This study was performed to investigate the effects of water molecules on ozone oxidation of acetaldehyde using a manganese oxide catalyst at room temperature. The catalytic ozone oxidation was conducted at different relative humidity (RH) conditions of 0%, 50%, and 80%. As the RH increased, both ozone and acetaldehyde removal efficiencies dropped due to competitive adsorption on the surface of the catalyst. At the highest RH of 80%, the oxidation reaction was severely retarded, and oxidation by-products such as acetic acid were formed and adsorbed on the surface. After the ozone oxidation of acetaldehyde, the regeneration of the catalyst using ozone alone was tested, and the further oxidation of accumulated organic compounds was investigated under the RH conditions of 0%, 50%, and 80%. When the highest relative humidity was introduced in the regeneration step, the ozonation reaction with the by-products adsorbed on the catalyst surface decreased due to the competitive reaction with water molecules. These findings revealed that, only when relative humidity was low to minimize the formation of by-products, the ozone oxidation of acetaldehyde using the manganese oxide catalyst at room temperature can be feasible as an effective control method.
고분자 전해질 연료전지의 연료에 포함된 일산화탄소의 선택적 산화를 위하여, 귀금속 촉매를 대체하기 위한 CuO-CeO2 복합 산화물 촉매를 졸-겔법과 공침법으로 제조하였다. 졸-겔법으로 촉매 제조 시 Cu/Ce의 비와 가수분해 비를 변화시켰다. 제조한 촉매의 활성은 귀금속 촉매(Pt/γ-Al2O3)와 비교하였다. Cu/Ce의 비를 변화시키면서 제조한 촉매 중 Cu/Ce의 비가 4:16인 촉매가 가장 높은 CO 전환율(90%)과 선택도(60%)를 나타내었다. 촉매의 제조에서 가수분해 비가 증가할수록 촉매 표면적이 증가하였고, 아울러 촉매 활성 또한 증가하였다. 공침법으로 제조한 촉매와 1wt% Pt/γ-Al2O3 촉매의 가장 높은 CO 전환율은 각각 82% 및 81%인 반면, 졸-겔법으로 제조한 촉매의 경우는 90%가 얻어졌다. 이는 졸-겔법으로 제조한 촉매가 공침법으로 제조한 촉매나 귀금속 촉매보다 더 높은 촉매활성을 보임을 의미한다. CO-TPD 실험을 통하여, 낮은 온도(140℃)에서 CO를 탈착하는 촉매가 본 반응에서 더 높은 촉매활성을 보임을 알 수 있었다.
본 연구에서는 배가스 내 존재하는 오염물질인 NO의 처리효율을 증대시키기 위하여 NO 산화 공정을 연구하였으며, 강력한 산화력의 건식산화제를 제조하는 방법으로 H2O2 촉매분해가 도입되었다. H2O2 분해공정 상에서 적용 가능한 K-Mn/Fe2O3 불균일계 촉매가 제조되었으며, 이들이 가지는 물리화학 적 특성이 H2O2 분해반응에 미치는 영향이 조사되었다. 제조된 건식산화제는 NO가 포함된 모사 배가스를 처리하기 위한 NO 산화공정에 적용되었으며, 다양한 모사 배가스의 유량(5, 10, 20 L/min)에서 약 100% 가까운 NO 전환율을 확인 하였다.
This study was performed to obtain high conversion efficiency of NH3 and minimize generation of nitrogen oxides using metal-supported catalyst with Ag : Cu ratio. Through structural analysis of the prepared catalyst with Ag : Cu ratio ((10-x)Ag–xCu (0≤ x ≤6)), it was confirmed that the specific surface area was decrease with increasing metal content. A prepared catalysts showed Type Ⅱ adsorption isotherms regardless of the ratio Ag : Cu of metal content, and crystalline phase of Ag2O, CuO and CuAl2O was observed by XRD analysis. In the low temperature(150∼200 ℃), a conversion efficiency of AC_10 recorded the highest(98%), whereas AC_5 (Ag : Cu = 5 : 5) also showed good conversion efficiency(93.8%). However, in the high temperature range, the amounts of by-products(NO, NO2) formed with AC_5 was lower than that of AC_10. From these results, It is concluded that AC_5 is more environmentally and economically suitable.
In this study, the used DOCs, which could remove the air pollutants such as CO and HC in the exhaust gas from diesel vehicle, were remanufactured by various conditions. Their catalytic performances and characterization were also investigated. The remanufacturing process of the deactivated DOCs includes high temperature cleaning of incineration, ultrasonic cleaning for washing with acid/base solutions to remove deactivating materials deposited to the surface of the catalysts, and active component reimpregnation for reactivating catalytic activity of them. The catalytic performance tests of the remanufactured DOCs were carried out by the diesel engine dynamo systems and chassi dynamo systems in CVS-75 mode. All prepared catalysts were characterized by the optical microscopes, SEM, EDX, porosimeter and BET to investigate correlations between catalytic reactivity and surface characteristics of them. The remanufactured DOCs at various conditions showed the improved catalytic performances reaching to 90% of fresh DOC, which is attributed to remove the deactivating materials from the surface of the used DOC through the analysis of catalytic performance test and their characterization.
Oxidation characteristics of benzene as a VOC were investigated using a fixed bed reactor system over transition metal catalysts. The transition metal catalysts were made by using transition metal nitrate reagent and various support materials such as γ-Al2O3, and TiO2. The parametric tests were conducted at the reaction temperature range of 200~500℃, benzene concentration of 2,000~3,000 ppm with space velocity of 10000 hr-1. The property analyses such as BET, SEM, TGA and the conversions of catalytic oxidation of VOC were examined. The experimental results showed that the BET surface areas of catalyst are 86.4∼167.7m2/g, the pore volumes are 0.049∼0.056cm3/g, and the average pore sizes of catalyst are 27∼44Å, which mean the meso pore. It was also found that the conversion of benzene oxidation reaction at 400∼500℃ with Cu/γ-Al2O3+TiO2 catalyst showed 90∼100%, which indicate that the transition metal catalyst with composite supports is very effective for the oxidation of benzene.
In this study, toluene catalytic oxidation was investigated using various metal components (Cu, Ce, Ni, La and Zr) supported on Used FCC zeolite for the application of the waste recycling and odor reduction. Among the metals, 5 wt% Cu/zeolite showed the best catalytic activity. 100 % conversion was achieved at 300℃ which was 50℃ lower than that of other metal components. As increasing the amount of doped Cu, the CuO was formed and the surface area and pore size were decreased. By the reduction treatment before toluene oxidation, the catalytic activity of the oxidation below 250℃ was improved. No decrease of conversion was observed during the continuos reaction at 300℃ for 48 h.
Oxidation characteristics of benzene as a VOC was investigated using a fixed bed reactor system over copper base catalysts. The copper base catalysts were made by using copper nitrate reagent and various support materials such as γ-Al2O3, TiO2, and zeolite. The parametric tests were conducted at the reaction temperature range of 200~500℃, benzene concentration of 1,000~2,000 ppm, and space velocity range of 5,000~20,000 hr-1. The property analyses such as BET, SEM, XRD and the conversions of catalytic oxidation of VOC were examined. XRD analysis on copper catalysts showed CuO crystal forms and the peak intensity of CuO increased as the impregnation weight of copper grew. The experimental results showed that the conversion was increased with decreasing space velocity. It was also found that Cu/γ-Al2O3+TiO2 catalyst showed the highest activity for the oxidation of benzene and 15% metal loading was the optimum impregnation level.
Electrochemical promotion of the reaction rate was investigated for CO oxidation in a solid electrolyte catalytic reactor where a thin film of Pt was deposited on the yttria stabilized zirconia as an electrode as well as a catalyst. It was shown under open circuit condition that potential was a mixed potential of O2exchange reaction and electrochemical reaction induced by CO. The effect of electrochemical modification on the CO oxidation rate was studied at various overpotentials and PCOPO2.
고도산화공정(Advanced Oxidation Process, AOP) 중 하나인 펜톤 산화법은 과산화수소(H2O2)와 2가철 이온(Fe2+)이 반응하여 OH 라디칼을 생성함으로써, OH 라디칼의 강한 산화력으로 유기물을 분해하는 방법이다(Kim et al., 2016). 펜톤 산화는 다양한 유기물과의 높은 반응성을 지닌다는 점과 생물학적으로 분해가 어려운 물질을 산화·분해시켜 생물학적 처리가 가능하도록 한다는 등의 장점을 지니고 있다(Lee et al., 2003, Sung et al., 2006). 그러나, 펜톤 산화는 유기물과의 반응 후 펜톤 슬러지를 부산물로 다량 생성하기 때문에 발생된 슬러지를 처리하는 공정이 추가적으로 요구된다. 또한, 펜톤 슬러지는 다량의 난분해성 물질과 철염 등을 함유하고 있기 때문에 처리하는 방법이 까다롭다. 펜톤 슬러지는 주로 ‘매립’으로 처리하고 있으나 매립지 크기의 한계 및 수명 단축, 비싼 처리비용 등의 문제가 뒤따르기 때문에 이에 대한 대책이 필요한 실정이다. 본 연구에서는 펜톤 슬러지를 처리하는 방안으로 펜톤 산화용 철 촉매로의 재이용을 제안하였고, 크게 슬러지 용해, 슬러지 내 철 이온 전환, 철 촉매 실사용 단계로 나눠 연구를 진행하였다. 본 연구는 ‘D’ 산업용수센터에서 발생하는 RO 농축폐수를 펜톤 산화법으로 처리한 후 발생하는 펜톤 슬러지를 대상으로 실시하였다. 반고체 형태의 펜톤 슬러지에 산(acid)을 가하면 용해액 상태로 바뀌는데 이는 펜톤 슬러지 사용을 용이하게 만든다. 이에 pH, 반응시간 등의 실험 인자를 바꿔가며 슬러지 용해 최적조건을 찾고자 하였다. 한편, 펜톤 슬러지를 펜톤 산화용 철 촉매로 재이용하기 위해서는 용해된 펜톤 슬러지 내 철 형태가 2가철 이온으로 존재하는 것이 유리하다. 용해된 펜톤 슬러지 내 철 이온은 대부분 3가철 형태로 존재하는데 Zn, Cd, Cu 등의 금속, 요오드산, 철편 등의 환원제를 투입함으로써 3가철을 2가철 이온으로 환원할 수 있다. 본 연구에서는 영가철을 환원제로 사용하여 용해된 슬러지 내 철 이온을 2가철 이온으로 환원하였다. 용해된 펜톤 슬러지에 영가철을 투입하였고 pH, 반응시간, 영가철 투입량 등 반응 인자를 바꿔가며 펜톤 슬러지 내 2가철 이온 전환의 최적조건을 찾고자 하였다. 두 단계를 거쳐 생성된 펜톤 슬러지 기반의 철 촉매는 실제 RO 농축폐수를 펜톤 산화로 처리할 때 펜톤 산화 시약으로 사용하였으며, 실제 펜톤 산화에서 사용하는 2가철 촉매(FeSO4)와 비교하여 펜톤슬러지 기반의 철 촉매의 효율성을 평가하였다.
A novel pretreatment technique was applied to the conventional Pt/alumina catalyst to prepare for the highly efficient catalyst for the preferential oxidation of carbon monoxide in hydrogen-rich condition. Their performance was investigated by selective CO oxidation reaction. CO conversion with the oxygen-treated Pt/Alumina catalyst increased remarkably especially at the low temperature below 100℃. This result is promising for the normal operation of the proton exchange membrane fuel cell (PEMFC) without CO poisoning of the anode catalyst. XRD analysis results showed that metallic Pt peaks were not observed for the oxygen-treated catalyst. This implies that well dispersed small Pt particles exist on the catalyst. This result was confirmed by high resolution transmission electron microscopy (HRTEM) analysis. Consequently, it can be concluded that highly dispersed Pt nanoparticles could be prepared by the novel pretreatment technique and thus, CO conversion could be increased considerably especially at the low temperatures below 100℃.
Advanced oxidation processes involving O3/H2O2 and O3/catalyst were used to compare the degradability and the effect of pH on the oxidation of 1,4-dioxane. Oxidation processes were carried out in a bubble column reactor under different pH. Initial hydrogen peroxide concentration was 3.52 mM in O3/H2O2 process and 115 g/L (0.65 wt.%) of activated carbon impregnated with palladium was packed in O3/catalyst column.
1,4-dioxane concentration was reduced steadily with reaction time in O3/H2O2 oxidation process, however, in case of O3/catalyst process, about 50~75% of 1,4-dioxane was degraded only in 5 minutes after reaction. Overall reaction efficiency of O3/catalyst was also higher than that of O3/H2O2 process.
TOC and CODCr were analyzed in order to examine the oxidation characteristics with O3/H2O2 and O3/catalyst process. The results of CODCr removal efficiency and ΔTOC/ΔThOC ratio in O3/catalyst process gave that this process could more proceed the oxidation reaction than O3/H2O2 oxidation process. Therefore, it was considered that O3/catalyst advanced oxidation process could be used as a effective oxidation process for removing non-degradable toxic organic materials.