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Evaluation of alkylimidazoles as physical solvents for CO2 / CH4 separation / Matthew S. Shannon in Industrial & engineering chemistry research, Vol. 51 N° 1 (Janvier 2012) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 51 N° 1 (Janvier 2012) . - pp. 515–522 Titre : Evaluation of alkylimidazoles as physical solvents for CO2 / CH4 separation Type de document : texte imprimé Auteurs : Matthew S. Shannon, Auteur ; Jason M. Tedstone, Auteur ; Scott P. O. Danielsen, Auteur Année de publication : 2012 Article en page(s) : pp. 515–522 Note générale : Chimie industrielle Langues : Anglais (eng) Mots-clés : Alkylimidazoles Résumé : 1-n-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-n-alkylimidazoles, and physical solvents currently used in industrial gas treating, the 1-n-alkylimidazole class of solvents warrants further investigation. Solubilities of CO2 and CH4 in a series of 1-n-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-n-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. DEWEY : 660 ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie202111k [article] Evaluation of alkylimidazoles as physical solvents for CO2 / CH4 separation [texte imprimé] / Matthew S. Shannon, Auteur ; Jason M. Tedstone, Auteur ; Scott P. O. Danielsen, Auteur . - 2012 . - pp. 515–522. Chimie industrielle Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 51 N° 1 (Janvier 2012) . - pp. 515–522 Mots-clés : Alkylimidazoles Résumé : 1-n-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-n-alkylimidazoles, and physical solvents currently used in industrial gas treating, the 1-n-alkylimidazole class of solvents warrants further investigation. Solubilities of CO2 and CH4 in a series of 1-n-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-n-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. DEWEY : 660 ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie202111k

Free volume as the basis of gas solubility and selectivity in imidazolium - based ionic liquids / Matthew S. Shannon in Industrial & engineering chemistry research, Vol. 51 N° 15 (Avril 2012) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 51 N° 15 (Avril 2012) . - pp. 5565-5576 Titre : Free volume as the basis of gas solubility and selectivity in imidazolium - based ionic liquids Type de document : texte imprimé Auteurs : Matthew S. Shannon, Auteur ; Jason M. Tedstone, Auteur ; Scott P. O. Danielsen, Auteur Année de publication : 2012 Article en page(s) : pp. 5565-5576 Note générale : Industrial chemistry Langues : Anglais (eng) Mots-clés : Ionic  liquid  Solubility  Free  volume Résumé : While molar volume-based models for gas solubility in ionic liquids (ILs) have been proposed, free volume within the IL can be shown to be the underlying property driving gas solubility and selectivity. Previously published observations as to the distinct differences in solubility trends for gases such as CH4 and N2 relative to CO2 in systematically varied ILs can be attributed to positive and negative effects arising from increasing free volume with increasing alkyl chain length. Through the use of COSMOtherm as a powerful and rapid tool to calculate free volumes in 165 existing and theoretical 1-n-alkyl-3- methylimidazolium ([Cnmim][X]) ILs, a previously unreported, yet speculated, critical underlying relationship between gas solubility in ILs is herein described These results build upon previous assertions that Regular Solution Theory is applicable to imidazolium-based ILs, which appeared to indicate that a global maximum had already been observed for CO2 solubility in imidazolium-based ILs. However, the findings of this computational study suggest that the perceived maximum in CO2 solubility might be exceeded through rational design of ILs. We observe that although Henry's constants in ILs are dependent on the inverse of molar volume and free volume, the volume-normalized solubility of CH4 and N2 are proportional to free volume, while CO2 is inversely proportional to the square root of free volume. Our free volume model is compared to experimental data for CO2/CH4 and CO2/N2 selectivity, and a nearly identical plot of selectivity relative to IL molar volume can be generated from the computational method alone. The overall implication is that large, highly delocalized anions paired with imidazolium cations that have minimally sized alkyl chains may hold the key to achieving greater CO2 solubility and selectivity in ILs. ISSN : 0888-5885 En ligne : http://cat.inist.fr/?aModele=afficheN&cpsidt=25815836 [article] Free volume as the basis of gas solubility and selectivity in imidazolium - based ionic liquids [texte imprimé] / Matthew S. Shannon, Auteur ; Jason M. Tedstone, Auteur ; Scott P. O. Danielsen, Auteur . - 2012 . - pp. 5565-5576. Industrial chemistry Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 51 N° 15 (Avril 2012) . - pp. 5565-5576 Mots-clés : Ionic  liquid  Solubility  Free  volume Résumé : While molar volume-based models for gas solubility in ionic liquids (ILs) have been proposed, free volume within the IL can be shown to be the underlying property driving gas solubility and selectivity. Previously published observations as to the distinct differences in solubility trends for gases such as CH4 and N2 relative to CO2 in systematically varied ILs can be attributed to positive and negative effects arising from increasing free volume with increasing alkyl chain length. Through the use of COSMOtherm as a powerful and rapid tool to calculate free volumes in 165 existing and theoretical 1-n-alkyl-3- methylimidazolium ([Cnmim][X]) ILs, a previously unreported, yet speculated, critical underlying relationship between gas solubility in ILs is herein described These results build upon previous assertions that Regular Solution Theory is applicable to imidazolium-based ILs, which appeared to indicate that a global maximum had already been observed for CO2 solubility in imidazolium-based ILs. However, the findings of this computational study suggest that the perceived maximum in CO2 solubility might be exceeded through rational design of ILs. We observe that although Henry's constants in ILs are dependent on the inverse of molar volume and free volume, the volume-normalized solubility of CH4 and N2 are proportional to free volume, while CO2 is inversely proportional to the square root of free volume. Our free volume model is compared to experimental data for CO2/CH4 and CO2/N2 selectivity, and a nearly identical plot of selectivity relative to IL molar volume can be generated from the computational method alone. The overall implication is that large, highly delocalized anions paired with imidazolium cations that have minimally sized alkyl chains may hold the key to achieving greater CO2 solubility and selectivity in ILs. ISSN : 0888-5885 En ligne : http://cat.inist.fr/?aModele=afficheN&cpsidt=25815836

Properties of alkylimidazoles as solvents for CO2 capture and comparisons to imidazolium-based ionic liquids / Matthew S. Shannon in Industrial & engineering chemistry research, Vol. 50 N° 14 (Juillet 2011) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 50 N° 14 (Juillet 2011) . - pp. 8665-8677 Titre : Properties of alkylimidazoles as solvents for CO2 capture and comparisons to imidazolium-based ionic liquids Type de document : texte imprimé Auteurs : Matthew S. Shannon, Auteur ; Jason E. Bara, Auteur Année de publication : 2011 Article en page(s) : pp. 8665-8677 Note générale : Chimie industrielle Langues : Anglais (eng) Mots-clés : Ionic  liquid  Carbon  dioxide Résumé : Density, viscosity, and CO2 solubility of a series of 10 1-n-alkylimidazoles with chain lengths ranging from methyl (C1) to tetradecyl (C14) were characterized. Density and viscosity values were comparable to many common organic solvents over a temperature range of 20-80 °C. The measured data were utilized to develop empirical models for these physical properties with respect to temperature and the contribution of the n-alkyl chain. Solubility of CO2 in 1-n-alkylimidazoles at ambient temperature (25 °C) and low pressures (3―7 atm) was found to be less than most common organic solvents, even though the 1-n-alkylimidazole motif offers opportunities to tune the molecule's solubility parameter. This effect was attributed to lower fractional free volume (FFV) that is available in molecules with systematically variable side chains. 1-n-Alkylimidazoles were less dense than most 1-n-alkyl-3-methylimidazolium-based ionic liquids (ILs), with differences ranging from 10 to 50%, based on contributions to increased density from the anion. However, much larger differences in viscosities were observed between the two classes of compounds, with ILs at least an order of magnitude more viscous than their neutral 1-n-alkylimidazole counterparts. Solubility levels of CO2 were similar in both types of solvents, indicating that no advantage (or disadvantage) in CO2 uptake is achieved by transforming a neutral 1-n-alkylimidazole to a charged IL solvent. While CO2 solubility levels in each are insufficient to provide a viable solvent for postcombustion CO2 capture applications, 1-n-alkylimidazoles can be used in combination with amines as a low-volatility, high-capacity solvent to capture CO2, using only inexpensive and readily available components. The viscosity of a highly CO2-rich liquid phase formed between monoethanolamine (MEA) and 1-butylimidazole was found to be 85―100 cP at 298 K, which is less viscous than many neat ILs. Initial data indicate 1-butylimidazole has a synergistic effect on CO2 capture as the solution can easily exceed the stoichiometric limitations of 2 mol of MEA/(1 mol of CO2), Thus, while certainly more volatile than IL-based analogues, 1-n-alkylimidazole solvents may offer some unique capabilities and advantages in CO2 capture processes. DEWEY : 660 ISSN : 0888-5885 En ligne : http://cat.inist.fr/?aModele=afficheN&cpsidt=24346905 [article] Properties of alkylimidazoles as solvents for CO2 capture and comparisons to imidazolium-based ionic liquids [texte imprimé] / Matthew S. Shannon, Auteur ; Jason E. Bara, Auteur . - 2011 . - pp. 8665-8677. Chimie industrielle Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 50 N° 14 (Juillet 2011) . - pp. 8665-8677 Mots-clés : Ionic  liquid  Carbon  dioxide Résumé : Density, viscosity, and CO2 solubility of a series of 10 1-n-alkylimidazoles with chain lengths ranging from methyl (C1) to tetradecyl (C14) were characterized. Density and viscosity values were comparable to many common organic solvents over a temperature range of 20-80 °C. The measured data were utilized to develop empirical models for these physical properties with respect to temperature and the contribution of the n-alkyl chain. Solubility of CO2 in 1-n-alkylimidazoles at ambient temperature (25 °C) and low pressures (3―7 atm) was found to be less than most common organic solvents, even though the 1-n-alkylimidazole motif offers opportunities to tune the molecule's solubility parameter. This effect was attributed to lower fractional free volume (FFV) that is available in molecules with systematically variable side chains. 1-n-Alkylimidazoles were less dense than most 1-n-alkyl-3-methylimidazolium-based ionic liquids (ILs), with differences ranging from 10 to 50%, based on contributions to increased density from the anion. However, much larger differences in viscosities were observed between the two classes of compounds, with ILs at least an order of magnitude more viscous than their neutral 1-n-alkylimidazole counterparts. Solubility levels of CO2 were similar in both types of solvents, indicating that no advantage (or disadvantage) in CO2 uptake is achieved by transforming a neutral 1-n-alkylimidazole to a charged IL solvent. While CO2 solubility levels in each are insufficient to provide a viable solvent for postcombustion CO2 capture applications, 1-n-alkylimidazoles can be used in combination with amines as a low-volatility, high-capacity solvent to capture CO2, using only inexpensive and readily available components. The viscosity of a highly CO2-rich liquid phase formed between monoethanolamine (MEA) and 1-butylimidazole was found to be 85―100 cP at 298 K, which is less viscous than many neat ILs. Initial data indicate 1-butylimidazole has a synergistic effect on CO2 capture as the solution can easily exceed the stoichiometric limitations of 2 mol of MEA/(1 mol of CO2), Thus, while certainly more volatile than IL-based analogues, 1-n-alkylimidazole solvents may offer some unique capabilities and advantages in CO2 capture processes. DEWEY : 660 ISSN : 0888-5885 En ligne : http://cat.inist.fr/?aModele=afficheN&cpsidt=24346905