• Membrane Journal
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• v.24 no.1
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• pp.1-9
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• 2014

In this study, four soluble homo- and co-polyimides using 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA) and 4,4'-diaminodiphenyl ether (ODA) monomers were synthesized to develop the gas separation membrane with good $CO_2/CH_4$ separation properties. To prepare the copolyimides, 20 mol% of three dianhydrides - (4,4'-(hexafluoroisoproplidene)diphthalic anhydride (6FDA), 4,4'-biphthalic anhydride (BPDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) - were added in DOCDA-ODA monomer mixture, respectively. All the synthesized homo- and co-polyimides were characterized by FT-IR. Their thermal properties were analyzed with differential scanning calorimeter (DSC). Dense membranes were prepared from these copolyimides to check their gas permeation properties for $CO_2$ and $CH_4$ gases using a time-lag method. The permeation testing results are as follows; DOCDA/ODA homopolymer showed 1.71 barrer of $CO_2$ permeability and 74.35 of $CO_2/CH_4$ selectivity. The three polyimide copolymers (DOCDA/6FDA-ODA, DOCDA/BPDA-ODA, DOCDA/BTDA-ODA) showed lower $CO_2/CH_4$ selectivities and higher $CO_2$ permeabilities than the homopolymer (DOCDA-ODA). DOCDA/6FDA-ODA showed twice times higher $CO_2$ permeabilities without severe $CO_2/CH_4$ selectivity loss than the DOCDA-ODA.

• Journal of Industrial and Engineering Chemistry
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• v.67
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• pp.156-163
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• 2018

High-performance mixed-matrix membranes that comprise both zeolitic imidazolate framework-8 (ZIF-8) and graphene oxide (GO) were synthesized with a solution casting technique to realize excellent $CO_2/CH_4$ separation. The incorporation of ZIF-8 nanocrystals alone in ODPA-TMPDA polyimide can be used to significantly enhance $CO_2$ permeability compared with that of pure ODPA-TMPDA. Meanwhile, the addition of a GO nanostack alone in ODPA-TMPDA contributes to improved $CO_2/CH_4$ selectivity. Hence, a composite membrane that contains both fillers displays significant enhancements in $CO_2$ permeability (up to 60%) and $CO_2/CH_4$ selectivity (up to 28%) compared with those of pure polymeric membrane. Furthermore, in contrast to the ZIF-8 mixed-matrix membrane, which showed decreased mechanical stability, it was found that the incorporation of GO could improve the mechanical strength of mixed-matrix membranes. Overall, the synergistic effects of the use of both fillers together are successfully demonstrated in this paper. Such significant improvements in the mixed-matrix membrane's $CO_2/CH_4$ separation performance and mechanical strength suggest a feasible and effective approach for potential biogas upgrading and natural gas purification.

• Korean Journal of Materials Research
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• v.28 no.7
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• pp.417-422
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• 2018

The stereotype of flexible MOFs(Amino-MIL-53) and carbonized porous carbon prepared from renewable resources is successfully synthesized for $CO_2$ reduction application. The textural properties of these microporous materials are investigated, and their $CO_2$ storage capacity and separation performance are evaluated. Owing to the combined effects of $CO_2-Amino$ interaction and its flexibility, a $CO_2$ uptake of $2.5mmol\;g^{-1}$ is observed in Amino-MIL-53 at 20 bar 298 K. In contrast, $CH_4$ uptake in Amino-MIL-53 is very low up to 20 bar, implying potential sorbent for $CO_2/CH_4$ separation. Carbonized samples contain a small quantity of metal residues(K, Ca, Mg, S), resulting in naturally doped porous carbon. Due to the trace metal, even higher $CO_2$ uptake of $4.7mmol\;g^{-1}$ is also observed at 20 bar 298 K. Furthermore, the $CH_4$ storage capacity is $2.9mmol\;g^{-1}$ at 298 K and 20 bar. To evaluate the $CO_2$ separation performance, the selectivity based on ideal adsorption solution theory for $CO_2/CH_4$ binary mixtures on the presented porous materials is investigated.

• Membrane Journal
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• v.30 no.4
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• pp.269-275
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• 2020

In this study, CO₂ separation experiment was performed on a CH₄/CO₂ mixed gas using a ceramic hollow fiber membrane contactor (HFMC). In order to fabricate high-performance HFMC, experiments were conducted to manufacture high-permeability hollow fiber membranes, and the prepared hollow fiber membranes were evaluated through N₂ gas permeation experiments. HFMC for CH₄/CO₂ mixed gas separation was manufactured using the manufactured high-permeability hollow fiber membrane. In the experiment, mixed gas of CH₄/CO₂ (34.5% CO₂, CH₄ balance) and monoetanolamine (MEA) was used, and the effect of CO₂ removal efficiency on the flow rate of the absorbent was evaluated. The CO₂ removal efficiency increased as the liquid flow rate increased, and the CO₂ absorption flux also increased with the liquid flow rate.

• Journal of Environmental Science International
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• v.20 no.8
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• pp.1011-1019
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• 2011

The objective of this research is to evaluate optimal conditions of permeability and selectivity on the polysulfone membrane for efficiency of separation of $CH_4$ by checking four factors which are temperature, pressure, gas compositions and gas flow rates. When higher pressure was applied at the input, lower efficiency of recovery of $CH_4$ and higher efficiency of separation of $CH_4$ were shown. It has the tendency to show lower efficiency of recovery of $CH_4$ and higher efficiency of separation of $CH_4$ at the output as higher temperature at input. The lower flow rates make higher efficiency of recovery of $CH_4$ and lower efficiency of separation of $CH_4$. Finally, over 90% efficiency for $CH_4$ separation and recovery conditions are temperature ($-5^{\circ}C$), pressure (8 bar), gas composition rate (6:4) ($CH_4:CO_2$) and gas flow rate ($5\ell$/min). These conditions make higher separation and recovery efficiency such as 90.1% and 92.1%, respectively.

• Membrane Journal
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• v.4 no.4
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• pp.197-204
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• 1994

In this study, permeation characteristics of pure $CH_4,\;CO_2$ and $CH_4/CO_2$ gas mixture were examined by permeation experiments through hollow fiber membrane module and experimental results were compared with simulation results. Permeation rate of pure gas increased with increaseing temperature in Arrhenius type. Activation energy was 6.61 kJ/mol for $CO_2$ and 25.26 kJ/mol for $CH_4$. In the permeation experiment of gas mixture, permeate flow rate and $CO_2$ concentration in permeate decreased and $CH_4$ concentration in reject increased with the increase of cut. Separation factor was in the range of 20~40 at 5~20 atm and 20% cut and it increased with pressure and against temperature Experimental values corresponded to numerical values with the deviation of 8% in permeate flow rate and $CO_2$ concentration in permeate and 15% in $CO_2$ concentration in reject.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.6
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• pp.614-619
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• 2005

The activated carbon fibers of different surface area and pore structures were modified by carbon deposition from the pyrolysis of benzene, in an attempt to obtain carbon molecular sieves of high adsorption capacity and selectivity for the separation of $CO_2/CH_4$ gas mixtures. The ACFs molecular sieves prepared from different temperature and time were tested by the static adsorption of $CO_2$ and $CH_4$ gas, and their pore structures were characterized by the $N_2$ adsorption isotherms. We are able to prepare ACF molecular sieve with good selectivity for $CO_2/CH_4$ separation and showing acceptable adsorption capacities from the change of porosity by carbon deposition of pyrolyzed benzene.

• Membrane Journal
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• v.21 no.4
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• pp.367-376
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• 2011

Huge amount of $CH_4$ mixtures has been emitted from landfills and organic wastes via anaerobic digestion. The recovery of high purity $CH_4$ from these gases has two merits: reduction of green house gases and production of renewable fuels. Membrane technology based on polymeric materials can be used in this application. In this study, asymmetric gas separation hollow fiber membranes were fabricated to develop the membrane-based bio-gas purification process. Polyethersulfone (PES) was chosen as a polymer materials because of high $CO_2$ permeability of 3.4 barrer and $CO_2/CH_4$ selectivity of 50[1]. Acetone was used as a non-solvent additive because of its unique swelling power for PES and highly volatile character. The prepared PES hollow fiber showed excellent separation properties: 36 GPU of $CO_2$ permeance and 46 of $CO_2/CH_4$ selectivity at optimized preparation conditions: 9wt% acetone content, 10cm air-gap and 4wt% PDMS coating processes. With the PES hollow fiber membranes developed, mixed $CO_2/CH_4$ test was done by changing various operating conditions such as pressures and feed compositions to meet the highest recovery of CH4 with 95% purity. High $CH_4$ recovery of 58 wt% was observed at 10 atm feed pressure for the 50 vol% of $CO_2$ in $CO_2/CH_4$ mixture.

• Membrane Journal
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• v.21 no.2
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• pp.177-192
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• 2011

Hollow fiber membrane using CTA polymers were prepared by the phase separation method for the separation and purification of biogas and the hollow fiber gas separation membrane modules with the effective surface area of 0.17 $m^2$ were prepared. The pure gas permeation properties of membrane modules for methane, oxygen and carbon dioxide were measured. The permeance of $CO_2$ and $CH_4$were 0.46 GPU and 18.52 GPU, respectively, therefore, the high $CO_2$/$CH_4$ selectivity of 40.4 was obtained. The separation and purification test for 4 different simulated mixed gases were carried out after the pure gas test and the gas concentration and flux of the permeate at the various stage-cut were measured from the 1 stage, 2 stage, and 3 stage cascade of membrane modules. In the 1 stage test, the concentration of $CH_4$ increased as the increase of the stage-cut, while the $CH_4$ recovery efficiency ratio decreased. In the 2 stage test, the $CH_4$ recovery efficiency ratio increased compared to the 1 stage. The 3 stage test was employed to reduce the loss of $CH_4$ in biogas and the result showed less than 5% of $CH_4$ recovery loss.

• Membrane Journal
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• v.23 no.1
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• pp.54-60
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• 2013

PEGDA/PETEDA dendrimer composite membranes was prepared by UV photopolymerizing of poly ethylene glycol diacrylate (PEGDA) containing 5~15 wt% pentaerythrityl tetraethylenediamine (PETEDA) dendrimer. The prepared composite membrane was characterized by FT-IR, $^1H$-NMR and DSC. The glass transition temperature ($T_g$) of PEGDA/PETEDA dendrimer composite decreased with the increment of PETEDA dendrimer content. The $CO_2$ separation properties over $CH_4$ were investigated by changing the PETEDA dendrimer content and pressure. The composite membrane containing 10 wt% PETEDA dendrimer exhibited on excellent $CO_2/CH_4$ ideal selectivity of 31.8 and a $CO_2$ permeability of 162.2 barrer.