• Membrane Journal
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• v.29 no.2
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• pp.88-95
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• 2019

Hydrocarbons containing carbon double bonds are generally called olefins and it is extensively used in petro-chemical industry as essential base material. Especially, olefins are essential in polymer synthesis and thus the effective separation and purification of olefins from gas mixture are very important and it gives significant positive effect on the future industrial development. In this study, we fabricated polymeric composite membrane based on poly(1-trimethylsilyl-1-propyne) (PTMSP) for propylene/nitrogen separation and enhancement of its separation performance by grafting amphiphilic copolymer. Furthermore, to accelerate facilitated transport for propylene molecules, Ag salt ($AgBF_4$) and ionic liquid ($EMIM-BF_4$) was incorporated to polymer composite membranes. The neat PTMSP membrane exhibited extremely high gas permeance and low gas selectivity due to its high free volume. To address this issue, PTMSP was grafted with poly(oxyethylene glycol methacrylate) (POEM) and poly(ethylene glycol) behenyl ether methacrylate (PEGBEM). Additionally, the additives such as $AgBF_4$ and $EMIM-BF_4$ further increased the propylene permeance, resulting in increment of propylene/nitrogen selectivity.

• Membrane Journal
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• v.30 no.6
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• pp.450-459
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• 2020

Membrane-based separations have the potential to reduce energy consumption and environmental impact associated with conventional processes. However, many researches have been done to develop new membrane materials with greater selectivity and permeability. Here, we report highly selective membranes by introducing bulky ethyl substituents into the polyimide. The ethyl group in the ortho position to the imide nitrogen interferes the chain packing and increases chain stiffness and the distance between the polymer chains. The polyimide membranes were synthesized from various aromatic dianhydrides and 4,4'-methylenebis(2,6-diethylaniline) (MDEA). The synthesized membranes with increased gas diffusion length due to bulky substituents showed improved propylene/propane (C3H6/C3H8) selectivity. Single gas permeation showed high C3H6/C3H8 selectivity of 14.5, and C3H6 permeability of 7.0 barrer was found in MDEA-polyimide. Mixed-gas permeation results also demonstrate that MDEA-polyimide can achieve high selectivity in mixed-gas environment. Furthermore, this approach could significantly increase the feasibility of economic propylene separation compared to conventional polymer materials.

• Membrane Journal
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• v.30 no.4
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• pp.252-259
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• 2020

Olefins are industrially important materials used for the synthesis of various petrochemicals. During the polymerization process, unreacted olefin monomers are discharged together with a large amount of nitrogen. For economic benefits, these olefin gases should be efficiently separated from nitrogen. In this study, a poly(glycidyl methacrylate-co-methyl methacrylate) (PGM) comb-like copolymer was synthesized and 4,4'-diaminoazobenzene (DAAB) was introduced to the copolymer to prepare a cross-linked membrane for C₃H₆/N₂ separation. PGM and DAAB were readily reacted at room temperature through an epoxide-amine reaction without additional thermal treatment. PGM-based membrane, which is a glassy polymer, showed a faster permeation of N₂ compared to C₃H₆. The pristine PGM membrane exhibited the N₂ permeability of 0.12 barrer and the high N₂/C₃H₆ selectivity of 32.4. As DAAB was introduced as a cross-linker, the thermal stability of the membrane was significantly improved, which was confirmed by TGA result. The N₂/C₃H₆ selectivity was decreased at 1 wt% of DAAB content, but the N₂ permeability increased by approximately 4.7 times. We analyzed N₂/C₃H₆ gas separation properties through a glassy polymer-based membrane, which has not been widely studied. Also, we proposed that thermal stability of the membrane can be greatly improved by the cross-linking method.

• Proceedings of the Membrane Society of Korea Conference
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• 2008.05a
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• pp.264-267
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• 2008

• 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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• 2003.07a
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• pp.137-138
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• 2003

The worldwide annual production of polyolefins amounted to 60 million tons in 2000. During the process, 1-2 wt% of the olefin monomers have been emitted and flared into the air, causing the huge energy consumption and severe carbon dioxide emission. Recently, membrane process has been proved to be the most competitive among other separation processes in terms of cost of equipments, energy consumption and safety in this application. The performance of membrane process highly depends on the membrane properties and thus, it is very important to develop good membrane materials and composite membranes. We prepared PMDS dense and composite membranes and studied basic permeation behaviors of a series of olefins(ethylene, propylene, 1 -butylene), nitrogen and hydrogen as model gases.

• Membrane Journal
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• v.15 no.2
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• pp.157-164
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• 2005

In this study, composite hollow fiber membranes were developed for the recovery of olefin monomers in polyolefin industry off-gases. Polyetherimide (PEI) hollow fiber support membranes were fabricated from spinning solutions containing PEI, NMP and polyethylene glycol (PEG). The influence of dope solution and inner coagulant composition on the permeation properties and structure of hollow fiber supports was examined. PDMS was used as a selective layer and coated on PEI hollow fiber support. The thickness of active layer was controlled by changing coating solution concentration. The permeation properties of hollow fiber supports and composite membranes were characterized with a pure gas permeation test. The optimized composite hollow fiber membrane has $10\;{\mu}m$ selective layer and shows excellent separation performance; the ideal selectivity of olefins over nitrogen is in the following order: 1-butylene (6.4) > propylene (17) > ethylene (97), which selectivity data are similar to the intrinsic olefin/nitrogen selectivities of PDMS. This confirms that the new composite hollow fiber membranes suitable for olefin off-gas recovery has developed successfully.