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Isabel M Marrucho - One of the best experts on this subject based on the ideXlab platform.
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Imidazolium-Based Copoly(Ionic Liquid) Membranes for CO2/N2 Separation
2019Co-Authors: Pothanagandhi Nellepalli, Liliana C. Tomé, Kari Vijayakrishna, Isabel M MarruchoAbstract:The development of efficient carbon dioxide capture and separation technologies is at the forefront of the priorities in climate change policies. Poly(ionic Liquid)s (PILs) have been emerging as extremely promising materials for the fabrication of Membranes for CO2 separation. This work is a step forward to evaluate the effect of the PIL-based copolymers chemical structures in the preparation and performance of Membranes for CO2/N2 separation. In particular, imidazolium-based homo- and copolymers were synthesized by reversible addition–fragmentation chain transfer (RAFT) copolymerization of different imidazolium salts and characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) analysis. The membrane forming ability of the synthesized PILs, as well as the influence of different side chain groups (ethyl, pentyl, benzyl, and naphthyl) at the imidazolium ring, were evaluated using the solvent casting technique. In order to improve membrane forming ability and CO2 separation performance, different amounts of free ionic Liquid (IL), [C2mim][NTf2], were added into the synthesized homo- and copolymers, and PIL–IL composite Membranes were prepared. The CO2 and N2 permeation properties of the prepared free-standing PIL–IL Membranes were measured at 20 °C and 100 kPa, and the results obtained were compared through the Robeson plot
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ionic Liquid based materials a platform to design engineered co2 separation Membranes
Chemical Society Reviews, 2016Co-Authors: Liliana C Tome, Isabel M MarruchoAbstract:During the past decade, significant advances in ionic Liquid-based materials for the development of CO2 separation Membranes have been accomplished. This review presents a perspective on different strategies that use ionic Liquid-based materials as a unique tuneable platform to design task-specific advanced materials for CO2 separation Membranes. Based on compilation and analysis of the data hitherto reported, we provide a judicious assessment of the CO2 separation efficiency of different Membranes, and highlight breakthroughs and key challenges in this field. In particular, configurations such as supported ionic Liquid Membranes, polymer/ionic Liquid composite Membranes, gelled ionic Liquid Membranes and poly(ionic Liquid)-based Membranes are detailed, discussed and evaluated in terms of their efficiency, which is attributed to their chemical and structural features. Finally, an integrated perspective on technology, economy and sustainability is provided.
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co2 separation applying ionic Liquid mixtures the effect of mixing different anions on gas permeation through supported ionic Liquid Membranes
RSC Advances, 2013Co-Authors: Liliana C Tome, Isabel M Marrucho, David J S Patinha, Carmen S R Freire, Luis Paulo N RebeloAbstract:In order to increase flexibility in tailoring the permeability and selectivity of supported ionic Liquid Membranes (SILMs) for flue gas separation and natural gas purification, this work explores the use of ionic Liquid mixtures. For that purpose, gas permeation properties of CO2, CH4 and N2 in several binary ionic Liquid mixtures based on a common cation ([C2mim]+) and different anions such as bis(trifluoromethylsulfonyl)imide ([NTf2]−), acetate ([Ac]−), lactate ([Lac]−), dicyanamide ([DCA]−) and thiocyanate ([SCN]−) were measured at 293 K using a time-lag apparatus. In addition to gas permeation results, the thermophysical properties of those mixtures, namely viscosity and density, were also determined so that trends between the two types of properties could be evaluated. The results show that mixing [Ac]− or [Lac]− with [NTf2]− promotes the decrease of gas permeability and diffusivity of the SILMs based on those binary mixtures, essentially due to their high viscosities. The pure ionic Liquids containing anions with nitrile groups, [DCA]− or [SCN]−, and also their mixtures with [C2mim][NTf2] exhibit permselectivities ranging from 19.1 to 23.0 for CO2/CH4, and from 36.6 to 67.8 for CO2/N2, as a consequence of a reduction in the CH4 and N2 permeabilities, respectively. Furthermore, it is shown that mixing anions with different chemical features allows variations in ionic Liquid viscosity and molar volume that impact the gas permeation properties of SILMs, offering a clear pathway for the optimization of their CO2 separation performances.
Koen Binnemans - One of the best experts on this subject based on the ideXlab platform.
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highly selective separation of carbon dioxide from nitrogen and methane by nitrile glycol difunctionalized ionic Liquids in supported ionic Liquid Membranes silms
Journal of Physical Chemistry B, 2014Co-Authors: Sandra D. Hojniak, Ivo F J Vankelecom, Asim Laeeq Khan, Ian P. Silverwood, Wim Dehaen, Sergei G. Kazarian, Koen BinnemansAbstract:Novel difunctionalized ionic Liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic Liquid Membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature Liquidity of the pyrrolidinium and imidazolium ILs, the two classes of ILs benefit from the presence of a nitrile group in different ways. The difunctionalized pyrrolidinium ILs exhibit an increase in CO2 permeance, whereas the permeances of the contaminant gases rise negligibly, resulting in high gas separation selectivities. In the imidazolium ILs, the presence of a nitrile group does not always increase the CO2 permeance nor does it increase the CO2 solubility, as showed in situ by the ATR-FTIR spectroscopic method. High selectivity of these ILs is caused by the cons...
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Highly Selective Separation of Carbon Dioxide from Nitrogen and Methane by Nitrile/Glycol-Difunctionalized Ionic Liquids in Supported Ionic Liquid Membranes (SILMs)
2014Co-Authors: Sandra D. Hojniak, Ivo F J Vankelecom, Asim Laeeq Khan, Ian P. Silverwood, Wim Dehaen, Sergei G. Kazarian, Koen BinnemansAbstract:Novel difunctionalized ionic Liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic Liquid Membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature Liquidity of the pyrrolidinium and imidazolium ILs, the two classes of ILs benefit from the presence of a nitrile group in different ways. The difunctionalized pyrrolidinium ILs exhibit an increase in CO2 permeance, whereas the permeances of the contaminant gases rise negligibly, resulting in high gas separation selectivities. In the imidazolium ILs, the presence of a nitrile group does not always increase the CO2 permeance nor does it increase the CO2 solubility, as showed in situ by the ATR-FTIR spectroscopic method. High selectivity of these ILs is caused by the considerably reduced permeances of N2 and CH4, most likely due to the ability of the −CN group to reject the nonpolar contaminant gases. Apart from the CO2 solubility, IL–CO2 interactions and IL swelling were studied with the in situ ATR-FTIR spectroscopy. Different strengths of the IL–CO2 interactions were found to be the major difference between the two classes of ILs. The difunctionalized ILs interacted stronger with CO2 than the glycol-functionalized ILs, as manifested in the smaller bandwidths of the bending mode band of CO2 for the latter
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separation of carbon dioxide from nitrogen or methane by supported ionic Liquid Membranes silms influence of the cation charge of the ionic Liquid
Journal of Physical Chemistry B, 2013Co-Authors: Sandra D. Hojniak, Ivo F J Vankelecom, Asim Laeeq Khan, Wim Dehaen, Oldamur Holloczki, Barbara Kirchner, Koen BinnemansAbstract:Supported ionic Liquid Membranes (SILMs) are promising tools for the separation of carbon dioxide from other gases. In this paper, new imidazolium, pyrrolidinium, piperidinium, and morpholinium ionic Liquids with a triethylene glycol side chain and tosylate anions, as well as their symmetrical dicationic analogues, have been synthesized and incorporated into SILMs. The selectivities for CO2/N2 and CO2/CH4 separations have been measured. The selectivities exhibited by the dicationic ionic Liquids are up to two times higher than the values of the corresponding monocationic ionic Liquids. Quantum chemical calculations have been used to investigate the difference in the interaction of carbon dioxide with monocationic and dicationic ionic Liquids. The reason for the increased gas separation selectivity of the dicationic ionic Liquids is two-fold: (1) a decrease in permeance of nitrogen and methane through the ionic Liquid layer, presumably due to their less favorable interactions with the gases, while the perm...
Paul Scovazzo - One of the best experts on this subject based on the ideXlab platform.
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determination of the upper limits benchmarks and critical properties for gas separations using stabilized room temperature ionic Liquid Membranes silms for the purpose of guiding future research
Journal of Membrane Science, 2009Co-Authors: Paul ScovazzoAbstract:Abstract The literature reports that supported ionic Liquid Membranes (SILMs) outperform standard polymers for the separations of CO 2 /N 2 and CO 2 /CH 4 , even under continuous flow mixed gas conditions. Before the expenditure of more resources to develop new room temperature ionic Liquids (RTILs) and SILMs, it is time to consider what benchmarks for SILM performance exist and if upper limits could be projected based on the physical chemistry of RTILs. At this juncture, we should ask if the current research efforts are properly focused based on the successes and failures in the literature. We summarize literature data, along with adding new data, on the SILM permeabilities and selectivities for the following gas pairs: CO 2 /N 2 , CO 2 /CH 4 , O 2 /N 2 , ethylene/ethane, propylene/propane, 1-butene/butane, and 1,3-butadiene/butane. The analysis predicts a maximum CO 2 -permeability for SILMs and an upper bound for permeability selectivity vs. CO 2 -permeability with respect to the CO 2 /N 2 and CO 2 /CH 4 separations. Also summarized are the representative successes and failures for improving the separation performance of SILMs via functionalization and facilitated transport in the context of the CO 2 /N 2 , CO 2 /CH 4 , and olefin/paraffin separations. In the context of the CO 2 -separations, the analysis recommends a number of future research foci including research into SILMs cast from RTILs with smaller molar volumes. In the context of olefin/paraffin separations, the preliminary data is encouraging when considering the use of facilitated transport via silver carriers. Since RTIL-solvent/solvent interactions dominate in terminating the overall SILM performance, past attempts at enhancing solute/solvent interactions via the addition of functional groups to the RTILs have not produced SILMs with better separation performance compared to the unfunctionalized RTILs. Future research into functionalized RTILs needs to consider the changes to the dominant solvent/solvent interactions and not just the solute/solvent interactions.
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long term continuous mixed gas dry fed co2 ch4 and co2 n2 separation performance and selectivities for room temperature ionic Liquid Membranes
Journal of Membrane Science, 2009Co-Authors: Paul Scovazzo, Drew Havard, Mike Mcshea, Sarah Mixon, David MorganAbstract:Abstract Previously, we reported on using room temperature ionic Liquids (RTILs) in place of traditional solvents in Liquid Membranes and showed that stabilized RTIL-Membranes outperformed standard polymers for the separations of CO 2 /CH 4 and CO 2 /N 2 (considering ideal gas permeabilities). Here, we report on mixed-gas permeances and selectivities for the gas pairs CO 2 /CH 4 and CO 2 /N 2 using continuous flows of the mixed gases at various carbon dioxide concentrations (up to 2 bars of CO 2 partial pressure). Under mixed-gas test conditions, three of the tested Membranes still operated with commercially attractive mixed-gas selectivity combined with CO 2 -permeability for CO 2 /CH 4 separations. In addition, one of the tested Membranes is, potentially, economically viable for CO 2 capture from flue gas. We answer three objections to reduction-to-practice of RTIL-Membranes for gas separations; namely, mixed-gas operations did not reduced the gas selectivities, Membranes give advantageous performance even under dry gas feed conditions, and we achieved long-term stability in continuous operation, up to 106 days, without performance degradation. Furthermore, the RTIL-Membranes operated under CO 2 -partial pressures of at least 207 kPa without decrease in separation ability. The RTIL-Membranes tested include [emim][BF 4 ], [emim][dca], [emim][CF 3 SO 3 ], [emim][Tf 2 N], and [bmim][BETI].
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gas separations using non hexafluorophosphate pf6 anion supported ionic Liquid Membranes
Journal of Membrane Science, 2004Co-Authors: Paul Scovazzo, Jesse Kieft, Daniel A Finan, Carl A Koval, Daniel L Dubois, Richard D NobleAbstract:Abstract Previously, we reported on using Room temperature ionic Liquids (RTILs) in place of traditional solvents for supported Liquid Membranes to take advantage of their unique properties. This previous work used RTILs with the hexafluorophosphate [PF 6 ] − anion. However, the [PF 6 ] − anion in the presence of water can break down into HF. In the current work, we studied RTIL-Membranes made from the following water stable anions: bis(trifluoromethanesulfonyl)amide [Tf 2 N] − , trifluoromethanesulfone [CF 3 SO 3 ] − , chloride [Cl] − , and dicyanamide [dca] − . We report CO 2 permeabilities of 350 barrers (for [Cl] − ) to 1000 barrers (for [Tf 2 N] − ) combined with CO 2 /N 2 ideal selectivities of 15 (for [Cl] − ) to 61 (for [dca] − ). Note that these permeability/selectivities place RTIL-Membranes above the upper-bound in a CO 2 /N 2 Robeson plot of representative polymers. The CO 2 /CH 4 ideal selectivities range from 4 (for [Cl] − ) to 20 (for [dca] − ), thereby placing the [dca]-membrane above the upper-bound for the CO 2 /CH 4 Robeson plot.
Sandra D. Hojniak - One of the best experts on this subject based on the ideXlab platform.
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highly selective separation of carbon dioxide from nitrogen and methane by nitrile glycol difunctionalized ionic Liquids in supported ionic Liquid Membranes silms
Journal of Physical Chemistry B, 2014Co-Authors: Sandra D. Hojniak, Ivo F J Vankelecom, Asim Laeeq Khan, Ian P. Silverwood, Wim Dehaen, Sergei G. Kazarian, Koen BinnemansAbstract:Novel difunctionalized ionic Liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic Liquid Membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature Liquidity of the pyrrolidinium and imidazolium ILs, the two classes of ILs benefit from the presence of a nitrile group in different ways. The difunctionalized pyrrolidinium ILs exhibit an increase in CO2 permeance, whereas the permeances of the contaminant gases rise negligibly, resulting in high gas separation selectivities. In the imidazolium ILs, the presence of a nitrile group does not always increase the CO2 permeance nor does it increase the CO2 solubility, as showed in situ by the ATR-FTIR spectroscopic method. High selectivity of these ILs is caused by the cons...
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Highly Selective Separation of Carbon Dioxide from Nitrogen and Methane by Nitrile/Glycol-Difunctionalized Ionic Liquids in Supported Ionic Liquid Membranes (SILMs)
2014Co-Authors: Sandra D. Hojniak, Ivo F J Vankelecom, Asim Laeeq Khan, Ian P. Silverwood, Wim Dehaen, Sergei G. Kazarian, Koen BinnemansAbstract:Novel difunctionalized ionic Liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic Liquid Membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature Liquidity of the pyrrolidinium and imidazolium ILs, the two classes of ILs benefit from the presence of a nitrile group in different ways. The difunctionalized pyrrolidinium ILs exhibit an increase in CO2 permeance, whereas the permeances of the contaminant gases rise negligibly, resulting in high gas separation selectivities. In the imidazolium ILs, the presence of a nitrile group does not always increase the CO2 permeance nor does it increase the CO2 solubility, as showed in situ by the ATR-FTIR spectroscopic method. High selectivity of these ILs is caused by the considerably reduced permeances of N2 and CH4, most likely due to the ability of the −CN group to reject the nonpolar contaminant gases. Apart from the CO2 solubility, IL–CO2 interactions and IL swelling were studied with the in situ ATR-FTIR spectroscopy. Different strengths of the IL–CO2 interactions were found to be the major difference between the two classes of ILs. The difunctionalized ILs interacted stronger with CO2 than the glycol-functionalized ILs, as manifested in the smaller bandwidths of the bending mode band of CO2 for the latter
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separation of carbon dioxide from nitrogen or methane by supported ionic Liquid Membranes silms influence of the cation charge of the ionic Liquid
Journal of Physical Chemistry B, 2013Co-Authors: Sandra D. Hojniak, Ivo F J Vankelecom, Asim Laeeq Khan, Wim Dehaen, Oldamur Holloczki, Barbara Kirchner, Koen BinnemansAbstract:Supported ionic Liquid Membranes (SILMs) are promising tools for the separation of carbon dioxide from other gases. In this paper, new imidazolium, pyrrolidinium, piperidinium, and morpholinium ionic Liquids with a triethylene glycol side chain and tosylate anions, as well as their symmetrical dicationic analogues, have been synthesized and incorporated into SILMs. The selectivities for CO2/N2 and CO2/CH4 separations have been measured. The selectivities exhibited by the dicationic ionic Liquids are up to two times higher than the values of the corresponding monocationic ionic Liquids. Quantum chemical calculations have been used to investigate the difference in the interaction of carbon dioxide with monocationic and dicationic ionic Liquids. The reason for the increased gas separation selectivity of the dicationic ionic Liquids is two-fold: (1) a decrease in permeance of nitrogen and methane through the ionic Liquid layer, presumably due to their less favorable interactions with the gases, while the perm...
Liliana C Tome - One of the best experts on this subject based on the ideXlab platform.
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ionic Liquid based materials a platform to design engineered co2 separation Membranes
Chemical Society Reviews, 2016Co-Authors: Liliana C Tome, Isabel M MarruchoAbstract:During the past decade, significant advances in ionic Liquid-based materials for the development of CO2 separation Membranes have been accomplished. This review presents a perspective on different strategies that use ionic Liquid-based materials as a unique tuneable platform to design task-specific advanced materials for CO2 separation Membranes. Based on compilation and analysis of the data hitherto reported, we provide a judicious assessment of the CO2 separation efficiency of different Membranes, and highlight breakthroughs and key challenges in this field. In particular, configurations such as supported ionic Liquid Membranes, polymer/ionic Liquid composite Membranes, gelled ionic Liquid Membranes and poly(ionic Liquid)-based Membranes are detailed, discussed and evaluated in terms of their efficiency, which is attributed to their chemical and structural features. Finally, an integrated perspective on technology, economy and sustainability is provided.
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co2 separation applying ionic Liquid mixtures the effect of mixing different anions on gas permeation through supported ionic Liquid Membranes
RSC Advances, 2013Co-Authors: Liliana C Tome, Isabel M Marrucho, David J S Patinha, Carmen S R Freire, Luis Paulo N RebeloAbstract:In order to increase flexibility in tailoring the permeability and selectivity of supported ionic Liquid Membranes (SILMs) for flue gas separation and natural gas purification, this work explores the use of ionic Liquid mixtures. For that purpose, gas permeation properties of CO2, CH4 and N2 in several binary ionic Liquid mixtures based on a common cation ([C2mim]+) and different anions such as bis(trifluoromethylsulfonyl)imide ([NTf2]−), acetate ([Ac]−), lactate ([Lac]−), dicyanamide ([DCA]−) and thiocyanate ([SCN]−) were measured at 293 K using a time-lag apparatus. In addition to gas permeation results, the thermophysical properties of those mixtures, namely viscosity and density, were also determined so that trends between the two types of properties could be evaluated. The results show that mixing [Ac]− or [Lac]− with [NTf2]− promotes the decrease of gas permeability and diffusivity of the SILMs based on those binary mixtures, essentially due to their high viscosities. The pure ionic Liquids containing anions with nitrile groups, [DCA]− or [SCN]−, and also their mixtures with [C2mim][NTf2] exhibit permselectivities ranging from 19.1 to 23.0 for CO2/CH4, and from 36.6 to 67.8 for CO2/N2, as a consequence of a reduction in the CH4 and N2 permeabilities, respectively. Furthermore, it is shown that mixing anions with different chemical features allows variations in ionic Liquid viscosity and molar volume that impact the gas permeation properties of SILMs, offering a clear pathway for the optimization of their CO2 separation performances.