• 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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• 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.

• Membrane Journal
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• v.25 no.5
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• pp.398-405
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• 2015

Facilitated transport is considered to be a possible solution to simultaneously improve permeability and selectivity, which is challenging in normal polymeric membranes based on solution-diffusion transport only. We investigated the effect of adding mesoporous $TiO_2$ ($m-TiO_2$) upon the separation performance of facilitated olefin transport membranes comprising poly(vinyl pyrrolidone), Ag nanoparticles, and 7,7,8,8-tetracyanoquinodimethane as the polymer matrix, olefin carrier, and electron acceptor, respectively. In particular, $m-TiO_2$ was prepared by means of a facile, mass-producible method using poly(vinyl chloride)-g-poly(oxyethylene methacrylate) graft copolymer as the template. The crystal phase of $m-TiO_2$ consisted of an anatase/rutile mixture, of crystallite size approximately 16 nm as determined by X-ray diffraction. The introduction of $m-TiO_2$ increased the membrane diffusivity, thereby increasing the mixed-gas permeance from 1.6 to 16.0 GPU ($1GPU=10^{-6}cm^3$(STP)/($s{\times}cm^2{\times}cmHg$), and slightly decreased the propylene/propane selectivity from 45 to 37. However, both the mixed-gas permeance and selectivity of the membrane containing $m-TiO_2$ rapidly decreased over time, whereas the membrane without $m-TiO_2$ had more stable long-term performance. This difference might be attributed to specific chemical interactions between $TiO_2$ and Ag nanoparticles, causing Ag to lose activity as an olefin carrier.

• 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.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.

• 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.

• Membrane Journal
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• v.26 no.3
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• pp.173-178
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• 2016

In this short review, the polymer electrolyte membranes consisting of polymer and Ag salts were introduced and various approaches to solve the long-term stability were summarized. In particular, utilizing $AgNO_3$ as carriers with ionic liquid, the replacement of polymer matrix as poly(ethylene phthalate) (PEP) for strong coordinative interactions with Ag ions and the introduction of $Al(NO_3)_3$ to $polymer/AgBF_4$ complexes were introduced for long-term stable facilitated olefin transport membranes. For the polymer nanocomposite membranes, the role of electron acceptors as polarizer on the surface of AgNPs and the approach to solve the low permeance were introduced.

• 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.27 no.3
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• pp.205-215
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• 2017

Polymer membranes are cheap and easy in fabrication, and show a high permeability and selectivity, thus play pivotal roles in gas separation as well as water purification. However, polymer membranes typically exhibit the trade-off relation between permeability and selectivity; i.e. when the permeability is high, the selectivity is low and vice versa. Facilitated transport has been considered one of the solutions to address this issue. Over the last decades, facilitated transport concept had played an important role in preparing the membranes and providing ideal and various models for the transport. Understanding the nature of carrier, the mobility of matrix and the physico-chemical properties of polymer composites are crucial for facilitated transport. Depending on the mobility of carrier, facilitated transport membrane is classified into three; mobile carrier membrane, semi-mobile carrier membrane, fixed-site carrier membrane. Also, there are four types of reversible reaction between the carrier and the specific target; proton transfer reaction, nucleophilic addition reaction, p-complexation reaction and electrochemical reaction. The facilitated transport membranes have been applied in the separation of CO2, O2 and olefin (propylene or ethylene). In this review, major challenges surrounding facilitated transport membranes and the strategies to tackle these challenges are given in detail.

• Membrane Journal
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• v.28 no.4
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• pp.265-270
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• 2018

In previous studies, a poly(ethylene oxide)(PEO)/Ag nanoparicles (AgNPs)(precursor $AgBF_4$)/p-benzoquinone (p-BQ) composite membrane was prepared for olefin/paraffin separation and the performance of this composite membrane was maintained at a selectivity of 10 and a permeability of 15 GPU. However, since the price of $AgBF_4$ precursor is high, this study used $AgNO_3$ as a precursor of Ag nanoparticles which is competitive in terms of price. As a result, it was observed that the separation performance was not obtained because the existing $NO_3{^-}$ could surround AgNPs. In this study, we fabricated PEO, poly(vinyl alcohol)(PVA), and polyether block amide-1657 (PEBAX-1657) polymer composite membrane using electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) for separation performance even when $AgNO_3$ was used as a precursor of Ag nanoparticles. As a result, it was analyzed that the performance was not observed regardless of the influence of the polymer and the electron acceptor, indicating that the anion of the precursor plays a crucial role in the separation performance.