• Korean Chemical Engineering Research
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• v.49 no.5
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• pp.521-529
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• 2011

Methanol-to-olefin (MTO) reaction was studied over MWW zeolite with independently developed two pores (circular and straight) and MFI zeolite with intercrossed sinusoidal and straight pores in order to investigate the effect of pore structure on their catalytic behavior. MWW and MFI zeolites with similar acidity exhibited commonly high conversion and slow deactivation in the MTO reaction, but their product selectivities were considerably different: linear hydrocarbons of $C_3-C_9$ were mainly produced on MWW, while the yield of $C_2{^=}$ and aromatics were high on MFI. Polyaroamatic hydrocarbons (PAHs) were accumulated on MWW, but a small amount of benzene and aromatics on MFI. The impregnation of phosphorous on MWW caused significant decreases in the catalytic activity and toluene adsorption, but the decreases were relatively small on MFI. Although the straight pores of MWW were inactive in the MTO reaction due to the accumulation of PAHs, its circular pores which suppressed the formation of PAHs sustained catalytic activity for the production of linear hydrocarbons. Therefore, the impregnation of phosphorous on the circular pores of MWW caused a significant decrease in catalytic activity. The phosphorous impregnation on the cross sections of MFI altered the product selectivity due to the neutralization of strong acid sites, but catalytic deactivation was negligible. The difference of MWW and MFI zeolites in the MTO reaction was explained by their difference in pore structure.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.155-155
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• 2011

용융탄산염 연료전지(MCFC)는 $650^{\circ}C$에서 작동하는 고온형 연료전지 시스템이다. 이 시스템은 천연가스 등을 개질하여 생산된 수소를 바로 전기로 생산할 수 있는 시스템으로 열효율이 높으며, 현재 대체 발전시스템으로 각광을 받고 있다. MCFC는 개질방식에 따라 내부개질 방식과 외부개질 방식이 있다. 내부개질 방식은 수소를 생산하는 개질기가 스택내부에 장착된 형식으로 천연가스를 스택내부에서 개질하여 바로 전기를 생산하는 방식이다. 이 내부개질반응에 사용되는 촉매로는 알루미나에 고함량 (약 50 wt.%)으로 담지된 니켈(Ni) 계열촉매이 주로 쓰이고 있다. 이 고함량으로 담지된 촉매는 대부분 높은 활성을 보인다. 비교적 낮은 온도 운전조건 (약 $580{\sim}620^{\circ}C$)을 가지는 MCFC 내부개질에 적용하기 위해서는 활성점인 니켈을 최대한 담지체에 고르게 분산 시켜야한다. 이를 위해서 MgO를 이용하여 촉매의 활성점을 높게 분산시키는 연구를 진행 하였다. 촉매를 제조하는 방법으로 요소(urea)를 이용한 균일용액침전법을 이용하였다. 니켈함량은 50 wt.%로 고정을 한 다음, MgO 양과 $Al_2O_3$ 양을 각각 0 ~ 45 wt.%와 5 ~ 50 wt.%로 조절하면서 촉매를 제조하여 그 특성들을 분석하였다. 물성을 비교하기 위해서, X-선 회절분석 (XRD) 및 TPR, 물리화학흡착 실험을 하였다. 촉매의 활성을 살펴보기 위해서, fresh 상태 및 피독 상태에서 메탄수증기 개질활성 실험을 실시하였다. MgO 함량이 없거나 적은 촉매에서는 높은 BET surface area와 작은 NiO, metallic Ni 결정 크기가 나타났다. 반면 MgO 함량이 높은 촉매에서 낮은 BET surface area와 비교적 큰 NiO, metallic Ni 결정 크기가 나타났다. 또한 XRD 분석에서 MgO 함량이 증가할 수 록 MgO 결정 피크가 명확히 나타났으며, $MgAl_2O_4$ 피크는 나타나지 않았다. TPR 분석에서 촉매들의 환원 피크를 측정한 결과, 저함량의 MgO를 포함한 촉매는 $700^{\circ}C$ 부근에 환원 피크가 관찰되었고 MgO가 고함량인 촉매는 환원 피크가 $400^{\circ}C$ 부근에서 관찰되었다. 촉매의 초기 fresh 상태에서의 활성은 고함량 MgO를 포함한 Ni-90M10A 샘플을 제외하고 모든 촉매가 거의 비슷하게 나타났다. 그러나 $K_2CO_3$ 피독 상태에서는 MgO 함량이 증가할 수 록 활성이 좋지 않았음을 알 수 있었다. 따라서 MgO가 소량 포함된 촉매의 경우 fresh 상태에서는 우수한 물성과 활성을 보이지만, 피독상태에서는 MgO가 포함되지 않은 Ni-$Al_2O_3$ 촉매가 우수한 활성을 보였다.

• Korean Chemical Engineering Research
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• v.53 no.6
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• pp.824-830
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• 2015

The influence of phosphorous precursors, $NH_4H_2PO_4$, $(NH_4)_2HPO_4$, $H_3PO_4$, $(C_2H_5)_3PO_4$, and $P_2O_5$, on the catalytic performance of the $BiFe_{0.65}MoP_{0.1}$ catalysts in the oxidative dehydrogenation of 1-butene to 1,3-butadiene was studied. The catalysts were characterized by XRD, $N_2$-sorption, ICP, SEM and TPRO analyses. It was not observed big difference on the physical properties of catalysts in accordance with used different phosphorous precursors, however, the catalytic performance was largely depended on the nature of the phosphorous precursors. Of various precursors, the $BiFe_{0.65}MoP_{0.1}$ oxide catalyst, which was prepared from a phosphoric acid precursor, showed the best catalytic performance. Conversion and yield to butadiene of the catalyst showed 79.5% and 67.7%, respectively, after 14 h on stream. The cation of phosphorous precursors was speculated to affect the lattice structure of the catalysts during catalyst preparation and this difference was influenced on the re-oxidation ability of the catalysts. Based on the results of TPRO, it was proposed that the catalytic performance could be correlated with re-oxidation ability of the catalysts.

• Journal of the Mineralogical Society of Korea
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• v.29 no.4
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• pp.209-220
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• 2016

Clay minerals are a major player to determine geochemical cycles of trace metals and carbon in the critical zone which covers the atmosphere down to groundwater aquifers. Molecular dynamics (MD) simulations can examine the Earth materials at an atomic level and, therefore, provide detailed fundamental-level insights related to physicochemical properties of clay minerals. In the current study, we have applied classical MD simulations with clayFF force field to dioctahedral clay minerals (i.e., gibbsite, kaolinite, and pyrophyllite) to analyze and compare structural parameters (lattice parameter, atomic pair distance) with experiments. We further calculated vibrational power spectra for the hydroxyls of the minerals by using the MD simulations results. The MD simulations predicted lattice parameters and interatomic distances respectively deviated less than 0.1~3.7% and 5% from the experimental results. The stretching vibrational wavenumber of the hydroxyl groups were calculated $200-300cm^{-1}$ higher than experiment. However, the trends in the frequencies among different surface hydroxyl groups of each mineral was consistent with experimental results. The angle formed by the surface hydroxyl group with the (001) plane and hydrogen bond distances of the surface hydroxyls were consistent with experimental result trends. The inner hydroxyls, however, showed results somewhat deviated from reported data in the literature. These results indicate that molecular dynamics simulations with clayFF can be a useful method in elucidating the roles of surface hydroxyl groups in the adsorption of metal ions to clay minerals.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.358-364
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• 2012

The kinetics of the Fischer-Tropsch synthesis and water gas shift reactions over a precipitated iron catalyst were studied in a 5 channel fixed-bed reactor. Experimental conditions were changed as follows: synthesis gas $H_2$/CO feed ratios of 0.5~2, reactants flow rate of 60~80 ml/min, and reaction temperature of $255{\sim}275^{\circ}C$ at a constant pressure of 1.5 MPa. The reaction rate of Fischer-Tropsch synthesis was calculated from Eley-Rideal mechanism in which the rate-determining step was the formation of the monomer species (methylene) by hydrogenation of associatively adsorbed CO. Whereas water gas shift reaction rate was determined by the formation of a formate intermediate species as the rate-determining step. As a result, the reaction rates of Fischer-Tropsch synthesis for the hydrocarbon formation and water gas shift for the $CO_2$ production were in good agreement with the experimental values, respectively. Therefore, the reaction rates ($r_{FT}$, $r_{WGS}$, $-r_{CO}$) derived from the reaction mechanisms showed good agreement both with experimental values and with some kinetic models from literature.

• Clean Technology
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• v.14 no.3
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• pp.176-183
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• 2008

The purpose of this study is to upgrade the catalysts for synthesizing mixed octenes using normal butene and the catalysts for synthesizing $C_9$-aldehyde through hydroformylation of mixed octenes with syngas. The in-line activation method with circulating activating solution was effective for activation of the $NiO/A1_{2}O_3$ catalyst. The reason for catalyst deactivation may be ascribed to physi-sorbed materials or oligomers which block pore entrance and then prevent active sites from participating a reaction. Continuous distillation apparatus was used for separating mixed octenes from dimerization products. When reflux ratio was above 3 : 1, mixed octene fraction of which purity was above 99.57% was obtained. In $C_9$-aldehyde synthesis through hydroformylation of mixed octenes, we investigated a performance of ligand which increased catalyst stability as well as activity of Co catalyst. The results indicated that TPPO, NMP, NDMA, and succinonitrile were suitable ligand for increasing initial activity and reducing loss of Co during catalyst recovery.

• Journal of the Korean Society of Marine Environment & Safety
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• v.25 no.7
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• pp.914-919
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• 2019

A mesocosm experiment considering water exchange was conducted to evaluate the change in the properties of contaminated coastal sediment. The contaminated coastal sediment sample was prepared by mixing with granulated coal ash(GCA), which is an alkaline industrial by-product. During one month of observation time, the phosphate concentration of the GCA sample case was measured to be 19.0 and 0.4 mg/L lower than that of the control sample at the pore water and overlying water, respectively. The hydrogen sulfide concentration of the GCA sample case was 5.0 mg/L, which is significantly lower than that of the control sample(112.5 mg/L). Further addition of GCA in the sediment reduced the concentrations of phosphate and hydrogen sulfide, and could enhance the adsorption reaction, when compared to the sediment without GCA. The dissolved oxygen concentration in the overlying water of the GCA sample was measured to be 3.47 mg/L higher than the control sample. From the above results, we confirmed that GCA is an effective material for reducing pollutants in coastal sediment.

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.629-633
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• 1998

The synthesis of 1,1-difluoroethane from acetylene as a function of HF/acetylene ratio, contact time and reaction temperature was studied on a fluorinated ${\gamma}-Al_2O_3$. The fluorination of ${\gamma}-Al_2O_3$ was treated with pure HF gas at high temperature. The crystallinity, the porosity, and the acid properties of the prepared samples were examined using XRD, the nitrogen adsorption, pyridine-IR and ammonia-TPD respectively. The activity was enhanced by further fluorination of alumina. The fraction of 1,1-difluoroethane was obtained above 90% at reaction temperature of about $200^{\circ}C$. The ratio of 1,1-difluoroethane to vinylfluoride over fluorinated ${\gamma}-Al_2O_3$ catalyst was increased with the mole ratio of HF/acetylene and contact time, and was found to be the highest ratio at reaction temperature of $200^{\circ}C$.

• Journal of the Korean Institute of Gas
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• v.25 no.4
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• pp.49-56
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• 2021

Liquefied Petroleum Gas is divided into liquefied gases containing propane (C₃H₈) and butane (C₄H₁₀). The quality of LPG varies greatly depending on the composition of the mixture, so it is important to measure the composition accurately. It is difficult to determine the composition of the mixture because liquid and gas coexist at room temperature. Therefore, the uncertainty in determining the concentration of hydrocarbons by component is high, and there are many problems that differ from the actual content standard. Therefore, it is necessary to develop a mixed liquid propane standard gas for the composition and accurate concentration of hydrocarbon substances. Mixed liquid propane standard gas is manufactured into bellows-type constant-pressure cylinders by ISO-6142 (2015). The homogeneity of the four standard gases manufactured was confirmed to be GC-FID. The manufacturer's uncertainty of expansion was 0.01 % to 0.30 % and homogeneity was 0.03 % to 0.25 %. In this mixed liquid propane standard gas, the relative expansion uncertainty of weight method, manufacturing consistency, cylinder adsorption and long-term stability was developed within 0.26 %-1.3 9% (95% of confidence level, k=2).

• Korean Chemical Engineering Research
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• v.46 no.3
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• pp.581-584
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• 2008

The catalyst carriers of the mesoporous layer compounds were prepared to carry out the partial oxidation of methane(POM) to hydrogen. The catalytic activities of POM to hydrogen were investigated over Ru(3)/SPK and Ru(3)/SPM catalyst in a fixed bed flow reactor under atmosphere. In addition, the catalysts and carriers were characterized by BET, TEM, TPR. The BET surface areas of the silica-pillared $H^+-kenyaite$(SPK) and the silica-pillared $H^+-magadite$(SPM) were $760m^2/g$ and $810m^2/g$, repectively, and the average pore sizes were 3.0 nm and 2.6 nm, repectively. The nitrogen adsorption isotherms were type IV with developed hysteresis. The TEM showed that the mesoporous layer compounds were formed well. The Ru(3)/SPK and the Ru(3)/SPM catalyst were obtained high hydrogen yields(90%, 87%), and were kept constant high hydrogen yields even about 60 hours at 973 K, $CH_4/O_2=2$, $1.25{\times}10^{-5}g-Cat.hr/ml$. The TPR peaks of Ru(3)/SPK and the Ru(3)/SPM catalyst showed the similar reducibilities around 453 K and 413 K. It could be suggested that SPK and SPM had the physicochemical properties as oxidation catalyst carries from these analysis data.