• 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.

• 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.

• 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)

• Membrane Journal
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• v.29 no.5
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• pp.246-251
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• 2019

Facilitated transport membranes using silver nanoparticles as carriers for olefin/paraffin separation have been interested. $AgBF_4$ has been used as a precursor of silver nanoparticles in previous studies. However, relatively expensive $AgBF_4$ is not suitable for commercialization, and thus, PEBAX-5513/AgNPs (precursor: $AgClO_4$)/7,7,8,8-tetracyanoquinodimethane (TCNQ) composite membranes were prepared using silver nanopaticles with relatively inexpensive $AgClO_4$ precursors. Composite membranes of various compositions were prepared for PEBAX-5513/AgNPs/TCNQ composites, but no separation performance was observed. As a result of FT-IR analysis, it was confirmed that silver nanoparticles were formed in the PEBAX-5513 polymer and the surface of Ag nanoparticles was polarized by TCNQ, but the formed silver nanoparticles were not stabilized. From these results, it was concluded that the anion of the precursor plays an important role in the olefin/paraffin separation.

• Membrane Journal
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• v.26 no.1
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• pp.38-42
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• 2016

Polyvinylpyrrolidone (PVP), which is glassy polymer to have amide functional group, was induced to fabricate the facilitated olefin transport membranes for olefin/paraffin separation. Separation performance for the mixed gas consisting of propylene and propane (50 : 50 vol%) was measured by gas chromatography and bubble flow meter. The properties of membranes were confirmed by scanning electron microscope and FT-IR. The results of long-term separation tests showed the selectivity of 15 and permeance of 1.3 GPU. The membranes was compared with poly(2-ethyl-2-oxazoline) $(POZ)/AgBF_4/Al(NO_3)_3$ membranes and the characteristics were confirmed as polymer matrix for facilitated transport membranes.

• Membrane Journal
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• v.24 no.6
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• pp.448-452
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• 2014

Nanocomposite membrane to show facilitated olefin transport was prepared for enhanced separation performance. Addtion of halogen molecules into PVP/AgNPs/ TCNQ nanocomposite membrane was expected to further polarize the surface of AgNPs for enhancing the separation performance. The formation of AgNPs and presence of iodine was confirmed by TEM and EDS analysis, respectively. The separation performance for propylene/propane mixture was compared with that of PVP/AgNPs/TCNQ nanocomposite membrane. The long-term stability of membrane was investigated with time.

• 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.

• Membrane Journal
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• v.25 no.6
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• pp.496-502
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• 2015

Facilitated transport is one of the possible solutions to simultaneously improve permeability and selectivity, which is challenging in conventional polymer-based membranes. Olefin/paraffin separation using facilitated transport membrane has received much attention as an alternative solution to the conventional distillation process. Herein, we report olefin separation composite membranes based on the polymer blends containing $AgBF_4/Al(NO_3)_3$ mixed salts. Free radical polymerization process was used to synthesize an amphiphilic graft copolymer of poly(dimethyl siloxane)-graft- poly(ethylene glycol) methyl ether methacrylate (PDMS-g-POEM). In addition, poly(ethylene oxide) (PEO) was introduced to the PDMS-g-POEM graft copolymer to form polymer blends with various ratios. The propylene/propane mixed-gas selectivity and permeance reached up to 5.6 and 10.05 GPU, respectively, when the PEO loading was 70 wt% in polymer blend. The improvement of olefin separation performance was attributed to the olefin facilitating silver ions as well as the highly permeable blend matrix. The stabilization of silver ions in the composite membrane was achieved through the introduction of $Al(NO_3)_3$ which suppressed the reduction of silver ions to silver particles.

• Membrane Journal
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• v.28 no.4
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• pp.260-264
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• 2018

Poly (ethylene oxide) (PEO)/Ag nanoparticles (AgNPs)(precursor : $AgBF_4$)/p-benzoquinone (p-BQ) composite membrane was prepared for olefin/paraffin separation. As a result, the performance of composite membrane was observed to be maintained at selectivity of 10 and permeance of 15 GPU up to 100 hours. The performance of the membrane was maintained for 100 hours was attributable to that Ag ions could be converted into stable Ag NPs by addition of p-BQ. Furthermore, the surface was partially polarized by the electron acceptor p-BQ, resulting in the formation of olefin carrier. In this study, since the cost of $AgBF_4$ used as a precursor of Ag NPs was relatively higher, $AgNO_3$ was utilized. As a result, it was confirmed that $AgNO_3$ couldn't show the stable formation of nanoparticle, resulting in the poor separation performance.

• Membrane Journal
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• v.25 no.1
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• pp.1-6
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• 2015

It was known that the polarlized surface of silver nanoparticles could be interacted revesibly with olefin molecules for facilitated olefin transport. However, it was thought that it can be regenerated by interaction between oxide surface of AgNPs and olefin molecules because the surface of the silver nanoparticles is easily oxidized in the air. In order to investigate the effect of the silver oxide, 5 wt% AgO or $Ag_2O$ was dispersed in polymer PVP solutions and 0.005~0.02% electron acceptor as TCNQ or p-BQ were added to fabricate the separation membrane. After the addition of the electron acceptor, it was expected to improve the polarity on the surface of the silver oxide and the degree of dispersion. The characteristics of the separation membrane were identified by the gas permeance, XPS and TEM.