• Macromolecular Research
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• v.12 no.2
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• pp.145-155
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• 2004

Facilitated transport membranes for the separation of olefin/paraffin mixtures have long been of interest in separation membrane science because olefins, such as propylene and ethylene, which are important chemicals in petrochemical industries, are currently separated by energy-intensive cryogenic distillation processes. Recently, solid polymer electrolyte membranes containing silver ions have demonstrated remarkable performance in the separation of olefin/paraffin mixtures in the solid state and, thus, they can be considered as alternatives to cryogenic distillation. Here, we review recent progress, and critical issues affecting in the use of facilitated olefin transport membranes; in particular, we provide a general overview with reference to carrier properties, transport mechanisms, and separation performance.

• Proceedings of the Membrane Society of Korea Conference
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• 2004.05a
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• pp.136-139
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• 2004

Olefin/paraffin separation by the facilitated transport membrane using silver salts as carriers has been considered as a promising alternative to the conventional energy intensive distillation process. The basis for the separation is the ability of silver ions to react reversibly with olefin forming silver-olefin complexes.(omitted)

• Macromolecular Research
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• v.11 no.5
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• pp.375-381
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• 2003

Silver salt complex membranes with glassy poly(methyl methacrylate) (PMMA) unexpectedly showed higher propylene permeance than those with rubbery poly(butyl methacrylate) (PBMA) where as neat PMMA is much less permeable to propylene than that of neat PBMA. Such unusual facilitated olefin transport has been systematically investigated by changing the side chain length of polymethacrylates (PMAs) from methyl, ethyl to butyl. The ab initio calculation showed almost the same electron densities of the carbonyl oxygens in the three PMAs, expecting very similar intensity of the interaction between carbonyl oxygen and silver ion. However, the interaction intensity decreases with the length of the alkyl side chain: PMMA > PEMA > PBMA according to wide angle X-ray scattering and FT-Raman spectroscopy. The difference in the interaction intensity may arise from the difference in the hydrophilicity of the three PMAs, as confirmed by the contact angle of water, which determines the concentrations of the ionic constituents of silver salts: free ion, contact ion pair and higher order ionic aggregate. However, propylene solubilities and facilitated propylene transport vary with the side chain length significantly even at the same concentration of the free ion, the most active olefin carrier, suggesting possible difference in the prohibition of the molecular access of propylene to silver ion by the side chains: the steric hindrance. Therefore, it may be concluded that both the hydrophilicity and the steric hindrance associated with the side chain length in the three PMAs are of pivotal importance in determining facilitated olefin transport through polymer/silver salt complex membranes.

• Proceedings of the Membrane Society of Korea Conference
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• 1999.07a
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• pp.15-18
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• 1999

A simple mathematical model for facilitated mass transport through a fixed site carrier membrane was derived by assuming an instantaneous, microscopic concentration (activity) fluctuation. The current model demonstrates that the facilitation factor depends on the extent of concentration fluctuation, the time scale ratios of diffusion to chemical reaction and the ratio of the carrier concentration to the solute solubility in matrix. The model was examined against the experimental data on oxygen transport in membranes containing metallo-porphyrin carriers, and the agreement was exceptional (within 10% error). The basic concept of this approach was applied to separate olefin from olefin/paraffin mixtures. A proprietaty carrier, developed here, resulted that the selectivity of propylene over propane was more than 120 and the propylene permeance exceed 40 gpu.

• Macromolecular Research
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• v.17 no.2
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• pp.104-109
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• 2009

Solid-state facilitated, olefin transport membranes were prepared by complexation of poly(styrene-b-iso-prene-b-styrene) (SIS) block copolymer and silver salt. Facilitated olefin transport was not observed up to a silver mole fraction of 0.14, representing a threshold concentration, above which transport increased almost linearly with increasing silver salt concentration. This was because firstly the silver ions were selectively coordinated with the C=C bonds of PI blocks up to a silver mole fraction of 0.20, and secondly the coordinative interaction of the silver ions with the aliphatic C=C bond was stronger than that with the aromatic C=C bond, as confirmed by FT-Raman spectroscopy. Small angle X-ray scattering (SAXS) analysis showed that the cylindrical morphology of the neat SIS block copolymer was changed to a disordered structure at low silver concentrations ($0.01{\sim}0.02$). However, at intermediate silver concentrations ($0.15{\sim}0.20$), disordered-ordered structural changes occurred and finally returned to a disordered structure again at higher silver concentrations (>0.33). These results demonstrated that the facilitated olefin transport of SIS/silver salt complex membrancs was significantly affected by their coordinative interactions and nano-structural morphology.

• Macromolecular Research
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• v.10 no.2
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• pp.80-84
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• 2002

Silver species other than the silver ion were formed by UV irradiation on polymer electrolyte membranes containing silver salts and their effect on complexation behavior between the silver and olefin was investigated through the separation performance of olefin/paraffin mixtures. The ideal propylene/propane separation factor reached 350 and the separation coefficient was ca.15 due to the high loading amount of silver ions into poly(2-ethyl-2-oxazoline) (POZ) without UV irradiation. On UV irradiation either in air or under nitrogen, the silver-POZ membranes became yellow-brown initially due to the formation of colloidal silver particles, and finally black and metal-like luster. Even when Ag$^{+}$ was converted, to some extent, to Ag$^{\circ}$ by UV irradiation in air at the early stage, the separation coefficient of olefin/paraffin mixtures was maintained. This suggests that silver species other than the silver ion is active for olefin carrier for facilitated transport. Meanwhile the steady decrease of the separation coefficient was observed in the silver/POZ membranes irradiated under $N_2$. It is suggested that the reduction of silver ions in POZ goes through a different photoreduction mechanism with UV irradiation depending on the environment.t.

• Membrane Journal
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• v.13 no.2
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• pp.125-129
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• 2003

A remarkable separation performance of olefin/paraffin mixtures has been observed through facilitated olefin transport membranes consisting of silver ions dissolved in polymer matrices. In this research, valine, an amino acid, was introduced in poly (2-ethyl-2-oxazoline) (POZ)/$AgBF_4$ membranes to increase the separation performance. FT-IR spectra show that the cationic sites ($-NH_3^+$) of valine interact with the counter anion of the silver salt, resulting in the enhanced activity of the silver ions and consequently improved separation perfornance. Therefore, the $POZ/AgBF_4$ membranes containing valines exhibit the higher permeance as well as the higher selectivity of propylene/propane than those without valine.

• Proceedings of the Membrane Society of Korea Conference
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• 2003.11a
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• pp.51-54
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• 2003

• Proceedings of the Membrane Society of Korea Conference
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• 2003.05a
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• pp.110-113
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• 2003

• Proceedings of the Membrane Society of Korea Conference
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• 2004.05a
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• pp.211-215
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• 2004

Olefins are the most important feedstock in the petrochemical industry and thus the separation of olefin/paraffin mixtures is crucial to that industry. At present, this separation is mostly carried out using cryogenic distillation processes that require enormous capital investment and have high operational costs.(omitted)