Evaluation of Alkylimidazoles as Physical Solvents for CO₂/CH₄ Separation

1-<i>n</i>-Alkylimidazoles are a class of tunable solvents with low volatility and low viscosities. Although imidazoles have been known for some time in the pharmaceutical industry, and as convenient precursors for synthesizing imidazolium-based ionic liquids (ILs), only recently have they been given consideration in some of the same solvent-based separations applications that ILs have been studied for, such as post-combustion CO₂ capture and natural gas treating. “Sweetening”, the removal of CO₂, H₂S, and other “acid” gases from natural gas (CH₄), is an existing industrial application where low volatility, low viscosity physical solvents are already applied successfully and economically at large scale. Physical solvents are also used for syngas cleanup and in the emerging application of pre-combustion CO₂ capture. Given the similarities in physical properties between 1-<i>n</i>-alkylimidazoles, and physical solvents currently used in industrial gas treating, the 1-<i>n</i>-alkylimidazole class of solvents warrants further investigation. Solubilities of CO₂ and CH₄ in a series of 1-<i>n</i>-alkylimidazoles were measured under conditions relevant to the use of physical solvents for natural gas treating: ∼5 atm partial pressure of CO₂ and temperatures of 30–75 °C. Solubilities of CO₂ and CH₄ were found to be strongly dependent on temperature, with the solubility of each gas in all solvents diminishing with increasing temperature, although CO₂ exhibited a stronger temperature dependence than CH₄. Ideal CO₂/CH₄ solubility selectivities were also more favorable at lower temperatures in 1-<i>n</i>-alkylimidazole solvents with shorter chain lengths. CO₂ solubility decreased with increasing chain length, while CH₄ solubility exhibited a maximum in 1-hexylimidazole. The solubility trends observed with temperature and chain length can be explained through calculation of solution enthalpies and solvent fractional free volume as approximated from van der Waals volumes as calculated via atomic contributions. Of the solvents examined, 1-methylimidazole displays the most favorable CO₂ solubility and CO₂/CH₄ selectivity, and has the lowest viscosity. A comparison of 1-methylimidazole to commercially used solvents reveals similar physical properties and the potential for use in industrial gas processing. Imidazolium-based ILs are also compared, although they appear less favorable for use within established process schemes given their higher viscosities and reduced capacity for CO₂

Properties and Performance of Ether-Functionalized Imidazoles as Physical Solvents for CO₂ Separations

Previously, we investigated 1-<i>n</i>-alkylimidazoles as low viscosity, low vapor pressure physical solvents for CO₂/CH₄ separation and noted a decrease in performance as the length of the <i>n</i>-alkyl chain was extended. Here, we examine imidazoles featuring oligo­(ethylene glycol) substituents (“PEG_<i>n</i>-imidazoles”) as an opportunity to improve upon the separation performance of this class of molecules. In the current work, we have characterized the density and the viscosity of PEG_<i>n</i>-imidazoles over the temperature range 20–80 °C. PEG_<i>n</i>-imidazoles are slightly more viscous than 1-<i>n</i>-alkylimidazoles but still fall below 20 cP. Ideal gas solubilities of CO₂ and CH₄ were measured in PEG_<i>n</i>-imidazoles at gas partial pressures of ∼5 bar and temperatures of 25–70 °C. Solubilities of CO₂ and CH₄ were both found to decrease with increasing temperature, with a stronger dependence for CO₂. However, better CO₂/CH₄ selectivity was achieved in PEG_<i>n</i>-imidazoles at lower operating temperatures than was observed for 1-<i>n</i>-alkylimidazoles. Physical properties and gas separation performances were correlated with fractional free volume calculated via COSMOtherm, as well as solubility parameters. The results show trends of decreased FFV when polar ether groups comprise the substituent, and that CO₂ solubility and solubility selectivity for CO₂/CH₄ are improved compared to their nonpolar, hydrocarbon-based analogues