Volatile organic compounds (VOCs) are a paramount factor in air pollution of the environment. VOCs are vastly present in the wastewater discharged by the pharmaceutical industries. As it is evaporative in nature, it enters the environment spontaneously and causes air pollution, global warming, acid rain and climate change. VOCs must be treated before discharging or any other aerobic methods using an efficient catalyst. As the catalytic oxidation in the liquid phase is facile compared to the gas phase, this study investigated on catalytic liquid-phase oxidation of VOCs in model and real pharmaceutical wastewater. The model compounds of toluene-, ethylbenzene- and chlorobenzene-contaminated waters were treated separately along with the VOCs present in real pharmaceutical wastewater using a tungsten-based carbon catalyst. The tungsten was impregnated on the low-cost activated carbon matrix as it has good selectivity and catalytic property toward VOCs for facile catalytic operations. The metal catalysts were characterised by Fourier transform infrared spectroscopy, X-ray diffraction studies, and scanning electron microscopy with elemental and mapping analysis. The treatability was monitored by total organic carbon, ultra-violet spectroscopy and high-pressure liquid chromatography analysis. The tungsten-impregnated activated carbon matrix (WACM) has a catalytic efficiency toward toluene by 85.45 ± 1.78%, ethylbenzene by 93.9 ± 1.16%, chlorobenzene by 85.9 ± 2.26% and pharmaceutical VOCs by 85.05 ± 1.73% in 20 treatment cycles. The results showed that WACM worked efficiently in VOCs treatment, preventing the environment from air pollution. Furthermore, liquid-phase oxidation could easily be implementable on an industrial scale.

Based on the M06-2X density functional, the catalytic oxidation of CO by O2 over Mo-embedded graphene was investigated in detail. The model with molybdenum atom embedded in double vacancy (DV) in a graphene sheet was considered. It is found that the complete CO oxidation reactions over Mo-DV-graphene include a two-step process, in which the first step prefers to Langmuir–Hinshelwood mechanism and followed the progress of CO oxidation with a remaining atomic Otop. Compared with the structure of Mo atom decorated at the single carbon vacancy on graphene (Mo-SV-graphene), the catalytic activity of Mo-DV-graphene is weaker. The present results imply that the catalytic activity of Mo-embedded graphene for CO oxidation can be improved by increasing the ratio of single vacancy (SV).

본 연구에서는 촉매 상 H2O2 전환에 의해 건식산화제가 생성되었으며, 이를 이용한 NO 산 화 공정에 대한 연구를 진행하였다. 건식산화제를 생성하기 위한 H2O2 촉매 전환에 관한 실험을 수행 한 결과, Mn계 촉매의 성능이 가장 우수하였으며, 이를 통해 생성된 건식산화제를 NO 산화공정에 주 입하여 다양한 운전조건에서 NO 산화특성을 조사하였다. 그 결과, H2O2 주입량, 산화반응온도, 그리고 공간속도가 NO 산화율에 크게 영향을 미치는 것을 확인하였다. 그리고, 산화반응온도와 H2O2 주입량 이 증가할수록 NO 산화효율이 증가하였으며, 공간속도가 증가할수록 NO 산화효율이 감소하였다.

In order to improve the selective oxidation reaction of gaseous ammonia at a low temperature, various types of metal-impregnated activated alumina were prepared, and also physical and chemical properties of the conversion of ammonia were determined. Both types of metal (Cu, Ag) impregnated activated alumina show high conversion rate of ammonia at high temperature (over 300℃). However, at lower temperature (200 ℃), Ag-impregnated catalyst shows the highest conversion rate (93%). In addition, the effects of lattice oxygen of the developed catalyst was studied. Ce-impregnated catalyst showed higher conversion rate than commercial alumina, but also showed lower conversion rate than Ag-impregnated sample. Moreover, 5 vol.% of Ag activation under hydrogen shows the highest conversion rate result. Finally, through high conversion at low temperature, it was considered that the production of NO and NO2, toxic by-products, were effectively inhibited.

본 연구는 VOC 배출원 중 도장, 인쇄 공정에서 주요 발생물질인 톨루엔을 저온 분해할 수 있는 귀금속 팔라듐촉매 개발에 목적을 두고 있다. 팔라듐은 톨루엔 제거에서 활성이 우수하지만 비용이 높다. 따라서 실용성의 방안으로 Pd 담지량의 최소화 비율(0.1~1.0wt%)로 제조한 촉매의 활성을 측정하였다. 그 결과 1.0wt% Pd(R) 촉매가 모든 조건에서 가장 높은 활성을 나타내었다. 이는 SEM 촬영과 XRD 분석을 통해 촉매 제조과정에서 Pd의 담지량 및 소성 분위기에 따른 분산 형태와 연관이 있는 것으로 사료된다.

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.

Methanol was synthesized by homogeneous and catalytic reactions of partial oxidation of methane. The effect of pressure, temperature and oxygen concentration on methanol synthesis was investigated. The catalyst used was Bi-Cs-Mg-Cu-Mo mixed oxide. The partial oxidation reaction was carried out in a fixed bed reactor at 20~46 bar and 450~480℃ and oxygen concentration of 5.3~7.7mol%. The results were compared with results of homogeneous reaction performed at the same conditions. Methane conversions of the homogeneous and catalytic reactions increased with temperature. Methanol selectivity of the homogeneous reaction decreased with increasing temperature. However, the methanol selectivity of catalytic reaction increased with temperature. For both homogeneous and catalytic reactions, the methane conversions were around 5%. This may be due to the low oxygen concentration. Methanol selectivity of the catalytic reaction was higher than that of homogeneous one.

TiO2 광촉매 산화 공정의 효율은 수산기 라디칼의 생성량에 따라 크게 의존한다. 따라서 생성되는 수산기 라디칼의 정확한 정량이 공정을 평가하는데 필수적이다. 하지만 아직까지 이러한 수산기 라디칼 정량법이 마련되지 못했다. 이에 본 연구는 TiO2 광촉매 산화 반응에서 생성되는 수산기 라디칼을 정량화하기 위한 기존 분석법들을 비교하고, 기존 분석법들의 단점을 극복할 수 있는 새로운 방법을 제안하고자 수행되었다. TiO2 광촉매 산화 반응을 모사하기 위하여, 표준 TiO2 광촉매로서 널리 이용되고 있는 Degussa P25를 사용하였으며, 투여량은 0.05 g/L이었다. 그리고 UVC 수은 저압램프(11 W, 2,975 mW/cm2)를 광원으로 이용하였다. 연구결과, 기존에 많이 활용되고 있는 요오드화칼륨(KI)/UV-vis 분광분석법과 테레프탈산(TPA)/형광 분광분석법은 각각 요오드이온(I-)과 테레프탈산을 공정 중 생성된 수산기 라디칼과 반응시켜 발생하는 삼중요오드이온(I3-)과 2-하이드록시 테레프탈산을 검출하여 수산기 라디칼의 생성여부만을 확인할 수 있는 정성적인 분석법들이었다. 하지만 본 연구에서 테레프탈산 방법을 고성능 액체 크로마토그래프(HPLC) 분석법과 연계하였을 때 수산기 라디칼의 정량화가 가능하였다. 이렇게 새롭게 개발된 TPA/HPLC 분석법을 이용하여 측정한 결과, 본 연구의 실험 조건에서 8시간의 광촉매 산화 공정에 의해서 0.013 M의 수산기 라디칼이 생성되는 것을 확인하였다. 본 연구에서 제안하는 수산기 라디칼 정량법은 광촉매 산화 공정의 성능을 평가하는데 기여할 것으로 기대된다.

광석에서 순도 높은 금은을 추출하기 위해 사용된 청화법으로부터 시안이 유출되어 광석 내 존 재하는 중금속들과 결합하여 다양한 형태의 시안화합물이 생성된다. 이러한 시안화합물은 난분해성 오염물질로서 인간을 포함한 생태계에 악영향을 끼친다. 결합력에 따라서 중금속과 결합한 시안화합 물은 공유결합성 화합물(weak acid dissociable, WAD)과 착화합물(strong acid dissociable, SAD) 등으 로 분류할 수 있다. 본 연구에서는 시안화합물의 존재 형태별 광촉매 산화 효율을 비교 평가하였다. 특히 자외선 LED 광원의 파장과 광촉매 표면 개질이 시안화합물의 분해에 미치는 영향을 살펴보았 다. 실험 결과, 동일한 광촉매 산화 조건에서 자유 시안보다는 중금속과 결합한 시안화합물의 광산화 분해 효율이 떨어짐을 알 수 있었다. 그리고 자유 시안의 경우에는 짧은 파장에서 광촉매 산화가 효과 적이었지만 중금속과 결합한 시안화합물의 경우에는 긴 파장에서 광산화 분해능이 더 높게 나타났다. 그리고 광촉매 표면 개질에 의하여 광촉매 산화 공정의 성능을 향상시킬 수 있음을 확인하였다.

광산에서 순도 높은 금은을 추출하기 위해 청화법을 이용해 왔다. 이러한 광산 활동에서 많은 양의 시안이 사용되어 왔으며 이에 따라 고농도의 시안을 함유한 광산폐수가 발생되어 광산 주변 지역의 수계를 오염시킬 수 있다. 본 연구에서는 이러한 시안함유 광산폐수 및 침출수로부터 시안을 제거하기 위하여 TiO2 광촉매와 UV-LED 광원을 이용한 광산화 공정에 대하여 연구하였다. 기존 광산화 공정에서는 주로 UV 램프가 광원으로 많이 사용되었지만 여러 가지 단점으로 인하여 본 연구에서는 그 대체 광원으로 UV-LED의 적용 가능성을 평가하였다. 세 종류의 TiO2의 광산화 효율을 평가한 결과, 아나타제와 루틸이 혼합된 Degussa P25가 광산화 효율이 가장 좋은 것으로 확인되었다. 또한 형태와 파장이 다른 네 종류의 UV-LED를 비교 평가한 결과, 365 nm 램프형 > 365 nm 캔형 > 280 nm 캔형 > 420 nm 램프형 순으로 제거효율이 좋은 것으로 나타났다. 본 연구는 UV-LED는 기존의 UV 램프의 단점을 극복할 수 있는 대체광원으로서 광산화 공정에 적용 가능하다는 것을 입증하였으며, 시안의 광산화 효율은 TiO2 광촉매의 종류에도 영향을 받는다는 것을 확인하였다.

In this study, the fundamental experiments were performed for catalytic oxidation of NO (50 ppm) on MnO2 in the presence of ozone. The experiments were carried out at various catalytic temperatures (30-120℃) and ozone concentrations (50-150 ppm) to investigate the behavior of NO oxidation. The honeycomb type MnO2 catalyst was rectangular with a cell density of 300 cells per squuare inch. Due to O3 injection, NO reacted with O3 to form NO2, which was adsorbed at the MnO2 surface. The excessive ozone was decomposed to O* onto the MnO2 catalyst bed, and then that O* was reacted with NO2 to form NO3-. It was found that the optimal O3/NO ratio for catalytic oxidation of NO on MnO2 was 2.0, and the NO removal efficiency on MnO2 was 83% at 30℃. As a result, NO was converted mainly to NO3-.

Hydrogen gas is used as a fuel for the proton exchange membrane fuel cell (PEMFC). Trace amount of carbon monoxide present in the reformate H₂ gas can poison the anode of the PEMFC. Therefore, preferential oxidation (PROX) of CO is essential for reducing the concentration of CO from a hydrogen-rich reformate gas. In this study, conventional Pt/Al₂O₃catalyst was prepared for the preferential oxidation of CO. The effects of catalyst preparation method, additive, and hydrogen on the performances of PROX reaction of CO were investigated. Water treatment and addition of Ce enhanced catalytic activity of the Pt/Al₂O₃ catalyst at low temperature below 100℃.

Cobalt titanates (CoTiOx), such as CoTiO3 and Co2TiO4, have been synthesized via a solid-state reaction and characterized using X-ray diffraction (XRD) and X-ray photoelectron spectroscopic (XPS) measurement techniques, prior to being used for continuous wet trichloroethylene (TCE) oxidation at 36℃, to support our earlier chemical structure model for Co species in 5 wt% CoOx/TiO2 (fresh) and (spent) catalysts. Each XRD pattern for the synthesized CoTiO3 and Co2TiO4 was very close to those obtained from the respective standard XRD data files. The two CoTiOx samples gave Co 2p XPS spectra consisting of very strong main peaks for Co 2p3/2 and 2p1/2 with corresponding satellite structures at higher binding energies. The Co 2p3/2 main structure appeared at 781.3 eV for the CoTiO3, and it was indicated at 781.1 eV with the Co2TiO4. Not only could these binding energy values be very similar to that exhibited for the 5 wt% CoOx/TiO2 (fresh), but the spin-orbit splitting (ΔE) had also no noticeable difference between the cobalt titanates and a sample of the fresh catalyst. Neither of all the CoTiOx samples were active for the wet TCE oxidation, as expected, but a sample of pure Co3O4 had a good activity for this reaction. The earlier proposed model for the surface CoOx species existing with the fresh and spent catalysts is very consistent with the XPS characterization and activity measurements for the cobalt titanates.

Activity of manganese oxide supported on γ-Al2O3 was increased when cerium was added. Also, cerium-added manganese oxide on γ-Al2O3 was more effective in oxidation of toluene than that without cerium. XRD result, it was observed that MnO2+CeO2 crystalline phases were present in the samples. For the used catalyst, a prominent feature has increased by XPS. TPR/TPO profiles of cerium-added manganese oxide on γ-Al2O3 changed significantly increased at a lower temperature. The activity of 18.2 wt% Mn+10.0 wt% Ce/γ-Al2O3 increased at a lower temperature. The cerium added on the manganese catalysts has effects on the oxidation of toluene.

In this study, the decomposition of gas-phase TCE, Benzene and Toluene, in air streams by direct UV Photolysis and UV/TiO2 process was studied. For direct UV Photolysis, by regressing with computer calculation to the experimental results the value of reaction rate constant k of TCE, Toluene and Benzene in this work were determined to be 0.00392s-1, 0.00230s-1 and 0.00126s-1, respectively. And the adsorption constant K of TCE, Toluene and Benzene in this work were determined to be 0.0519mol-1 ,0.0313mol-1 and 0.0084mol-1, respectively. For UV/TiO2 system by regressing with computer calculation to the experimental results the value of reaction rate constant k of TCE, Toluene, and Benzene in this work were determined to be 5.74g/ℓ․min, 3.85g/ℓ․min, and 1.18g/ℓ․min, respectively. And the catalyst adsorption constant K of TCE, Toluene, and Benzene in this work were determined to be 0.0005m3/mg, 0.0043m3/mg and 0.0048m3/mg, respectively.

The present study was performed to develop the removal system of the offensive gases, including hydrogen sulfide of acid gas, ammonia or amine of base gas, from the nightsoil treatment plant. In order to remove the offensive gases, the Fe-EDTA system liquid phase catalytic oxidation method with the bubble lift column reactor was employed. From the results obtained it was confirmed that the offensive gases can be deodorized simultaneously and also hydrogen sulfide of acid gas, ammonia of base gas completely removed at pH 6.45. In addition, as input gases feed rate the efficiency of acid gas did not change but the efficiency of base gases decreased to approximately 90% at pH 6.0. From the result of particle size analyzer, it was found that the particle sizes including sulfur and other impurites grew up to 21μm over 72hour reaction time.