고분자전해질형 연료전지에서 촉매의 활성을 증가시키기 위하여 기존에 사용되고 있는 백금과 전이금속인 chromium, nickel과의 합금을 제조하였다. XRD를 이용하여 합금의 구조가 33˚에서 superlattice line을 가지고 있는 것으로 보아 face centered cubic 구조를 가진 ordered alloy로 이루어졌다는 것을 알 수 있었다. 열처리 온도가 증가할수록 합금의 입자 크기는 증가하였으며, 결정 격자 상수는 감소하였다. 전지성능테스트, cyclic voltammogram 등을 통하여 mass activity, specific activity, Tafel slope, 개회로 전압을 측정한 결과, 합금촉매의 활성이 순수한 백금촉매보다 크게 향상되었음을 알 수 있었다.

The selective catalytic reduction(SCR) of nitric oxide by ethane in the presence of oxygen was investigated on Cu-ZSM-5, Co-ZSM-5 and Ga-ZSM-5 catalysts over a range of 400, 450 and 500℃. The catalysts were prepared by ion-exchange method. The composition of the reactant gases were 1000 ppm of NO, 1000 ppm of C2H6 and 2.5% of O2, and the reaction was conducted in a fixed-bed reactor at 1 atm. For the 20wt% Co-ZSM-5(50) catalyst, the NO conversion reached up to 100%, while the C2H6 conversion and the CO selectivity were about 50% and 25%, respectively, at 450℃. For the 20wt% Cu-ZSM-5(50) catalyst, the NO conversion and the C2H6 conversion were about 80% and 100%, respectively, but there was no CO produced. The metal ion-exchanged ZSM-5 catalysts exhibited a tendency to increase the NO conversion with the Si/Al ratio of the ZSM-5, that is, NO conversion was inversely proportional to the acidity of the catalysts. But, the effect of the acidity on NO conversion was not so large. From the XRD results of the catalysts before and after SCR reaction it was found that there was no structural change.

CuxFe3-xO4 catalyst and ZnxFe3-xO4 catalyst were synthesized by the air oxidation method with various C(II) and Zn(II) weights. Activated catalysts decomposed carbon dioxide to carbon at 350℃, 380℃, 410℃ and 440℃. The value of carbon dioxide decomposition rate for Cu0.003Fe2.997O4 and Zn0.003Fe2.997O4 catslysts than was better catalysts. The decomposed rate of the catalysts is about 85%~90%. The reaction rate constant(4.00 psi1-α/min) and activation energy(2.62 kcal/mole) of Cu0.003Fe2.997O4 catalyst are better than Zn0.003Fe2.997O4

The Cuo-Magnetite and ZnO-Magnetite catalysts with various of Cuo and ZnO mole% for Carbon Dioxide decomposed reaction synthesized. The catalysts were reduced by H2 at 350℃ for 3 hours. The temperature was obtained by TGA and DSC experiments. The structures of catalysts were confirmed by X-ray diffraction experiment. The surface area of catalysts is 15~27 m2/g. The results of Carbon Dioxide decomposed ability was better H2-reduced magnetite catalysts with 0.03 mole% CuO and 0.03 mole% ZnO than others catalysts. After Carbon Dioxide decomposed reaction, catalysts were reacted H2 and created only methane.

Transesterification reaction between dimethyl phthalate and ethylene glycol was kinetically investigated in the presense of various metal nitrate catalysts at 170℃. The reaction rates measured by the amount of distilled methanol from the reaction vessel. The transesterification reaction was carried out under the first order conditions respect to the concentration of dimethyl phthalate and catalyst, respectively. The over all order was 2nd. By Arrhenius plot, the activation energy was calculated as 17.4kcal/mole and 17.2kcal/mole on the transesterification reaction with zinc nitrate and lead nitrate, respectively. Apparent rate constant, k' was appeared linear about concentration of catalyst.

Transesterification reactions (methyl methacrylate with diethanolamine, ethylene glycol with dimethylphthalate) were kinetically investigated in the presence of zinc compound catalysts at 120~170℃ The amount of reactants was measured by gas chromatography. and the reaction rates also measured from the amount of reaction products and reactants upon each catalyst. The transesterification reactions were carried out under the first order conditions respect to the concentration of reactants, respectively, The overall reaction order was 2nd. The apparent rate constant (k') was found to obey first kinetics with respect to the concentration of catalyst. It shows that according to an increase in basicity of anionic species the rate constant increase, and that a linear relationship exists between ln k and pKa in transesterification reaction of methyl methacrylate with diethanolamine.

상업적으로 HTS (High Temperature Shift reaction) 반응에서 사용되는 Fe2O3/Cr2O3 촉매는 사용 후 6가 크롬 (Cr6+)의 침출에 따른 환경적/인체적 문제를 일으킬 수 있는 잠재성을 가지고 있어 친환경 크롬-프리 촉매개발을 위한 연구가 활발히 진행되고 있다. 본 연구에서는 크롬을 사용하지 않고 우수한 성능을 나타낼 수 있는 Fe/Al, Fe/Al/Cu, 그리고, Fe/Al/Ni 촉매를 제조하고 성능을 비교 평가하였다. 단계함침법으로 금속산화물(Cu와 Ni)과 알루미늄이 함유된 Fe계 촉매를 제조하고 촉매반응장치를 이용하여 각 촉매의 활성을 분석하였다. 그 결과 Fe/Al/Cu 촉매는 가혹한 조건(COconc. = 38.2%; 천연가스 대비 약 5.7 배 높은 CO 농도)에서도 탁월한 성능(XCO = 84.3% at 400 ℃)을 나타내었다. 이 결과는 Fe/Al/Cu 촉매의 강한 환원력과 활성종인 Fe3O4의 높은 열적 안정성에 기인한 것으로 확인되었다. 또한 강한 소결 저항성을 가진 Fe/Al/Cu 촉매는 400°C에서 100시간 동안 뚜렷한 비활성화를 보이지 않아 높은 안정성을 지닌 것으로 확인되었다.

본 연구에서는 폐자원 합성가스를 이용한 고온전이반응용 Ce가 첨가된 Cu/γ-Al2O3 촉매의 물리 화학적 특성을 비교 분석하였다. 합성방법에 따른 촉매의 특성을 비교하기 위해 활성물질의 담지 순서를 변경하여 Ce/Cu/γ-Al2O3, Ce-Cu/γ-Al2O3, Cu/Ce/γ-Al2O3, Cu/γ-Al2O3 촉매를 제조하였다. 제조된 촉매 중 Ce/Cu/γ-Al2O3 촉매가 가장 높은 활성도 및 안전성을 나타냈다. 제조된 촉매의 물리-화학적 특성은 XRD, H2-TPR, XPS, Raman, Photoluminescence 등으로 분석하였다. 그리고 CO 전환율에서도 CeO2로 첨가된 모든 Cu/γ-Al2O3 촉매는 Cu/γ-Al2O3보다 높은 CO 전환율을 보였다. 이 연구결과는 CeO2의 첨가가 고온전이반응에서 Cu/γ-Al2O3 촉매의 성능을 향상 시킨 것을 나타낸다. 또한, Ce/Cu/γ-Al2O3 촉매의 높은 촉매 활성은 주로 고농도 산소저장능 및 환원된 Cu종과 관련이 있음을 알 수 있었다.

질소산화물 등의 배출규제 강화로 인한 사용처의 확대로 SCR(선택적 촉매 환원) 촉매 수요가 증가하고 있으며, 이에 따라 폐촉매 발생량도 증가할 것으로 예상된다. 폐촉매는 지정폐기물로 분류되어 처리시에 비용이 발생하여, 물리적으로 재생하여 재사용 하거나 유가금속을 회수하는 방법으로 재활용하고 있다. 그러나 재생의 횟수가 제한적이고, 유가금속 회수는 비용이 고가이며 촉매의 85~90%를 차지하는 TiO2가 폐기된다는 문제점이 있다. 따라서, 본 연구에서는 SCR 촉매를 경제적이며 지속적으로 사용하기 위해 피독된 SCR 촉매 내 피독물질만 화학적으로 수세 및 정제하고 유가금속/TiO2의 함량을 높이는 최적의 세정 용매를 도출하는 촉매 재활성을 위한 기초연구를 수행하였다. 비교대상 촉매인 Poisoned 촉매를 5가지 세정용매로 화학적 처리결과, acetic acid 용매가 V2O5 1.19 wt%의 높은 함량과 57.6%의 높은 피독물질 제거효율을 나타내며 다른 산 처리 용매에 비해 촉매 재생성이 높은 것으로 분석되었다. 세정 용매의 농도와 세정 시간에 따른 V2O5 함량과 피독물질 제거효율에 미치는 영향을 알아보기 위해 각각 변수를 두어 실험을 진행하였다. 본 연구를 통해 0.1 N acetic acid로 처리한 촉매가 가장 높은 NOX전환율을 나타냈으며, 유가금속/TiO2 함량 또한 높게 나타나 본 연구 목표에 가장 적합한 세정용매로 판단되었다.

본 연구에서는 폐기물가스화 후 생성되는 합성가스의 고순도 수소화를 위해 고온 수성가스전이반응(HT-WGS : High Temperature-Water Gas Shift) 반응용 특정 산화물(CeO2, ZrO2, TiO2 및 Al2O3)에 코발트를 담지한 촉매를 제조하고 그 산화환원특성을 비교 분석하였다. 특정 산화물에 Co를 함침법을 이용하여 담지하여 Co/CeO2, Co/ZrO2, Co/Al2O3, Co/TiO2 촉매를 각각 제조하였다. 제조된 Co 기반 촉매의 물리적 특성 분석은 BET 비표면적과 XRD 분석을 통해 수행하였고 CO 화학흡착과 H2-TPR 분석을 통해 산화환원 특성을 파악하고 동시에 물리-화학적 특성간의 상관관계를 해석하였다. H2-TPR 분석 및 CO 화학흡착 분석 결과, 코발트의 분산이 지지체 산화물의 환원성과 밀접한 상관관계를 가지고 있음을 알 수 있었다. 이 연구 결과는 Co/CeO2가 반응온도 350 ~ 550℃에서 활성 평가한 촉매 중에서 가장 우수한 활성을 나타내었다. 또한, Co/CeO2 촉매가 Co/ZrO2 및 Co/Al2O3 촉매보다 높은 촉매 활성 및 안정성을 나타내었다. Co/CeO2 촉매의 탁월한 활성 및 안정성은 지지체의 환원성과 높은 Co 금속의 분산에 기인하는 것으로 나타났다. 결과적으로 폐기물가스화로부터 생산된 합성가스를 고순도 수소로 전환하기 위한 HT-WGS 반응에서 Co/CeO2 촉매는 매우 유망한 촉매임을 알 수 있었다.

Combustion of ethanol (EtOH) at low temperatures has been studied using titania- and silica-supported platinum nanocrystallites with different sizes in a wide range of 1~25 nm, to see if EtOH can be used as a clean, alternative fuel, i.e., one that does not emit sulfur oxides, fine particulates and nitrogen oxides, and if the combustion flue gas can be used for directly heating the interior of greenhouses. The results of H2-N2O titration on the supported Pt catalysts with no calcination indicate a metal dispersion of 0.97±0.1, corresponding to ca. 1.2 nm, while the calcination of 0.65% Pt/SiO2 at 600 and 900℃ gives the respective sizes of 13.7 and 24.6 nm when using X-ray diffraction technique, as expected. A comparison of EtOH combustion using Pt/TiO2 and Pt/SiO2 catalysts with the same metal content, dispersion and nanoparticle size discloses that the former is better at all temperatures up to 200℃, suggesting that some acid sites can play a role for the combustion. There is a noticeable difference in the combustion characteristics of EtOH at 80~200℃ between samples of 0.65% Pt/SiO2 consisting of different metal particle sizes; the catalyst with larger platinum nanoparticles shows higher intrinsic activity. Besides the formation of CO2, low-temperature combustion of EtOH can lead to many other pathways that generate undesired byproducts, such as formaldehyde, acetaldehyde, acetic acid, diethyl ether, and ethylene, depending strongly on the catalyst and reaction conditions. A 0.65% Pt/SiO2 catalyst with a Pt crystallite size of 24.6 nm shows stable performances in EtOH combustion at 120℃ even for 12 h, regardless of the space velocity allowed.

The purpose of this study was to investigate the effect of the preparation method on CeO2-promoted Cu/γ -Al2O3 catalysts for the high temperature shift reaction using simulated waste-derived syngas (H2 + CO). To investigate the effect of preparation method on the CeO2-promoted Cu/γ-Al2O3 catalyst, we compared catalytic performance over Ce/Cu/γ-Al2O3, Ce-Cu/γ-Al2O3, Cu/Ce/γ-Al2O3, and Cu/γ-Al2O3 catalysts, and tried to explain the differences in catalytic performance with various characterization methods. The physico-chemical properties of the CeO2-promoted catalysts were characterized using surface spectroscopies such as BET, XRD, TPR, XPS, Raman spectroscopy, photoluminescence spectroscopy, and N2O-chemisorption. The catalyst characterizations were correlated with activity results in the high temperature shift reaction.

Most of the commercial SCR technology is very efficient in the temperature range of 250∼350℃. However, the flue gas temperature after waste heat recovery system or wet desulfurization system is in general under 200℃. The performance of SCR system is very poor and there are slip ammonia problem at low temperature. Low temperature SCR technology is necessary to save the flue gas reheating energy and reduce the greenhouse gas emission. The SCR catalyst operating at low temperature has been developed for the new waste flue gas heat recovery system of the existing incinerator. The flue gas temperature is under 170℃ after the flue gas heat recovery. The SCR catalyst is made by key component Mn impregnated on γ-Al2O3 of which the diameter is 1.7mm~2.8mm. The dimension of cylindrical SCR reactor is inside diameter 22.1mm and height 350mm. The effects of reducing agent injection rates, space velocity at different reaction temperature were studied on the De-NOx performance and slip ammonia to get a design data. It was found that the Mn based SCR catalyst is effective in low temperature flue gas without ammonia slip. The outlet concentration of NOx in the flue gas decreased to 12ppm from inlet 150ppm at space velocity 10,000 hr-, NH3/NO = 1 and reaction temperature 170℃. The De-NOx efficiency is 92% at reaction temperature 170℃ which is much higher than 82% at 150℃. At the SCR reaction temperature 170℃, the NOx removal efficiency was 78~99% in the space velocity range 5,000~12,500hr-, and 79~92% at NH3/NO ratio range 0.5~1.0.

The effect of the metal oxide catalyst in the dimerization of waste vegetable oil was investigated. The high efficiency and recyclability has allowed different metal oxides to be used as catalysts in numerous synthetic reactions. Herein, clay, aluminum, titanium, calcium, magnesium and silicon oxide micro/nanoparticles are used in a Diels-Alder reaction to catalyze the production of the dimer acids. The metal oxides assist the electron transfers during cyclization to produce the desired product. Liquid chromatography mass spectroscopy (LC-MS) and gel permeation chromatography (GPC) were used to verify the production of dimer acids. For the confirmation of cyclization, compounds were analyzed using the nuclear magnetic resonance (NMR) spectroscopy. From the analysis, silylated or pristine clay showed its effectiveness as a catalyst in dimerization. Furthermore, alumina and alumina/silica composite showed successful performance in the reaction to yield cyclic dimer acids. These result suggested that metal oxides and montmorillonite might be used in synthesis of dimer acids for the recycle of waste vegetable oils.

Titania-supported chromium oxides with different loadings have been embarked in catalytic oxidation of trichloroethylene (TCE) to inquire association of the formation of crystalline Cr2O3 with catalytic performances. A better activity in the oxidative TCE decomposition at chosen temperatures was represented when chromium oxides (CrOx) had been dispersed on pure anatase-type TiO2 (DT51D) rather than on phase-mixed and sulfur-contained ones such as P25 and DT51. The extent of TCE oxidation at temperatures below 350℃ was a strong function of CrOx content in CrOx/DT51D TiO2, and a noticeable point was that the catalyst has two optimal CrOx loadings in which the lowest T50 and T90 values were measured for the TCE oxidation. This behavior in the activity with respect to CrOx amounts could be associated with the formation of crystalline Cr2O3 on the support surface, that is less active for the oxidation reaction, and an easier mobility of the surface oxygen existing in noncrystalline CrOx species with higher oxidation states, such as Cr2O8 and CrO3.

Magnetite (Fe3O4) has been prepared directly to avoid the reduction process prior to the H2 production from the high temperature water gas shift reaction of the simulated waste derived synthesis gas. Citric acid has been employed as a complexing agent for the direct synthesis of magnetite. Notably, without the reduction process, the catalyst prepared at the citric acid molar ratio of 1.0 showed 80% CO conversion at 350℃ at a gas hourly space velocity of 40,057 h-1.

Metal oxide promoted ceria-zirconia (Ce/Zr = 6/4) catalysts was applied to deoxygenation (DO) of oleic acid in batch mode at 300℃ under 1 bar of 20% H2/N2 condition. Metal oxide promoted ceria-zirconia catalysts were prepared by a co-precipitation method. As a result, Ni-Ce0.6Zr0.4O2 catalyst exhibited much higher oleic acid conversion, selectivity to C9 ~ C17 compounds (diesel fuel range), and oxygen removal efficiency than the others. This is due to the presence of free NiO species, synergy effect of nickel and Ce0.6Zr0.4O2, highest BET surface area, and the strong metal to support interaction (SMSI).

Ce(1-x)Zr(x)O2 catalysts were investigated for bio-diesel production from oleic acid using catalytic deoxygenation. In this study, deoxygenation reaction has been carried out at 300 oC under 1 bar of 20% H2/N2 pressure in batch mode. Ce(1-x)Zr(x)O2 catalysts were prepared by co-precipitation method. Ce0.6Zr0.4O2 catalyst showed the highest oleic acid conversion and C9~C17 selectivity. It has been found that the deoxygenation reaction depends strongly on the reduction property and depends partly on the crystallite size of Ce(1-x)Zr(x)O2. Thus, Ce0.6Zr0.4O2 can be selected as the most promising catalyst for deoxygenation reaction.

Recently biodiesel has drawn much attraction as renewable enegy due to its environmental benefits and the fact that it is made from renewable resources. However, the production cost of biodiesel is one of the main hurdle to commercialize it. One of the way to reduce the biodiesel production cost is to use the waste cooking oil as feedstock. In the conventional transesterification process of waste cooking oils for biodiesel production, the presence of free fatty acids and water causes severe problems such as formation of soap and decreasing of catalyst yield. Much effort has been devoted to solve the above problems and one of the promising way is the supercritical methanol treatment which is performed at the methanol supercritical environment (>239.45℃, >8.10 Mpa)one of the serious problems of the application of SCM process for the biodiesel production is the tough operation condition(high pressure, high temperature. In this study, we have studied about the supercritical methanol treatment for the biodiesel production with the soybean waste cooking oil as a feedstock in the present of various heterogeneous solid catalysts such as mesoporous silica and acid-doped mesorpous silica. Biodiesel conversion was increased at more mild opreation condition to the previous studies by using the catalysts. The conversion was more enhanced by modifying the catalysts.

Alumina-supported catalysts containing different transition metals such as Cu, Cr, Mn, Zn, Co, W were investigated for their activity in the selective oxidation of toluene. Catalytic oxidation of toluene was investigated at atmospheric pressure in a fixed bed flow reactor system over transition metals with Al2O3 catalyst. The result showed the order of catalytic activities for the complete oxidation of toluene was Mn > Cu> Cr> Co> W> Zn for 5wt.% transition metals/Al2O3. Mn/Al2O3 catalysts containing different amount of Mn were characterized by X-ray diffraction spectroscopy for decision of loading amount of metal to alumina. 5 wt.%Mn/Al2O3 catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289℃.