• Energy Research

The nonionic Type V deep eutectic solvent (DESs) thymol + menthol is experimentally and computationally studied aiming to clarify the relation between its liquid phase structure and its thermodynamic nonideality. 1H NMR, Raman, and X-ray scattering analysis of the thymol + menthol system, supported by molecular dynamics simulations, show complex intermolecular interactions dominated by sterically hindered H-bonded clusters. For temperatures greater than or equal to room temperature, a quasi-linear evolution of the eutectic system properties between the pure compounds is observed, suggesting the absence of a magic stoichiometric composition in the eutectic solvent. However, temperature dependent Raman spectroscopy indicates a notable increase in thymol-menthol H-bonding as temperatures approach the eutectic point. This study shows that nonionic Type V DESs present an important temperature-dependent nonideality originating from the change in the intermolecular H-bonding with temperature. These findings have significant implications for the design and growing application of Type V DESs.

Isobaric vapor-liquid equilibria of 1-butyl-3-methylimidazolium thiocyanate ([C4C1im][SCN]), 1-butyl-3-methylimidazolium dicyanamide ([C4C1im][N(CN)2]), 1-butyl-3-methylimidazolium tricyanomethanide ([C4C1im][C(CN)3]), and 1-ethyl-3-methylimidazolium tetracyanoborate ([C2C1im][B(CN)4]), with water and ethanol were measured over the whole concentration range at 0.1, 0.07, and 0.05 MPa. Activity coefficients were estimated from the boiling temperatures of the binary systems, and the data were used to evaluate the ability of COSMO-RS for describing these molecular systems. Aiming at further understanding the molecular interactions on these systems, molecular dynamics (MD) simulations were performed. On the basis of the interpretation of the radial and spatial distribution functions along with coordination numbers obtained through MD simulations, the effect of the increase of CN-groups in the IL anion in its capability to establish hydrogen bonds with water and ethanol was evaluated. The results obtained suggest that, for both water and ethanol systems, the anion [N(CN)2](-) presents the higher ability to establish favorable interactions due to its charge, and that the ability of the anions to interact with the solvent, decreases with further increasing of the number of cyano groups in the anion. The ordering of the partial charges in the nitrogen atoms from the CN-groups in the anions agrees with the ordering obtained for VLE and activity coefficient data.

a b s t r a c t Increasing pollutants emissions, along with the limitations present on the existing control methods and stricter legislation to come, demand the development of new methods to reduce them. Ionic liquids (ILs) have been attracting an outstanding attention during the last decade and rose as a promising class of viable solvents to capture pollutants and for gas separation processes. As part of a continuing effort to develop an ionic liquid based process for high pressure capture of greenhouse gases, the phase equilibria of carbon dioxide (CO2), nitrous oxide (N2O), methane (CH4) and nitrogen (N2) in 1-ethyl-3-methylimidazolium methyl-phosphonate ((C2mim)(CH3OHPO2)) were studied in this work. Experimental measurements for the CO2, N2O, CH4 and N2 solubilities in (C2mim)(CH3OHPO2) were carried out for gases mole fractions ranging from (0.018 to 0.504), in the temperature range (293.23 to 363.34) K and for pressures from (1.16 to 87.61) MPa. The particular behavior of the selected highly polar ionic liquid is here shown for the first time through the reported experimental data. The low N2, CH4 and CO2 solubilities, with the later system presenting positive deviations to ideality, show the ionic liquid unfavorable interactions with the studied gases and the necessity to find a proper compromise between the solvent polarity and its molar volume in order to achieve high CO2/N2 or CO2/CH4 separation selectivities. The good soft-SAFT EoS performance in describing the thermophysical properties of ionic liquids and the phase equilibria of their mixtures with gases was extended in this work for the description of the experimental data reported. New and reliable molecular schemes for N2O and (C2mim)(CH3OHPO2), not yet studied within the soft-SAFT framework, were proposed. Using no more than one binary interaction parameter, the soft-SAFT EoS is able to take into account the particular pressure and temperature behavior of the different gases solubilities in the selected ionic liquid. This empowers the equation to be reliably used for other similar systems, as tool to optimize the given process, searching for the best conditions for capture.

Aiming at designing ionic liquids for the purification of natural gas, the solubility of methane in ionic liquids is investigated here through the measurement of the solubilities of methane in four ionic liquids (ILs), in a wide range of molar fractions, temperature and pressures. With the exception of the phosphonium-based IL, which behaves as an almost ideal solution, the other ionic liquids show strong positive deviations from ideality, resulting from non-favorable interactions between CH4 and the ILs. The results indicate that the non-ideality of the solution increases, and the solubility decreases, with the polarity of the ionic liquid. The effect of the ionic liquid polarity on the CO2/CH4 and H2S/CH4 selectivities is evaluated here. The ionic liquids studied here present the largest CO2/CH4 and H2S/CH4 selectivities ever reported. The selectivity models previously proposed in the literature are tested against these new experimental data and are shown to fail. Furthermore, it is shown that describing the ILs' polarity using the Kamlet–Taft parameters, the CO2/CH4 and H2S/CH4 selectivities correlate well with the β-parameter providing a key to the design of ionic liquids with enhanced selectivities.