• Title/Summary/Keyword: Catalytic Wet Oxidation

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1,4-Dioxane Decomposition by Catalytic Wet Peroxide Oxidation using Cu Wire Catalysts (Cu wire 촉매를 이용한 촉매습식과산화공정에 의한 1,4-다이옥산의 분해)

  • Lee, Dong-Keun;Kim, Dul Sun
    • Clean Technology
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    • v.22 no.4
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    • pp.281-285
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    • 2016
  • Cu wire catalyst was highly reactive toward catalytic wet peroxide oxidation of the highly refractory 1,4-dioxane. While complete removal of 1,4-dioxane could be achieved with the catalyst, the removed 1,4-dioxane could not totally mineralized into $CO_2$ and $H_2O$. In accordance with the disappearance of 1,4-dioxane, formaldehyde and oxalic acid were formed gradually with reaction time and they went through maxima. At around the time of maximum concentrations of these two intermediates acetaldehyde concentration was increased drastically and showed maximum value. With the disappearance of these three intermediates, formic acid together with ethylene glycol diformate began to increase gradually. The Cu wire catalyst was proved also to be highly stable against deactivation during the reaction.

Decomposition of Sulfamethoxazole by Catalytic Wet Peroxide Oxidation (촉매습식과산화(CWPO)를 이용한 설파메톡사졸의 분해)

  • Kim, Dul Sun;Lee, Dong-Keun;Kim, Jin Sol
    • Clean Technology
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    • v.24 no.4
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    • pp.293-300
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    • 2018
  • Sulfamethoxazole (SMX) is sulfaamide-based synthetic antibiotics, which are widely prescribed pharmaceutical compound to treat bacterial infections in both human and animals. Most of them are not completely decomposed as refractory substances. The environmental impact of pharmaceuticals as emerging contaminants has generated severe concerns. In this study, catalytic wet peroxide oxidation (CWPO) of SMX was carried out with $Cu/Al_2O_3$ catalyst and investigated the optimum reaction conditions of temperature, dosage of catalyst and concentration of $H_2O_2$ to completely decompose the SMX. It was observed that SMX was completely decomposed within 20 min using 0.79 mM $H_2O_2$ and 6 g $Cu/Al_2O_3$ catalyst at 1 atm and $40^{\circ}C$, but SMX was not fully mineralized and converted to intermediates as hydroylated-SMX, sulfanilic acid, 4-aminobenzenesulfinic acid and nitrobenzene. After that these are completely mineralized through organic acid. We proposed the decomposition reaction path ways of SMX by analyzing the behavior of these intermediates. To investigate the durability of heterogeneous catalyst, decomposition of SMX was observed by continuously recycling catalysts. When the heterogeneous catalyst of 10 wt% $Cu/Al_2O_3$ was continuously reused 5 times, decomposition of SMX was a little lowered, but the activity of catalyst was overall very stable.

Pillared clays from natural resources as catalysts for catalytic wet peroxide oxidation: Characterization and kinetic insights

  • Kalmakhanova, Marzhan Seitovna;Diaz de Tuesta, Jose Luis;Kabykenovna, Bakytgul;Gomes, Helder Teixeira
    • Environmental Engineering Research
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    • v.25 no.2
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    • pp.186-196
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    • 2020
  • Pillared clays with Zr and Fe/Cu/Zr polycations have been prepared from natural clays found in large deposits of Kazakhstan and assessed as catalysts for the catalytic wet peroxide oxidation (CWPO), using 4-nitrophenol (4-NP) as model compound. The performance of the catalysts was followed by measuring the concentration of 4-NP, H2O2 and the total organic carbon (TOC), considering C4-NP = 5 g L-1, $C_{H_2O_2}$ = 17.8 g L-1, Ccat = 2.5 g L-1, initial pH = 3.0 and T = 50℃. At those selected conditions, the pillared clays showed higher activity than natural clays in the CWPO of 4-NP. The conversion of the model pollutant was complete when Fe/Cu/Zr-PILCs were used, with the TOC removal reaching 78.4% after 24 h with the best Fe/Cu/Zr-PILC. The H2O2, 4-NP and TOC time-evolution was well described by a kinetic model based on TOC lumps in three blocks, considering the initial TOC (corresponding to 4-NP), the production of oxidizable intermediates and the formation of refractory products.

Photocatalytic Activity of $TiO_2$ Powder with an Oxygen Deficiency in the Visible-Light Region (산소 결함형 $TiO_2$ 분말의 가시광에 대한 광촉매 활성)

  • Yang, Chun-Hoe
    • Journal of the Korean Applied Science and Technology
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    • v.24 no.1
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    • pp.1-9
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    • 2007
  • It prepared the $TiO_2$ powder which has photo-catalytic activity in the visible-light by the wet process with titanium oxysulfate. The titanium $dioxide(TiO_2)$ by the wet process creates a new absorption band in the visible light region, and is expected to create photocatalytic activity in this region. Anatase $TiO_2$ powder which has photocatalytic activity in the visible light region, is treated using microwave and radio-frequency(RF) plasma. But, the $TiO_2$ powder for the visible light region, which also can be easily produced by wet process. The wet process $TiO_2$ absorbed visible light between 400nm and 600nm, and showed a high activity in this region, as measured by the oxidation removal of aceton from the gas phase. The AH-380 sample appears the yellow color to be strong, the catalytic activity in the visible ray was excellent in comparison with the plasma-treated $TiO_2$. The AH-380 $TiO_2$ powder, which can be easily produced on a large scale, is expected to have higher efficiency in utilizing solar energy than the plasma-treated $TiO_2$ powder.

Catalytic Oxidation of Trichloroethylene over Pd-Loaded Sulfated Zirconia

  • Park, Jung-Nam;Lee, Chul-Wee;Chang, Jong-San;Park, Sang-Eon;Shin, Chae-Ho
    • Bulletin of the Korean Chemical Society
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    • v.25 no.9
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    • pp.1355-1360
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    • 2004
  • The oxidative decomposition of trichloroethylene (TCE) was investigated using palladium catalysts supported on pure and sulfated zirconia. The reactions were performed under dry and wet conditions in the temperature between 200 and $550^{\circ}C$ keeping GHSV of 14,000 $h^{-1}.$ The products such as $C_2Cl_4,\;C_2HCl_5,\;CO\;and\;CO_2$ were observed in the reaction. The addition of water in the feed affected the distribution of reaction product with dramatically improved catalytic activity. The spectroscopic investigations gave an evidence that the strong acid sites play an important role on controlling the catalytic activity. Among the catalysts investigated, the Pd-loaded sulfated zirconia catalyst with 1 wt% Pd was found to exhibit the highest catalytic activity in the presence of water vapor having the stability for 30 h of the reaction at $500^{\circ}C$. The successful performance of the catalyst might be attributed to promotional effect of Pd active sites and strong acid sites induced from surface sulfate species on zirconia.

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.

Preparation of Ag/TiO2 Particle for Aerobic Benzyl Alcohol Oxidation (Aerobic Benzyl Alcohol Oxidation 반응용 Ag/TiO2 제조)

  • Kim, Chang-Soo;Yoo, Kye Sang
    • Applied Chemistry for Engineering
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    • v.24 no.6
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    • pp.663-667
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    • 2013
  • $Ag/TiO_2$ particle was prepared using various ionic liquids by wet impregnation. The properties of the particles were significantly affected by the composition of ionic liquids. This is mainly attributed to different abilities of an ionic liquid to coordinate with the silver particle, leading to various coagulation of silver particles. The catalytic activity of the prepared samples was examined for the aerobic benzyl alcohol oxidation. Among the particles, $Ag/TiO_2$ prepared with 1-octyl-3-methylimidazolium tetrafluoroborate showed the best catalytic performance.

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.

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.

Catalytic Oxidation of Methane Using the Manganese Catalysts (망간촉매를 이용한 메탄의 산화반응)

  • Jang, Hyun-Tae;Cha, Wang-Seong
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.12 no.1
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    • pp.537-544
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    • 2011
  • This work was conducted to investigate the oxidation characteristics of methane having the highest ignition temperature among the other hydrocarbon gases using transition metal catalysts. The catalyst used for methane oxidation was manganese oxide having a various oxidation number, such as MnO, $MnO_2$, $Mn_2O_3$, $Mn_3O_4$, $Mn_4O_5$. The manganese oxide(MnxOy) catalyst is impregnated on $TiO_2$, $Al_2O_3$ for methane oxidation. To enhanced both of activity and life time of catalysts, Ni and Co was used as a promoter. In this study, various co-catalysts were synthesized by using excess wet impregnation method. The effect of reaction temperature and space velocity was measured to calculate the activity of catalysts such as, activation energy of $T_{50}$, and $T_{90}$. The life time of bi-metallic manganese mixture, such as Mn-Co and Mn-Ni catalysts, were increased more 10 % than manganese oxide catalyst, but activity of those was decreased slightly.