leach solution, showing selectivity towards Re(VII) over Cu(II) and Fe(III) at very low extractant concentration. The stripping of Re(VII) from the loaded phase was also studied achieving 60% stripping in only one equilibrium step when using . Conclusion: This novel extracting phase, free of volatile organic, shows promising Re(VII) extraction for future industrial applications.
Analysis of microwave-assisted heating and water extraction from imidazolium and phosphonium based ionic liquids
Ionic liquids have attracted widespread attention due to their low melting points, low vapor pressure, and non-flammability. However, their application at industrial scale is uncommon due to high costs and low recovering efficiency of the ionic liquids within the process. To reduce the costs and environmental effects of ionic liquids, this study proposes to use industrial microwave irradiation to recover eight different ionic liquids from water. The heating kinetics and identification between dielectric and convective heat properties were studied. Imidazolium-based ionic liquids showed the best results, reaching higher temperatures in shorter periods of time. Ionic liquid (bis(trifluoromethylsulfonyl) trihexyl(tetradecyl) phosphonium imide ([P6,6,6,14][Tf2N]) reached a temperature of 398 K in 360 s). On the other hand, the ionic liquid (1-butyl-3-methylimidazolium methylsulfate ([bmim][CH3OSO3]) reached a temperature of 417 K in 150 s). the ionic liquid Microwave heating experiments (water/ionic liquids) demonstrated a 90% recovery in ∼200 s for 1-octyl-3-methylimidazolium chloride ([omim][Cl]). Finally, the time used to heat-up ionic liquids with microwave irradiation was 15 times shorter than the time employed with vacuum-assisted distillation. Therefore, microwave-assisted heating has shown to be an excellent form to heat ionic liquids to decrease the cost of the extraction process and improve their reusability.
Hybrid cross-linked chitosan/protonated-proline: Glucose DES membranes with superior pervaporation performance for ethanol dehydration
This work explores a protonated L-proline: glucose (molar ratio 5:1) deep eutectic solvent (DES) in fabricating biopolymer membranes utilizing chitosan (CS). Initially, the miscibility of CS and DES to prepare homogeneous dense blend membranes has been investigated. Different techniques, such as scanning electron microscopy, contact angle (CA), atomic force microscopy (AFM), Fourier transformed infrared spectroscopy (FTIR) and swelling degree (uptake), were used to characterize the structure of the resulting membranes. Within the pervaporation performance for ethanol dehydration, Arrhenius and mass transfer analysis were analysed in detail. Interestingly, the addition of DESs provided superior performance to crosslinked CS: DES membranes compared with the ones lacking DES. Based on the morphology and properties observed, this new concept of CS-based membranes can be alternatively applied in other solvent separations requiring hydrophilic membranes.
Effects of extraction methods on phenolic content, antioxidant and antiplatelet activities of tomato pomace extracts
Aqueous and ethanolic extracts of tomato pomace were examined with the aim of optimizing the extraction process of compounds with cardioprotective activity. Once the results of the ORAC response variables, total polyphenols, ◦Brix, and antiplatelet activity of the extracts were obtained, a multivariate statistical analysis was performed using the Statgraphics Centurion XIX software. This analysis showed that the most relevant positive effects in the inhibition of platelet aggregation were 83 ± 2% when using the agonist TRAP-6, when the working conditions were the type of tomato pomace conditioning (drum-drying process at 115 ◦C), phase ratio (1/8), type of solvent (ethanol 20%), and type of extraction (ultrasound-assisted solid–liquid extraction). The extracts with the best results were microencapsulated and characterized by HPLC. The presence of chlorogenic acid (0.729 mg/mg of dry sample) was found, a compound that has a potential cardioprotective effect documented in various studies, in addition to rutin (2.747 mg/mg of dry sample) and quercetin (0.255 mg/mg of dry sample). These results show that the extraction efficiency of compounds with cardioprotective activity depends largely on the polarity of the solvent, thus playing an important role in the antioxidant capacity of the extracts of tomato pomace.