Post-combustion gas capture/separation by gas-liquid membrane contactors using non-volatile solvents.

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Solid-liquid phase behavior of eutectic solvents containing sugar alcohols

Publication . Silva, Liliana P.; Martins, Mónia A.R.; Abranches, Dinis O.; Pinho, Simão; Coutinho, João A.P.

Mixtures of carbohydrates are often reported in the literature as deep eutectic solvents yet, in most cases, their solid–liquid phase diagrams are poorly characterized and no evidence is available to validate this classification. In this work, the phase diagrams of the binary systems composed of the sugar alcohols mannitol or maltitol and meso-erythritol, xylitol, or sorbitol, were experimentally determined. The results obtained reveal that these systems have a thermodynamic ideal behavior, questioning their classification as deep eutectic solvents and showing that intermolecular hydrogen bonding between the components of a mixture is not a sufficient condition to prepare deep eutectic solvents. The phase diagrams of the systems composed of mannitol or maltitol and cholinium chloride were also measured in this work. In sharp contrast to the mixtures composed solely by sugar alcohols, and unlike numerous other choline-based eutectic systems reported in the literature, these systems revealed significant deviations to thermodynamic ideality, leading to significant melting temperature depressions. The Cl-OH interaction between cholinium chloride and the sugar alcohols is identified as the main reason for these deviations to ideality, paving the way for the rational choice of hydrogen bond acceptors to prepare deep eutectic solvents.

2021Journal article

Open access

Eutectic mixtures based on polyalcohols as sustainable solvents: screening and characterization

Publication . Silva, Liliana P.; Martins, Mónia A.R.; Conceição, João H.F.; Pinho, Simão; Coutinho, João A.P.

Despite some promising potential applications of eutectic systems containing choline chloride ([Ch]Cl) and a polyalcohol, a detailed investigation of the thermodynamic behavior of these systems is still missing. In this work, the solid-liquid equilibria phase diagrams of binary systems containing [Ch]Cl and one from six different polyalcohols (ethylene glycol (EG), 1,3-propanediol, glycerol (Gly), meso-erythritol, xylitol, and sorbitol) were measured in the full composition. Except for the mixtures with Gly or EG, a quasi-ideal behavior in the [Ch]Cl solubility curve is observed. In the polyalcohol solubility curve, the mixtures present small negative deviations from ideality, except for [Ch]Cl + EG, which is slightly positive. The solid-liquid phase diagrams show a large liquid composition window, and not a fixed stoichiometry for the eutectic points, where the mixtures can be used as solvents close to, or below, room temperature. Aiming at their application, viscosities and densities were measured at the eutectic point in the temperature range from 278.15 to 373.15 K. All systems present densities and viscosities higher than water, which is directly related to the strong interactions between the components. Solvatochromic parameters were measured to characterize the solvents, and they show that solvent tunability can be achieved by varying the polyalcohol mole fraction.

2020Journal article

Open access

The role of the anion in imidazolium-based ionic liquids for fuel and terpenes processing

Publication . Zambom, Aline; Vilas-Boas, Sérgio M.; Silva, Liliana P.; Martins, Mónia A. R.; Ferreira, Olga; Pinho, Simão

Abstract: The potentialities of methylimidazolium-based ionic liquids (ILs) as solvents were evaluated for some relevant separation problems—terpene fractionation and fuel processing—studying selectivities, capacities, and solvent performance indices. The activity coefficients at infinite dilution of the solute (1) in the IL (3), g¥ 13, of 52 organic solutes were measured by inverse gas chromatography over a temperature range of 333.2–453.2 K. The selected ILs are 1-butyl-3-methylimidazolium hexafluorophosphate, [C4mim][PF6], and the equimolar mixture of [C4mim][PF6] and 1-butyl-3-methylimidazolium chloride, [C4mim]Cl. Generally, low polar solutes follow g¥ 1,[C4mim]Cl > g¥ 1,[C4mim][PF6]+[C4mim]Cl > g¥ 1,[C4mim][PF6] while the opposite behavior is observed for alcohols and water. For citrus essential oil deterpenation, the results suggest that cations with long alkyl chains, such as [C12mim]+, promote capacity, while selectivity depends on the solute polarity. Promising results were obtained for the separation of several model mixtures relevant to fuel industries using the equimolar mixture of [C4mim][PF6] and [C4mim]Cl. This work demonstrates the importance of tailoring the polarity of the solvents, suggesting the use of ILs with mixed anions as alternative solvents for the removal of aliphatic hydrocarbons and contaminants from fuels.

2023Journal article

Open access

The role of ionic vs. non-ionic excipients in APIs-based eutectic systems

Publication . Martins, Mónia A.R.; Silva, Liliana P.; Jorge, Patrícia S.; Abranches, Dinis O.; Pinho, Simão; Coutinho, João A.P.

Aiming to contribute to drug pre-formulation, new eutectic mixtures were developed. Thymol, coumarin, or quaternary ammonium chlorides as excipients, were combined with the active pharmaceutical ingredients (APIs) acetylsalicylic acid, acetaminophen, ibuprofen, ketoprofen, or lidocaine. Their solid-liquid equilibrium (SLE) binary phase diagrams were measured to study eventual phase separation between the compounds, preventing manufacturing problems, and to study the molecular interactions between the APIs and ionic or non-ionic excipients. The Conductor-like Screening Model for Real Solvents (COSMO-RS) capability to predict the SLE of mixtures containing non-ionic excipients was further evaluated. COSMO-RS gives a good quantitative description of the experimental SLE being a tool with great potential in the screening of eutectic systems containing APIs and non-ionic excipients. While thymol presents strong interactions with the APIs, and consequently negative deviations to thermodynamic ideality, systems containing coumarin follow a quasi-ideal behavior. Regarding the ionic excipients, both choline chloride and the tetraalkylammonium chlorides are unable to establish relevant interactions with the APIs, and no significant negative deviations to ideality are observed. The liquefaction of the APIs here studied is favored by using non-ionic excipients, such as thymol, due to the strong interactions it can establish with the APIs.

2021Journal article

Open access