• Clean Technology
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• v.28 no.4
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• pp.269-277
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• 2022

With the recent development of the biological enzymatic reaction industry, lactic acid (LA) can be mass-produced from biomass sources. In particular, a catalytic process that converts LA into acrylic acid (AA) is receiving much attention because AA is used widely in the petrochemical industry as a monomer for superabsorbent polymers (SAP) and as an adhesive for displays. In the LA conversion process, NaY zeolites have been previously shown to be a high-activity catalyst, which improves AA selectivity and long-term stability. However, NaY zeolites suffer from fast deactivation due to severe coking. Therefore, the aim of this study is to modify the acid-base properties of the NaY zeolite to address this shortcoming. First, base promoters, Ca ions, were introduced to the NaY zeolites to tune their acidity and basicity via ion exchange (IE) and incipient wetness impregnation (IWI). The IWI method showed superior catalyst selectivity and stability compared to the IE method, maintaining a high AA yield of approximately 40% during the 16 h reaction. Based on the NH₃- and CO₂-TPD results, the calcium salts that impregnated into the NaY zeolites were proposed to exit as an oxide form mainly at the exterior surface of NaY and act as additional base sites to promote the dehydration of LA to AA. The NaY zeolites were further treated with KOH before calcium impregnation to reduce the total acidity and improve the dispersion of calcium through the mesopores formed by KOH-induced desilication. However, this KOH treatment did not lead to enhanced AA selectivity. Finally, calcium loading was increased from 1wt% to 5wt% to maximize the amount of base sites. The increased basicity improved the AA selectivity substantially to 65% at 100% conversion while maintaining high activity during a 24 h reaction. Our results suggest that controlling the basicity of the catalyst is key to obtaining high AA selectivity and high catalyst stability.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2018.06a
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• pp.62-62
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• 2018

Pt is still considered as one of the most active electrocatalysts for ORR in alkaline fuel cells. However, the high cost and scarcity of Pt hamper the widespread commercialization of fuel cells. As a strong candidate for the replacement of Pt catalyst, silver (Ag) has been extensively studied due to its high activity, abundance, and low cost. Ag is more stable than Pt in the pH range of 8~14 as the equilibrium potential of Ag/Ag+ being ${\approx}200mV$ higher than that of Pt/PtO. However, Ag is the overall catalytic activity of Ag for oxygen reduction reaction(ORR) is still not comparable to Pt catalyst since the surface Ag atoms are approximately 10 times less active than Pt atoms. Therefore, further enhancement in the ORR activity of Ag catalysts is necessary to be competitive with current cutting-edge Pt-based catalysts. We demonstrate the architectural design of Ag catalysts, synthesized using plasma discharge in liquid phase, for enhanced ORR kinetics in alkaline media. An attractive feature of this work is that the plasma status controlled via electric-field could form the Ag nanowires or dendrites without any chemical agents. The plasma reactor was made of a Teflon vessel with an inner diameter of 80 mm and a height of 80 mm, where a pair of tungsten(W) electrodes with a diameter of 2 mm was placed horizontally. The stock solutions were made by dissolving the 5-mM AgNO3 in DI water. For the synthesis of Agnanowires, the electricfield of 3.6kVcm-1 in a 200-ml AgNO3 aqueous solution was applied across the electrodes using a bipolar pulsed power supply(Kurita, Seisakusyo Co. Ltd). The repetition rate and pulse width were fixed at 30kHz and 2.0 us, respectively. The plasma discharge was carried out for a fixed reaction time of 60 min. In case of Ag nanodendrites, the electric field of 32kVcm-1 in a 200-ml AgNO3 aqueous solution was applied and other conditions were identical to the plasma discharge in water in terms of electrode configuration, repetition rate and discharge time. Using SEM and STEM, morphology of Ag nanowires and dendrites were investigated. With 3.6 kV/cm, Ag nanowire was obtained, while Ag dendrite was constructed with 32 kV/cm. The average diameter and legth of Ag nanowireses were 50 nm and 3.5 um, and thoes values of Ag dendrites were 40 nm and 3.0 um. As a results of XPS analysis, the surface defects in the Ag nanowires facilitated O2 incorporation into the surface region via the interaction between the oxygen and the electron cloud of the adjacent Ag atoms. The catalytic activity of Ag for oxygen reduction reaction(ORR) showed that the catalytic ORR activity of Ag nanowires are much better than Ag nanodendrites, and electron transfer number of Ag nanowires is similar to that of Pt (${\approx}4$).

• Clean Technology
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• v.26 no.2
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• pp.91-95
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• 2020

A new eco-friendly synthetic method for N-hydroxysuccinimide (NHS), widely used in the pharmaceutical and fine chemical industries, is developed. Conventional synthesis method yields NHS of about 70% after its reaction with NH₂OH to succinic acid. In this method, NHS can be obtained using low-cost succinic acid, but a great deal of solvents are required as an extraction method to purify NHS, while the work-up process is complicated, resulting in low yield. In addition, there is a safety risk due to the high reaction temperature for commercial production, and it is not economical due to the high cost of production from the generation of much waste because of an acid catalyst and the use of various solvents. In order to make up for this shortcoming, this study used succinic anhydride as a raw material under low temperature reaction and developed a new eco-friendly industrial synthesis method using isobutyl alcohol for a single solvent and non-catalytic reaction. The economic evaluation confirms that there is a cost reduction effect of about 20%. In the future, based on this result, studies may establish a commercial production technology through scale-up research and proceed with foreign technology transfer.

• Journal of Energy Engineering
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• v.20 no.1
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• pp.13-20
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• 2011

The high fuel flexibility of Micro Gas Turbine(MGT) has boosted their use in a wide variety of applications. Recently, the demand for biogas generated from the digestion of organic wastes and landfill as a fuel for gas turbines has increased. We researched the influence of firing landfill gas(LFG) on the performance and operating characteristics of a micro gas turbine combined heat and power system. $CH_4$ and $CO_2$ simultaneous recovery process has been developed for field plant scale to provide an isothermal, low operating cost method for carrying out the contaminants removal in Land Fill Gas(LFG) by liquid phase catalyst for introduce into the green house for the purpose of $CO_2$ rich cultivation of the plants. Methane purification and carbon dioxide stripping by muti panel autocirculation bubble lift column reactor utilizing Fe-EDTA was conducted for evaluate optimum conditions for land fill gas. Based on inflow rate of LFG as 0.207 $m^3$/min, 5.5 kg/$cm^2$, we designed reactor system for 70% $CH_4$ and 27% $CO_2$ gas introduce into MGT system with $H_2S$ 99% removal efficiency. A green house designed for four different carbon dioxide concentration from ambient air to 1500 ppm by utilizing the exhaust gas and hot water from MGT system.

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1653-1668
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• 2005

Assembly of hybrid mesophases through the combination of amphiphilic block copolymers, acting as structuredirecting agents, and silicon sources using low acid catalyst concentration regimes is a versatile strategy to produce large quantities of high-quality ordered large-pore mesoporous silicas in a very reproducible manner. Controlling structural and textural properties is proven to be straightforward at low HCl concentrations with the adjustment of synthesis gel composition and the option of adding co-structure-directing molecules. In this account, we illustrate how various types of large-pore mesoporous silica can easily be prepared in high phase purity with tailored pore dimensions and tailored level of framework interconnectivity. Silica mesophases with two-dimensional hexagonal (p6mm) and three-dimensional cubi (Fm$\overline{3}$m, Im$\overline{3}$m and Ia$\overline{3}$d) symmetries are generated in aqueous solution by employing HCl concentrations in the range of 0.1−0.5 M and polyalkylene oxide-based triblock copolymers such as Pluronic P123 $(EO_{20}-PO_{70}-EO_{20})$ and Pluronic F127 $(EO_{106}-PO_{70}-EO_{106})$. Characterizations by powder X-ray diffraction, nitrogen physisorption, and transmission electron microscopy show that the mesoporous materials all possess high specific surface areas, high pore volumes and readily tunable pore diameters in narrow distribution of sizes ranging from 4 to 12 nm. Furthermore, we discuss our recent advances achieved in order to extend widely the phase domains in which single mesostructures are formed. Emphasis is put on the first synthetic product phase diagrams obtained in $SiO_2$-triblock copolymer-BuOH-$H_2O$ systems, with tuning amounts of butanol and silica source correspondingly. It is expected that the extended phase domains will allow designed synthesis of mesoporous silicas with targeted characteristics, offering vast prospects for future applications.

• Clean Technology
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• v.11 no.2
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• pp.57-67
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• 2005

Epoxy resins are produced by the dehydro condensated reaction with ECH (Epichlorohydrin) and BPA(Bisphenol-A) as raw reactants under sodium hydroxide(NaOH) as a catalyst, and from this reaction, salted water named of brine, which contains ECH derivatives in condition of emulsion as likely as glycidol and polymer resins, is produced as an undesired side product. This brine water is alkaline wastewater and causes process fouling problems by plugging and chemically depositing polymer particles on the surface of inner wall of reactors and pipes, and decreases the biodegradable efficiency in the wastewater process. In this study, the optimization of coagulation and sediment reactions, using inorganic and organic polymer coagulants, were performed to remove the causes occurring the process fouling phenomena. And also, based on this study, the methodologies applicable to the commercial processes including economical analysis were presented.

• Journal of Electrochemical Science and Technology
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• v.6 no.3
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• pp.95-105
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• 2015

In the present work, Carbon supported Pt₁₀₀, Pt₈₀Sn₂₀, Pt₈₀Ni₂₀ and Pt₈₀Sn₁₀Ni₁₀ electrocatalysts with different atomic ratios were prepared by ethylene glycol-reduction method to study the electro-oxidation of ethanol in membraneless fuel cell. The electrocatalysts were characterized in terms of structure, morphology and composition by using XRD, TEM and EDX techniques. Transmission electron microscopy measurements revealed a decrease in the mean particle size of the catalysts for the ternary compositions. The electrocatalytic activities of Pt₁₀₀/C, Pt₈₀Sn₂₀/C, Pt₈₀Ni₂₀/C and Pt₈₀Sn₁₀Ni₁₀/C catalysts for ethanol oxidation in an acid medium were investigated by cyclic voltammetry (CV) and chronoamperometry (CA). The electrochemical results showed that addition of Ni to Pt/C and Pt-Sn/C catalysts significantly shifted the onset of ethanol and CO oxidations toward lower potentials. The single membraneless ethanol fuel cell performances of the Pt₈₀Sn₁₀Ni₁₀/C, Pt₈₀Sn₂₀/C and Pt₈₀Ni₂₀/C anode catalysts were evaluated at room temperature. Among the catalysts investigated, the power density obtained for Pt₈₀Sn₁₀Ni₁₀/C (37.77 mW/cm² ) catalyst was higher than that of Pt₈₀Sn₂₀/C (22.89 mW/cm² ) and Pt₈₀Ni₂₀/C (16.77 mW/ cm² ), using 1.0 M ethanol + 0.5 M H₂SO₄ as anode feed and 0.1 M sodium percarbonate + 0.5 M H₂SO₄ as cathode feed.

• 한국신재생에너지학회:학술대회논문집
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• 2007.06a
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• pp.53-56
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• 2007

미량의 Ru을 증진제로 첨가하여 니켈 촉매의 반응 활성을 증진시킴으로써, 저온 환원성과 장시간 반응에 대한 안정성을 확보하고자 하였다. Ni의 담지량은 12 wt%로 고정하였으며 이에 Ru을 각각 0.1, 0.3, 0.5 wt%로 변화시켜 2차 담지하였다. 메탄의 수증기/이산화탄소 복합 개질 반응에 있어 니켈 촉매에 Ru을 2차 담지 한 촉매는 800 $^{\circ}C$, GHSV(gas hourly space velocity) 265,000 $h^{-1}$ 하에서 100 %에 가까운 $CH_{4}$ 전환율을 보였으며, GHSV 1,060,000 $h^{-1}$ 일 때에도 10시간 동안 90 %의 $CH_{4}$ 전환율을 기록하였다. 또한 이 중 0.3 wt%의 Ru를 담지한 경우가 1,060,000 $h^{-1}$의 조건하에서도 95 %이상으로 가장 높은 $CH_{4}$ 전환율로 유지되었다. $H_{2}-TPR$ 분석 결과, Ni(12)/$MgAl_{2}O_{4}$ 와 비교해 볼 때 Ru(0.5)/Ni(12)/$MgAl_{2}O_{4}$와 Ru(0.3)/Ni(12)/$MgAl_{2}O_{4}$ 촉매의 경우 150 $^{\circ}C$에서 저온 환원이 가능한 $RuO_{2}$의 존재를 확인할 수 있었다.

• Transactions of the Korean Society of Automotive Engineers
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• v.16 no.1
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• pp.14-21
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• 2008

Synthetic gas is defined as reformed gas from hydrocarbon-based fuel and the major chemical species of the synthetic gas are $H_2$, CO and $N_2$. Among them, hydrogen from synthetic gas is very useful species in chemical process such as combustion. It is a main reason that many studies have been performed to develop an effective reforming device. Furthermore, other technologies have been studied for synthetic gas application, such as the ESGI(Exhaust Synthetic Gas Injection) technology. ESGI injects and burns synthetic gas in the exhaust pipe so that heat from hydrogen combustion helps fast warmup of the close-coupled catalyst and reduction of harmful emissions. However, it is very hard to understand combustion characteristic of hydrogen under low oxygen environment and complicated variation in chemical species in exhaust gas. This study focuses on the characteristics of hydrogen combustion under ESGI operating conditions using a CVC(Constant Volume Chamber). Measurements of pressure variation and flame speed have been performed for various oxygen and hydrogen concentrations. Results have been analyzed to understand ignition and combustion characteristics of hydrogen under lower oxygen conditions. The CVC experiments showed that under lower oxygen concentration, amount of active chemicals in the combustion chamber was a crucial factor to influence hydrogen combustion as well as hydrogen/oxygen ratio. It is also found that increase in volume fraction of oxygen is effective for the fast and stable burning of hydrogen by virtue of increase in flame speed.

• Korean Journal of Materials Research
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• v.20 no.9
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• pp.472-477
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• 2010

$Al_2O_3$ has received wide attention with established use as a catalyst and growing application in structural or functional ceramic materials. On the other hand, the boehmite (AlO(OH)) obtained by sol-gel process has exhibited a decrease in surface area during phase transformation due to a decline in surface active site at high temperature. In this work, $Al_2O_3$-CuO/ZnO (ACZ) and $Al_2O_3$-CuO/CeO (ACC) composite materials were synthesized with aluminum isopropoxide, copper (II) nitrate hemi (pentahydrate), and cerium (III) nitrate hexahydrate or zinc (II) nitrate hexahydrate. Moreover, the Span 80 as the template block copolymer was added to the ACZ/ACC composition to make nano size particles and to keep increasing the surface area. The ACZ/ACC synthesized powders were characterized by Thermogravimetry-Differential Thermal analysis (TG/DTA), X-ray Diffractometer (XRD), Field-Emmision Scanning Electron Microscope (FE-SEM), Bruner-Emmett-Teller (BET) surface analysis and thermal electrical conductivity (ZEM-2:M8/L). An enhancement of surface area with the addition to Span 80 surfactant was observed in the ACZ powders from 105 $m^2$/g to 142 $m^2$/g, and the ACC powders from 103 $m^2$/g to 140 $m^2$/g, respectively.