• Title/Summary/Keyword: Continuous Wet Oxidation

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Synthesis of CoTiOx and Its Catalytic Activity in Continuous Wet TCE Oxidation (CoTiOx의 합성 및 연속 습식 TCE 산화반응에서의 촉매활성)

  • Kim, Moon-Hyeon
    • Journal of Environmental Science International
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    • v.16 no.12
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    • pp.1431-1437
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    • 2007
  • Cobalt titanates($CoTiO_x$), such as $CoTiO_3$ and $Co_2TiO_4$, 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 $36^{\circ}C$, to support our earlier chemical structure model for Co species in 5 wt% $CoO_x/TiO_2$(fresh) and(spent) catalysts. Each XRD pattern for the synthesized $CoTiO_3$ and $Co_2TiO_4$ was very close to those obtained from the respective standard XRD data files. The two $CoTiO_x$ samples gave Co 2p XPS spectra consisting of very strong main peaks for Co $2p_{3/2}$ and $2p_{1/2}$ with corresponding satellite structures at higher binding energies. The Co $2p_{3/2}$ main structure appeared at 781.3 eV for the $CoTiO_3$, and it was indicated at 781.1 eV with the $Co_2TiO_4$. Not only could these binding energy values be very similar to that exhibited for the 5 wt% $CoO_x/TiO_2$(fresh), but the spin-orbit splitting(${\Delta}E$) had also no noticeable difference between the cobalt titanates and a sample of the fresh catalyst. Neither of all the $CoTiO_x$ samples were active for the wet TCE oxidation, as expected, but a sample of pure $Co_3O_4$ had a good activity for this reaction. The earlier proposed model for the surface $CoO_x$ species existing with the fresh and spent catalysts is very consistent with the XPS characterization and activity measurements for the cobalt titanates.

Carbon bead-supported copper-dispersed carbon nanofibers: An efficient catalyst for wet air oxidation of industrial wastewater in a recycle flow reactor

  • Yadav, Ashish;Verma, Nishith
    • Journal of Industrial and Engineering Chemistry
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    • v.67
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    • pp.448-460
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    • 2018
  • Copper nanoparticle-doped and graphitic carbon nanofibers-covered porous carbon beads were used as an efficient catalyst for treating synthetic phenolic water by catalytic wet air oxidation (CWAO) in a packed bed reactor over 10-30 bar and $180-230^{\circ}C$, with air and water flowing co-currently. A mathematical model based on reaction kinetics assuming degradation in both heterogeneous and homogeneous phases was developed to predict reduction in chemical oxygen demand (COD) under a continuous operation with recycle. The catalyst and process also showed complete COD reduction (>99%) without leaching of Cu against a high COD (~120,000 mg/L) containing industrial wastewater.

Continuous Wet Oxidation of TCE over Supported Metal Oxide Catalysts (금속산화물 담지촉매상에서 연속 습식 TCE 분해반응)

  • Kim, Moon Hyeon;Choo, Kwang-Ho
    • Korean Chemical Engineering Research
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    • v.43 no.2
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    • pp.206-214
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    • 2005
  • Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.

Evaluation Method for Graphene Grain Boundary by UV/ozone-oxidation Chemical-etching Process (UV/ozone 산화처리 및 화학적 식각공정을 적용한 그래핀 Grain Boundary 평가 방법)

  • Kang, Jaewoon;Park, Hongsik
    • Journal of Sensor Science and Technology
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    • v.25 no.4
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    • pp.275-279
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    • 2016
  • Chemical vapor deposited (CVD) polycrystalline graphene is widely used for various sensor application because of its extremely large surface-to-volume ratio. The electrical properties of CVD-graphene is significantly affected by the grain size and boundaries (GGBs), but evaluation of GGB of continuous monolayer graphene is difficult. Although several evaluation methods such as tunneling electron microscopy, confocal Raman, UV/ozone-oxidation are typically used, they still have issues in evaluation efficiency and accuracy. In this paper, we suggest an improved evaluation method for precise and simple GGB evaluation which is based on UV/ozone-oxidation and chemical etching process. Using this method, we could observe clear GGBs of CVD-graphene layers grown by different process conditions and statistically evaluate average grain sizes varying from $1.69{\sim}4.43{\mu}m$. This evaluation method can be used for analyzing the correlation between the electrical properties and grain size of CVD-graphene, which is essential for the development of graphene-based sensor devices.

On-stream Activity and Surface Chemical Structure of CoO2/TiO2 Catalysts for Continuous Wet TCE Oxidation (습식 TCE 분해반응에서 CoO2/TiO2 촉매의 반응활성 및 표면화학적 구조)

  • Kim Moon Hyeon;Choo Kwang-Ho
    • Journal of Environmental Science International
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    • v.14 no.2
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    • pp.221-230
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    • 2005
  • Catalytic wet oxidation of trichloroethylene (TCE) in water has been conducted using $TiO_2-supported$ cobalt oxides at $36^{\circ}C$ with a weight hourly space velocity of $7,500\;h^{-1}.\;5\%\;CoO_x/TiO_2$, prepared by using an incipient wetness technique, might be the most promising catalyst for the wet oxidation although it exhibited a transient behavior in time on-stream activity. Not only could the bare support be inactive for the wet decomposition reaction, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. XPS spectra of both fresh and used Co surfaces gave different surface spectral features for each $CoO_x,\;Co\;2P_{3/2}$ binding energy for Co species in the fresh catalyst appeared at 781.3 eV, which is very similar to the chemical states of $CoTiO_x$ such as $CO_2TiO_4\;and\;CoTiO_3$. The used catalyst exhibited a 780.3-eV main peak with a satellite structure at 795.8 eV. Based on XPS spectra of reference Co compound, the TCE-exposed Co surfaces could be assigned to be in the form of mainly $Co_3O_4$. XRD patterns for $5\%\;CoO_x/TiO_2$ catalyst indicated that the phase structure of Co species in the catalyst even before reaction is quite comparable to the diffraction lines of external $Co_3O_4$ standard. A model structure of $CoO_x$ present predominantly on titania surfaces would be $Co_3O_4$, encapsulated in thin-film $CoTiO_x$ species consisting of $Co_2TiO_4$ and $CoTiO_3$, which may be active for the decomposition of TCE in a flow of water.

A Study on the Characteristics of the Functional Groups of the Alkanethiol Molecules in UV Laser Photochemical Patterning and Wet Etching Process (UV Laser를 이용한 광화학적 패터닝과 습식에칭에 따른 알칸티올 분자 작용기의 특성 연구)

  • Huh, Kab-Soo;Chang, Won-Seok
    • Journal of the Korean Society for Precision Engineering
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    • v.24 no.5
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    • pp.104-109
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    • 2007
  • Photochemical patterning of self-assembled mono layers (SAMs) has been performed by diode pumped solid state (DPSS) 3rd harmonic Nd:$YVO_4$ laser with wavelength of 355 nm. SAMs patternings of parallel lines have subsequently been used either to generate compositional chemical patterns or fabricate microstructures by a wet etching. This paper describes a selective etching process with patterned SAMs of alkanetiolate molecules on the surface of gold. SAMs formed by the adsorption of alkanethiols onto gold substrate employs as very thin photoresists. In this paper, the influence of the interaction between the functional group of SAMs and the etching solution is studied with optimal laser irradiation conditions. The results show that hydrophobic functional groups of SAMs are more effective for selective chemical etching than the hydrophilic ones.

Supported Metal Oxides for Continuous Cat-alytic Wet Oxidation of TCE

  • 김문현;추광호
    • Proceedings of the Korean Environmental Sciences Society Conference
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    • 2004.05a
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    • pp.40-45
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    • 2004
  • 액상 TCE 제거반응을 위한 Hetero-CWO 촉매들 중에서 $CoO_{x}$/$TiO_2$$CuO_{x}$/$TiO_2$가 상대적으로 유망한 것으로 보여졌으며, 특히 5% $CoO_{x}$/$TiO_2$ 촉매의 경우에 반응시간에 따른 활성추이는 TCE 제거반응에서 주요 역할을 할 수 있는 반응 활성점의 변화를 암시하고 있다. $FeO_{x}$ /$TiO_2$와 Fe-MFI 촉매상에서 TCE 제거반응에 대한 시간에 따른 활성거동으로부터 활성점의 redox cycle를 어떻게 제어하는가 하는 점이 매우 중요함을 알 수 있었으며, 촉매표면에서 이를 유지.증진시킬 수 있는 촉매 디자인 기법이 요구되었다.

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Treatment of Wastewater Containing Cu(II)-EDTA Using Ferrate in Sequencing Batch Scale System (연속회분식 반응 장치에서 Ferrate를 이용한 Cu(II)-EDTA 함유 폐수 처리 연구)

  • Kim, Hyoung-Uk;Kim, Byeong-Kwon;Lee, Seung-Mok;Yang, Jae-Kyu;Kim, Hyun-Ook;Kwan, Jung-An;Im, Hang-Sik
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.7
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    • pp.729-734
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    • 2008
  • The higher valence state of iron i.e., Fe(VI) was employed for the treatment of Cu(II)-EDTA in the aqueous/waste waters. The ferrate(VI) was prepared through wet oxidation of Fe(III) by sodium hypochlorite. The purity of prepared Fe(VI) was above 93%. The stability of Fe(VI) solution decreased as solution pH decreased through self decomposition. The reduction of Fe(VI) was obtained by using the UV-Visible measurements. The dissociation of Cu(II)-EDTA complex through oxidation of EDTA using Fe(VI) and subsequent treatment of organic matter and metal ions by Fe(III) reduced from Fe(VI) in bench-scale of continuous flow reactor were studied. The removal efficiencies of copper were 69% and 79% in pH control basin and reactor, respectively, at 120 minutes as retention time. In addition, Cu(II)-EDTA in the reactor was decomplexated more than 80% after 120 minutes as retention time. From this work, a continuous treatment process for the wastewater containing metal and EDTA by employing Fe(VI) as muluti-functional agent was developed.

Photocatalytic removal of NOx using TiO2-coated zeolite

  • Mendoza, Joseph Albert;Lee, Dong Hoon;Kang, Joo-Hyon
    • Environmental Engineering Research
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    • v.21 no.3
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    • pp.291-296
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    • 2016
  • Application of photocatalytic nanoparticles has been recently gaining an increased attention as air purifying material for sustainable urban development. The present work reports the photocatalytic removal of gaseous phase nitrogen oxides ($NO_x$) using $TiO_2$-coated zeolite to be applied as a filter media for the urban green infrastructure such as raingardens. The $TiO_2$-coated zeolite was synthesized by simple wet chemistry method and tested in a continuous-flow photo-reactor for its removal efficiency of $NO_x$ under different conditions of the weight percentage of $TiO_2$ coated on the zeolite, and gas retention time. The removal efficiency of $NO_x$ in general increased as the weight percentage of $TiO_2$ coated on the zeolite increased up to 15-20%. Greater than 90% of $NO_x$ was removed at a retention time of one minute using the $TiO_2$-coated zeolite ($TiO_2$ weight percentage = 20%). Overall, $TiO_2$-coated zeolite showed greater efficiency of $NO_x$ removal compared to $TiO_2$ powder probably by providing additional reaction sites from the porous structure of zeolite. It was presumed that the degradation of $NO_x$ is attributed to both the physical adsorption and photocatalytic oxidation that could simultaneously occur at the catalyst surface.

Catalytic Reduction of Oxidized Mercury to Elemental Form by Transition Metals for Hg CEMS (수은 연속측정시스템에서 전이금속에 의한 산화수은의 원소수은으로의 촉매환원)

  • Ham, Sung-Won
    • Clean Technology
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    • v.20 no.3
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    • pp.269-276
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    • 2014
  • This study was aimed to develop catalytic system for the dry-based reduction of oxidized mercury ($Hg^{2+}$) to elemental mercury ($Hg^0$) which is one of the most important components comprising mercury continuous emission monitoring system (Hg-CEMS). Based on the standard potential in oxidation-reduction reaction, transition metals including Fe, Cu, Ni and Co were selected as possible candidates for catalyst proceeding spontaneous reduction of $Hg^{2+}$ into $Hg^0$. These transition metal catalysts revealed high activity for reduction of $Hg^{2+}$ into $Hg^0$ in the absence of oxygen in reactant gases. However, their activities were greatly decreased in the presence of oxygen, which was attributed to the transformation of transition metals by oxygen to the corresponding transition metal oxides with less catalytic activity for the reduction of oxidized mercury. Hydrogen supplied to the reactant gases significantly enhanced $Hg^{2+}$ reduction activity even in the presence of oxygen. It might be due to occurrence of combustion reaction between $H_2$ and $O_2$ causing the consumption of $O_2$ at such high reaction temperature at which oxidized mercury reduction reaction took place. Because the system showed high activity for $Hg^{2+}$ reduction to $Hg^0$, which was compatible to that of wet-chemistry technology using $SnCl_2$ solution, the catalytic reduction system of Fe catalyst with the supply of $H_2$ could be employed as a commercial system for the reduction of oxidized mercury to elemental mercury.