Defect-free asymmetric Matrimid® gas separation membranes using dihydrolevoglucosenone (Cyrene™) as a greener polar aprotic solvent than traditional solvents

Alexander T. Bridge; Noah P. Wamble; Matthew S. Santoso; Joan F. Brennecke; Benny D. Freeman

doi:10.1016/j.memsci.2023.122221

Defect-free asymmetric Matrimid® gas separation membranes using dihydrolevoglucosenone (Cyrene™) as a greener polar aprotic solvent than traditional solvents

Alexander T. Bridge, Noah P. Wamble, Matthew S. Santoso, Joan F. Brennecke, Benny D. Freeman

Research output: Contribution to journal › Article › Research › peer-review

4 Citations (Scopus)

Abstract

Industrial membrane manufacturing via nonsolvent-induced phase separation (NIPS) generates large volumes of solvent-contaminated wastewater. An effective solution is to reduce the inherent toxicity of NIPS casting solutions, or dopes, by substituting traditional polar aprotic solvents with potentially benign alternatives such as dihydrolevoglucosenone (Cyrene™). This study demonstrates the reproducible preparation of high-flux defect-free asymmetric Matrimid® gas separation membranes via dry/wet NIPS using Cyrene™ as a majority dope formulation component. Defect-free membrane performance, as benchmarked for pure gas H₂/N₂ and O₂/N₂ separations, is maximized with high loadings of Cyrene™ relative to the volatile co-solvent tetrahydrofuran (THF) in casting solutions (volume ratios up to 3.20:1), which exceed the value of 1.68:1 used for Udel® polysulfone in our previous study. Cyrene™'s poor thermodynamic compatibility with the water coagulant and ability to produce highly viscous dopes ensure minimization and/or elimination of sublayer macrovoids while enabling defect-free membrane preparation at low (i.e., 12–14 wt %) Matrimid® and THF concentrations. Defect-free H₂ permeance values up to 164 ± 14 GPU were achieved with a combination of high Cyrene™:THF volume ratios, low Matrimid® concentrations, and short dry step times (i.e., <15 s). Membrane performance achieved in this study matches or exceeds other literature reports of defect-free asymmetric Matrimid® membranes prepared with traditional NIPS solvents.

Original language	English
Article number	122221
Number of pages	13
Journal	Journal of Membrane Science
Volume	691
DOIs	https://doi.org/10.1016/j.memsci.2023.122221
Publication status	Published - 5 Feb 2024
Externally published	Yes

Keywords

Defect-free
Dihydrolevoglucosenone (Cyrene™)
Gas separation
Matrimid®
Nonsolvent-induced phase separation

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10.1016/j.memsci.2023.122221

Cite this

@article{62f60ef42f2a4cae84d3e588b737d921,

title = "Defect-free asymmetric Matrimid{\textregistered} gas separation membranes using dihydrolevoglucosenone (Cyrene{\texttrademark}) as a greener polar aprotic solvent than traditional solvents",

abstract = "Industrial membrane manufacturing via nonsolvent-induced phase separation (NIPS) generates large volumes of solvent-contaminated wastewater. An effective solution is to reduce the inherent toxicity of NIPS casting solutions, or dopes, by substituting traditional polar aprotic solvents with potentially benign alternatives such as dihydrolevoglucosenone (Cyrene{\texttrademark}). This study demonstrates the reproducible preparation of high-flux defect-free asymmetric Matrimid{\textregistered} gas separation membranes via dry/wet NIPS using Cyrene{\texttrademark} as a majority dope formulation component. Defect-free membrane performance, as benchmarked for pure gas H2/N2 and O2/N2 separations, is maximized with high loadings of Cyrene{\texttrademark} relative to the volatile co-solvent tetrahydrofuran (THF) in casting solutions (volume ratios up to 3.20:1), which exceed the value of 1.68:1 used for Udel{\textregistered} polysulfone in our previous study. Cyrene{\texttrademark}'s poor thermodynamic compatibility with the water coagulant and ability to produce highly viscous dopes ensure minimization and/or elimination of sublayer macrovoids while enabling defect-free membrane preparation at low (i.e., 12–14 wt %) Matrimid{\textregistered} and THF concentrations. Defect-free H2 permeance values up to 164 ± 14 GPU were achieved with a combination of high Cyrene{\texttrademark}:THF volume ratios, low Matrimid{\textregistered} concentrations, and short dry step times (i.e., <15 s). Membrane performance achieved in this study matches or exceeds other literature reports of defect-free asymmetric Matrimid{\textregistered} membranes prepared with traditional NIPS solvents.",

keywords = "Defect-free, Dihydrolevoglucosenone (Cyrene{\texttrademark}), Gas separation, Matrimid{\textregistered}, Nonsolvent-induced phase separation",

author = "Bridge, {Alexander T.} and Wamble, {Noah P.} and Santoso, {Matthew S.} and Brennecke, {Joan F.} and Freeman, {Benny D.}",

note = "Funding Information: The dry/wet NIPS process produces membranes with an asymmetric structure characterized by a porous sublayer supporting a nonporous gas-selective skin layer. The skin layer is typically limited to ∼10–100 nm of effective thickness to maximize gas flux [1,2,10]. The porous sublayer ranges from 10 to 100+ μm in thickness and mechanically supports the skin layer. The sublayer can exhibit one of several morphologies ranging from a “spongy” network of closed cell isolated spherical pores to an open and highly interconnected network of micropores and finger-like macrovoids [ 11–14]. More open sublayers are amenable to high penetrant flux at the expense of mechanical stability. Conversely, less porous and/or interconnected sublayers favor mechanical integrity at the expense of flux and, in some cases, selectivity [9,15,16]. Macrovoid-free sublayers are typically favored for gas separation membranes, which typically encounter high pressure gradients in operation [1,2,17].Powdered Matrimid{\textregistered} 5218 PI was kindly provided by Air Liquide and used as received. A low cyclic dimer grade of Udel{\textregistered} P3500 MB7 PSf was kindly provided by Solvay S.A. and used as received. Triple detection gel permeation chromatography absolute molecular weight measurements, which are reported in Section S1 of the supporting information (SI), were performed on PI by EAG Laboratories (Maryland Heights, MO). Molecular weight data for PSf is available elsewhere [9]. PI powder was dried under vacuum at 150 °C prior to use in membrane preparation to remove any residual water.Presently, no water-Cyrene{\texttrademark} or EtOH-Cyrene{\texttrademark} VLE behavior has been reported in the literature. In aqueous systems, Cyrene{\texttrademark} reversibly reacts to form CGD, as shown in Fig. 1. The water-Cyrene{\texttrademark} reaction rate and equilibrium depend on the initial mixture composition, as discussed in Section S5 of the SI and in other studies [36]. Because the complex ternary mixture resulting from this binary pairing prevented experimental VLE characterization, UNIFAC χ12 estimates are used instead to describe theoretical binary mixtures of water with pure Cyrene{\texttrademark} and pure CGD. As discussed in Section S5 of the supporting information (SI), no reaction is observed between Cyrene{\texttrademark} and EtOH, so EtOH-CGD χ12 values are not needed.If significant amounts of CGD are formed then the effective thermodynamic compatibility of water and Cyrene{\texttrademark} should be enhanced via hydrogen bonding between water and CGD's diol group. This hypothesis is supported by the lower UNIFAC χ12 value predicted for water-CGD mixtures than for water-Cyrene{\texttrademark} mixtures (i.e., 0.33 vs. 0.92 in Table 2). However, the FTIR analysis set forth in SI Section S5 indicates that CGD formation is slow (i.e., equilibrium is reached over a timescale of minutes) when Cyrene{\texttrademark} is present in excess relative to water, which is expected within the membrane phase during NIPS. Moreover, based on light transmission measurements discussed in Section S9 of the SI, Cyrene{\texttrademark}-based dry/wet NIPS membranes prepared in this study generally form on a timescale of seconds (cf. Fig. S12 and Table S5) after immersion in water. Therefore, we conclude that the influence of CGD on water influx/Cyrene{\texttrademark} outflux during NIPS is likely negligible. As a result, the thermodynamic compatibility when using Cyrene{\texttrademark} as a solvent and water as a coagulant is best described by χ12 between Cyrene{\texttrademark} and water, χ12 = 0.92, neglecting any impact of CGD formation.The authors thank Ed Sanders and Air Liquide for providing the Matrimid{\textregistered} used for this study. The authors also thank Adrian Rylski for assistance with NMR experiments. This manuscript is based upon work supported by the National Science Foundation (NSF) under Cooperative Agreement No. EEC-1647722. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF. The author also thanks the NSF Center for Dynamics and Control of Materials for providing equipment for rheology and light scattering measurements. Funding Information: The authors thank Ed Sanders and Air Liquide for providing the Matrimid{\textregistered} used for this study. The authors also thank Adrian Rylski for assistance with NMR experiments. This manuscript is based upon work supported by the National Science Foundation (NSF) under Cooperative Agreement No. EEC-1647722 . Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF. The author also thanks the NSF Center for Dynamics and Control of Materials for providing equipment for rheology and light scattering measurements. Publisher Copyright: {\textcopyright} 2023 Elsevier B.V.",

year = "2024",

month = feb,

day = "5",

doi = "10.1016/j.memsci.2023.122221",

language = "English",

volume = "691",

journal = "Journal of Membrane Science",

issn = "0376-7388",

publisher = "Elsevier BV",

}

Defect-free asymmetric Matrimid® gas separation membranes using dihydrolevoglucosenone (Cyrene™) as a greener polar aprotic solvent than traditional solvents. / Bridge, Alexander T.; Wamble, Noah P.; Santoso, Matthew S. et al.
In: Journal of Membrane Science, Vol. 691, 122221, 05.02.2024.

Research output: Contribution to journal › Article › Research › peer-review

TY - JOUR

T1 - Defect-free asymmetric Matrimid® gas separation membranes using dihydrolevoglucosenone (Cyrene™) as a greener polar aprotic solvent than traditional solvents

AU - Bridge, Alexander T.

AU - Wamble, Noah P.

AU - Santoso, Matthew S.

AU - Brennecke, Joan F.

AU - Freeman, Benny D.

N1 - Funding Information: The dry/wet NIPS process produces membranes with an asymmetric structure characterized by a porous sublayer supporting a nonporous gas-selective skin layer. The skin layer is typically limited to ∼10–100 nm of effective thickness to maximize gas flux [1,2,10]. The porous sublayer ranges from 10 to 100+ μm in thickness and mechanically supports the skin layer. The sublayer can exhibit one of several morphologies ranging from a “spongy” network of closed cell isolated spherical pores to an open and highly interconnected network of micropores and finger-like macrovoids [ 11–14]. More open sublayers are amenable to high penetrant flux at the expense of mechanical stability. Conversely, less porous and/or interconnected sublayers favor mechanical integrity at the expense of flux and, in some cases, selectivity [9,15,16]. Macrovoid-free sublayers are typically favored for gas separation membranes, which typically encounter high pressure gradients in operation [1,2,17].Powdered Matrimid® 5218 PI was kindly provided by Air Liquide and used as received. A low cyclic dimer grade of Udel® P3500 MB7 PSf was kindly provided by Solvay S.A. and used as received. Triple detection gel permeation chromatography absolute molecular weight measurements, which are reported in Section S1 of the supporting information (SI), were performed on PI by EAG Laboratories (Maryland Heights, MO). Molecular weight data for PSf is available elsewhere [9]. PI powder was dried under vacuum at 150 °C prior to use in membrane preparation to remove any residual water.Presently, no water-Cyrene™ or EtOH-Cyrene™ VLE behavior has been reported in the literature. In aqueous systems, Cyrene™ reversibly reacts to form CGD, as shown in Fig. 1. The water-Cyrene™ reaction rate and equilibrium depend on the initial mixture composition, as discussed in Section S5 of the SI and in other studies [36]. Because the complex ternary mixture resulting from this binary pairing prevented experimental VLE characterization, UNIFAC χ12 estimates are used instead to describe theoretical binary mixtures of water with pure Cyrene™ and pure CGD. As discussed in Section S5 of the supporting information (SI), no reaction is observed between Cyrene™ and EtOH, so EtOH-CGD χ12 values are not needed.If significant amounts of CGD are formed then the effective thermodynamic compatibility of water and Cyrene™ should be enhanced via hydrogen bonding between water and CGD's diol group. This hypothesis is supported by the lower UNIFAC χ12 value predicted for water-CGD mixtures than for water-Cyrene™ mixtures (i.e., 0.33 vs. 0.92 in Table 2). However, the FTIR analysis set forth in SI Section S5 indicates that CGD formation is slow (i.e., equilibrium is reached over a timescale of minutes) when Cyrene™ is present in excess relative to water, which is expected within the membrane phase during NIPS. Moreover, based on light transmission measurements discussed in Section S9 of the SI, Cyrene™-based dry/wet NIPS membranes prepared in this study generally form on a timescale of seconds (cf. Fig. S12 and Table S5) after immersion in water. Therefore, we conclude that the influence of CGD on water influx/Cyrene™ outflux during NIPS is likely negligible. As a result, the thermodynamic compatibility when using Cyrene™ as a solvent and water as a coagulant is best described by χ12 between Cyrene™ and water, χ12 = 0.92, neglecting any impact of CGD formation.The authors thank Ed Sanders and Air Liquide for providing the Matrimid® used for this study. The authors also thank Adrian Rylski for assistance with NMR experiments. This manuscript is based upon work supported by the National Science Foundation (NSF) under Cooperative Agreement No. EEC-1647722. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF. The author also thanks the NSF Center for Dynamics and Control of Materials for providing equipment for rheology and light scattering measurements. Funding Information: The authors thank Ed Sanders and Air Liquide for providing the Matrimid® used for this study. The authors also thank Adrian Rylski for assistance with NMR experiments. This manuscript is based upon work supported by the National Science Foundation (NSF) under Cooperative Agreement No. EEC-1647722 . Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF. The author also thanks the NSF Center for Dynamics and Control of Materials for providing equipment for rheology and light scattering measurements. Publisher Copyright: © 2023 Elsevier B.V.

PY - 2024/2/5

Y1 - 2024/2/5

N2 - Industrial membrane manufacturing via nonsolvent-induced phase separation (NIPS) generates large volumes of solvent-contaminated wastewater. An effective solution is to reduce the inherent toxicity of NIPS casting solutions, or dopes, by substituting traditional polar aprotic solvents with potentially benign alternatives such as dihydrolevoglucosenone (Cyrene™). This study demonstrates the reproducible preparation of high-flux defect-free asymmetric Matrimid® gas separation membranes via dry/wet NIPS using Cyrene™ as a majority dope formulation component. Defect-free membrane performance, as benchmarked for pure gas H2/N2 and O2/N2 separations, is maximized with high loadings of Cyrene™ relative to the volatile co-solvent tetrahydrofuran (THF) in casting solutions (volume ratios up to 3.20:1), which exceed the value of 1.68:1 used for Udel® polysulfone in our previous study. Cyrene™'s poor thermodynamic compatibility with the water coagulant and ability to produce highly viscous dopes ensure minimization and/or elimination of sublayer macrovoids while enabling defect-free membrane preparation at low (i.e., 12–14 wt %) Matrimid® and THF concentrations. Defect-free H2 permeance values up to 164 ± 14 GPU were achieved with a combination of high Cyrene™:THF volume ratios, low Matrimid® concentrations, and short dry step times (i.e., <15 s). Membrane performance achieved in this study matches or exceeds other literature reports of defect-free asymmetric Matrimid® membranes prepared with traditional NIPS solvents.

AB - Industrial membrane manufacturing via nonsolvent-induced phase separation (NIPS) generates large volumes of solvent-contaminated wastewater. An effective solution is to reduce the inherent toxicity of NIPS casting solutions, or dopes, by substituting traditional polar aprotic solvents with potentially benign alternatives such as dihydrolevoglucosenone (Cyrene™). This study demonstrates the reproducible preparation of high-flux defect-free asymmetric Matrimid® gas separation membranes via dry/wet NIPS using Cyrene™ as a majority dope formulation component. Defect-free membrane performance, as benchmarked for pure gas H2/N2 and O2/N2 separations, is maximized with high loadings of Cyrene™ relative to the volatile co-solvent tetrahydrofuran (THF) in casting solutions (volume ratios up to 3.20:1), which exceed the value of 1.68:1 used for Udel® polysulfone in our previous study. Cyrene™'s poor thermodynamic compatibility with the water coagulant and ability to produce highly viscous dopes ensure minimization and/or elimination of sublayer macrovoids while enabling defect-free membrane preparation at low (i.e., 12–14 wt %) Matrimid® and THF concentrations. Defect-free H2 permeance values up to 164 ± 14 GPU were achieved with a combination of high Cyrene™:THF volume ratios, low Matrimid® concentrations, and short dry step times (i.e., <15 s). Membrane performance achieved in this study matches or exceeds other literature reports of defect-free asymmetric Matrimid® membranes prepared with traditional NIPS solvents.

KW - Defect-free

KW - Dihydrolevoglucosenone (Cyrene™)

KW - Gas separation

KW - Matrimid®

KW - Nonsolvent-induced phase separation

UR - http://www.scopus.com/inward/record.url?scp=85176230493&partnerID=8YFLogxK

U2 - 10.1016/j.memsci.2023.122221

DO - 10.1016/j.memsci.2023.122221

M3 - Article

AN - SCOPUS:85176230493

SN - 0376-7388

VL - 691

JO - Journal of Membrane Science

JF - Journal of Membrane Science

M1 - 122221

ER -

Defect-free asymmetric Matrimid® gas separation membranes using dihydrolevoglucosenone (Cyrene™) as a greener polar aprotic solvent than traditional solvents

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Keywords

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