Hydrogen sorption in polymers for membrane applications

Smith, Zachary P.; Tiwari, Rajkiran R.; Murphy, Thomas M.; Sanders, David; Gleason, Kristofer L.; Paul, Donald R; Freeman, Benny D.

doi:10.1016/j.polymer.2013.04.006

Cited by 47 publications

(98 citation statements)

References 49 publications

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“…Previously reported solubility values by Chiou et al 29 and Fan et al 30 were calculated from the diffusion time-lag method, which is prone to errors especially for polymers with low gas solubility. 51 The solubility data for He and H 2 , measured using the barometric method in this study agree reasonably well with the gravimetrically measured values reported by Smith et al polymers. The deviation in slope for Nafion ® compared to other perfluorinated polymers may be due to the hydrophilic sulfonic acid group that creates an additional unfavorable environment for sorption of the hydrocarbon penetrants in the polymer matrix.…”

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confidence: 91%

Gas Sorption, Diffusion, and Permeation in Nafion

2015

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The gas permeability of dry Nafion ® films was determined at 2 atm and 35 °C for He, H 2 , N 2 , O 2 , CO 2 , CH 4 , C 2 H 6 and C 3 H 8 . In addition, gas sorption isotherms were determined by gravimetric and barometric techniques as a function of pressure up to 20 atm. Nafion Barrer, respectively; all other gases exhibited low permeability that decreased significantly as penetrant size increased. Dry Nafion ® was characterized by extraordinarily high selectivities:He/H 2 = 5.2, He/CH 4 = 445, He/C 2 H 6 = 1275, He/C 3 H 8 = 7400, CO 2 /CH 4 = 28, CO 2 /C 2 H 6 = 79,

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confidence: 91%

Gas Sorption, Diffusion, and Permeation in Nafion

2015

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“…Hydrogen solubility in HAB-6FDA was reported by Smith et al 25 . As typically observed for light gas sorption in polymers, hydrogen sorption isotherms are almost linear with pressure, and solubility decreases with increasing temperature.…”

Section: Estimation Of Lattice Fluid Parameters For Hab-6fda and Tr-smentioning

confidence: 74%

“…2 was used to simultaneously fit, for each polymer, experimental infinite dilution solubility coefficients for different light gases, i.e. H2, He, N2, CH4 and CO2, at multiple temperatures, ranging from -10 to 50°C 25,26,27 . In this procedure, the polymer characteristic lattice fluid parameters, T*, p* and *, were treated as fitting parameters and adjusted to the experimental sorption data, while the polymer-penetrant interaction parameter, 12 k , was set equal to zero 12 .…”

Section: Estimation Of Lattice Fluid Parameters For Hab-6fda and Tr-smentioning

confidence: 99%

“…In summary, hydrogen, nitrogen and methane solubility isotherms in HAB-6FDA can be predicted at multiple temperatures and up to 6MPa with one adjustable parameter per gas (i.e., k from zero for hydrogen might also be partially due to the uncertainty in the hydrogen sorption data, which is greater than that of other more condensable gases, since hydrogen is only sparingly soluble in polymers 17,25,26 .…”

Section: Estimation Of Lattice Fluid Parameters For Hab-6fda and Tr-smentioning

confidence: 99%

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Nonequilibrium Lattice Fluid Modeling of Gas Solubility in HAB-6FDA Polyimide and Its Thermally Rearranged Analogues

et al. 2016

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For the first time, a theoretical analysis of gas sorption, based on the non-equilibrium lattice fluid (NELF) model, in chemically-imidized HAB-6FDA polyimide and its thermally rearranged analogs is presented. Due to the inaccessibility of pVT data in the rubbery region, the characteristic lattice fluid parameters of the polymers considered in this study were obtained from a collection of infinite dilution solubility data at multiple temperatures. Hydrogen, nitrogen and methane sorption isotherms at 35°C were fit to the NELF model using one adjustable parameter, i.e., the polymer-penetrant binary interaction parameter, 12 k . The optimal value of 12 k for each polymer-penetrant pair was used to predict hydrogen, nitrogen and methane sorption isotherms at other temperatures and at pressures up to 6 MPa. For carbon dioxide, a second adjustable parameter, the swelling coefficient, was introduced to account for sorption-induced matrix dilation. The ideal solubility-selectivity is also predicted for several gas pairs. The increase in gas sorption in thermally rearranged samples relative to their polyimide precursor is essentially due to entropic effects, i.e., to the increase in non-equilibrium fractional free volume during thermal rearrangement.

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“…Hydrogen and helium sorption in polymers has attracted interest because of the importance of these gases in membrane-based separation processes [1,2]. In many industrial processes, hydrogen needs to be recovered from purge gas streams or have its composition adjusted for syngas feeds [3].…”

Section: Introductionmentioning

confidence: 99%

Predictive calculation of hydrogen and helium solubility in glassy and rubbery polymers

Galizia

Smith

Sarti

et al. 2015

Journal of Membrane Science

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a b s t r a c tHydrogen sorption isotherms in selected glassy and rubbery polymers, available over a wide range of temperatures ( À 20 to 70 1C) and pressures (0-60 atm) have been modeled and correlated using equilibrium and non-equilibrium thermodynamic models based on the lattice fluid theory. A good representation of the experimental data can be obtained for the systems considered over the whole range of pressures and temperatures inspected by using just one fitting parameter, under the fundamental assumption that hydrogen behaves as a non-swelling penetrant. The theoretical estimates of infinite dilution solubility coefficients are in excellent agreement with the experimental data. Remarkably, the model analysis allows a reliable estimate of the isosteric heat of sorption and its dependence on the hydrogen concentration over the whole range of pressures considered. A similar theoretical analysis has been performed by considering the helium sorption data available at 35 1C for a series of polymers considered for membrane-based gas separations. Finally, He/H 2 solubility-selectivity at 35 1C has been correctly predicted: as expected, the glassy Teflon s AF-series perfluorinated copolymers display a higher He/H 2 solubility selectivity compared to the hydrocarbon-based polymers.

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Hydrogen sorption in polymers for membrane applications

Cited by 47 publications

References 49 publications

Gas Sorption, Diffusion, and Permeation in Nafion

Gas Sorption, Diffusion, and Permeation in Nafion

Nonequilibrium Lattice Fluid Modeling of Gas Solubility in HAB-6FDA Polyimide and Its Thermally Rearranged Analogues

Predictive calculation of hydrogen and helium solubility in glassy and rubbery polymers

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