• Title/Summary/Keyword: $CH_4$ oxidation

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An Environmentally Benign Synthesis of 1-Benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane Tribromide and Its Application as an Efficient and Selective Reagent for Oxidation of Sulfides to Sulfoxides in Solution and Solvent-free Conditions

  • Pourmousavi, S.A.;Salehi, P.
    • Bulletin of the Korean Chemical Society
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    • v.29 no.7
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    • pp.1332-1334
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    • 2008
  • Stable crystalline 1-Benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane tribromide (BABOT), can be readily synthesized from the reaction of the corresponding bromide with $HNO_3$ and aqueous KBr. Selective Oxidation of a variety of dialkyl and alkyl Aryl sulfides to the corresponding sulfoxides in high yield was achieved by this reagent in solution ($CH_3CN/H_2O$) and solvent free conditions. The reaction proceeds under neutral and mild conditions and can be carried out easily at room temperature with regeneration of BABOT. In this method purification of products is straightforward and no over oxidation to sulfone was noted.

Synthesis and Characterization of Tetrathiafulvalene Charge Transfer Compounds with Iron and Antimony Halides

  • Kim Young In;Choi Sung Nak;Jung Woo Sung
    • Bulletin of the Korean Chemical Society
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    • v.15 no.6
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    • pp.465-468
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    • 1994
  • The charge transfer compounds $(TTF)_4FeCl_3{\cdot}CH_3OH,\;(TTF)_4SbCl_4\;and\;(TTF)_5(SbBr_4)_2{\cdot}CH_3COCH_3$ were prepared from reactions of the TTF (tetrathiafulvalene) and metal halides. The compounds were characterized by spectroscopic (UV,IR, EPR and XPS) methods, magnetic susceptibility and electrical conductivity measurements. The d.c electrical conductivities of the pressed pellets are in the order of $10^{-1}-10^{-3} Scm^{-1}$, which lies in the range of semiconductor region at room temperature. It means that the partially ionized TTF has stacked in low-dimensional chain in each compound. Spectroscopic properties also indicate that TTF molecules are partially ionized and charge transfer has occurred from (TTF)n to Fe(III) center in $(TTF)_4FeCl_3{\cdot}CH_3OH$ whereas to the $-SbX_4^-$ entity in $(TTF)_4SbCl_4\;and\;(TTF)_5(SbBr_4)_2{\cdot}CH_3COCH_3$. The EPR g values are consistent with TTF radical formation and EPR linewidths suggest the delocalization of unpaired electrons along TTF stacks. A signal arised from metal (Fe and Sb) ions were not detected in EPR spectra, indicating that metal ion is in the diamagnetic state in each compound. The diamagnetic state was also examined by the magnetic susceptibility measurement. The magnetic properties reveal the significant interaction between the $TTF^+$ radical cations in the stacks. The oxidation state of metal ions was also investigated by XPS spectra.

Oxidation of trans-[FeH(NCS(Me)-S)(dppe)2]I to trans trans-[FeNCS)2(Ph2P(O)CH2CH2P(O)Ph2)2][I3](dppe=PPh2CH2CH2PPh2) (trans-[FeH(NCS(Me)-S)(dppe)2]I 화합물의 trans-[FeNCS)2(Ph2P(O)CH2CH2P(O)Ph2)2][I3]로 산화)

  • Lee, Ji Hwa;Lee, Soon W.
    • Journal of the Korean Chemical Society
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    • v.44 no.4
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    • pp.311-315
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    • 2000
  • The Fe(II)-isothiocyanato complex $trans-[FeH(NCS)(dppe)_2]$ (1) eactedwith iodomethane(Mel) to give methyl isothiocyanide-Fe(n) complex, $trans-FeH(NCS(Me)-S)(dppe)_2]I(2)$. Compound 2 was oxidized to $trans-[Fe(NCS)_2(Ph_2P(O)CH_2CH_2P(O)Ph_2)_2][I_3]$ (3), which was structurally characterized by X-ray diffraction. The molecular structure of 3 showed a bent Fe-NCS group, Crystallographic data for 3: triclinic space group P1,a=11.071(2) A,b=12.054(2)A,c=12.121(1)A, $\alpha=101.02(1){\circ}C{\beta}=95.887(9){\circ}Cr=110.34(1){\circ}C$, $Z=1R(wR_2)=0.0567(0.1294)$.

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Synthesis, ESR and Electrochemical Characterization of Dioxygen Binding to Dirhodium Complexes with 2-anilinopyridinato Bridging Ligand (2-아닐리노 피리딘을 배위자로 하는 이핵 로듐착물의 두 산소첨가 생성물에 대한 합성 및 전기화학적 성질)

  • Kwang Ha Park;Moo Jin Jun;John. L. Bear
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.633-643
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    • 1989
  • The R$Rh_2(ap)_4$(2,2-trans) isomer (ap = 2-anilinopyridinate), which has two anilino nitrogens and two pyridyl nitrogens bound to each rhodium ion trans to their own kind, shows activation towards the one electron reduction of dioxygen at -0.40 V vs SCE. The ESR spectrum taken at 123 K proves the formation of a $[Rh_2(ap)_4(O_2)]$ ion with oxygen axially bound to one rhodium ion and the complex is at a RhⅡ2 oxidation state. The complex will form [$Rh_2(ap)_4(O_2)(CH_3CN)]^-$ in presence of $CH_3CN/CH_2Cl_2$ mixture without breaking the Rh-$O_2^-$ bond. When oxidized at -0.25 and 0.55 V, $[Rh_2(ap)_4(O_2)]$ will undergo two one electron oxidations to form $Rh_2(ap)_4(O_2)[Rh_2(ap)_4(O_2)]^+$. Both species have an axially bound superoxide ion but the former is at $Rh^{II}Rh^{III }$and the later at $Rh^{III}_2$ oxidation states. The ESR spetra and $CH_3CN$ addition study, on the other hand, show that the later complex is better described as $[Rh_{II}Rh^{III}(ap)_4(O_2)]^+$ with the odd electron localized on rhodium ion and the complex has an axially coordinated molecular oxygen. The electrochemical and ESR studies also show that the degree of dioxygen activation is a function of electrochemical redox potential.

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Characteristics of VOCs Oxidation using Copper Phthalocyanine Catalysts (구리 프탈로시아닌 촉매의 VOCs 산화 특성)

  • 서성규;윤형선
    • Journal of Korean Society for Atmospheric Environment
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    • v.20 no.4
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    • pp.515-521
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    • 2004
  • The catalytic oxidation of volatile organic compounds (methanol. acetaldehyde) has been characterized using the copper phthalocyanine catalyst in a fixed bed flow reactor under atmospheric pressure. The catalytic activity for pretreatment conditions was examined by this reaction system. The catalytic activity was ordered as follows: metal free-PC<Cu ($\alpha$)-PC<Cu ($\beta$)-PC The formaldehyde, carbon monoxide as a partial oxidation product of methanol and acetaldehyde over Cu ($\alpha$)-PC catalyst were detected and the conversions of methanol and acetaldehyde were accomplished above 95% over Cu ($\alpha$) -PC, Cu ($\beta$) - PC catalyst at 35$0^{\circ}C$. The pretreated metal free -PC, Cu($\alpha$)-PC, Cu($\beta$)-PC catalysts have been characterised by TGA, EA and XRD analysis. The catalytic activity pretreated with air and $CH_3$OH mixture (P-4) or air only (P-5) was very excellent. XRD and EA results showed that Cu($\alpha$)-PC, Cu($\beta$)-PC were destroyed an(1 new metal oxide such as CuO were formed.

Experimental Study on the Partial Oxidation Reforming of CH4/O2 Mixture in Two-Section Porous Media (CH4/O2 혼합기의 2단 다공체 내 부분산화 개질에 관한 실험적 연구)

  • Guahk, Young Tae;Lee, Dae Keun;Ko, Chang-Bog
    • 한국연소학회:학술대회논문집
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    • 2014.11a
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    • pp.249-251
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    • 2014
  • Synthesis gas such as hydrogen and carbon monoxide was produced from $CH_4//oxygen$ mixture using two-section porous media combustor. Heat recirculation through the inner foam structure could extend the flow velocity of stable region over the laminar burning velocity. $H_2/CO$ ratio and module M from concentration of flue gas measured by Gas Chromatography was similar to those calculated by equilibrium. But it was made sure that the heat loss effect becomes more influential than heat recirculation effect as the mixture gets richer. To generate synthesis gas appropriate for methanol production, insulated pressurized porous media combustor will be designed and built in the future.

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Unsteady Flamelet Modeling for Flame Structure and Soot Formation of Lanimar Non-premixed CH4/Air Flame (비정상 화염편 모델을 이용한 대기압 층류 비예혼합 CH4/Air 화염장의 매연입자 생성 특성 및 화염구조 해석)

  • Kim, Taehoon;Jeon, Sangtae;Kim, Yongmo
    • 한국연소학회:학술대회논문집
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    • 2012.11a
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    • pp.137-138
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    • 2012
  • The two-equation soot model based on the transient laminar flamelet model is implemented for soot formation of laminar non-premixed $CH_4/Air$ flame with detailed chemical reaction mechanism and complex thermodynamic properties. The soot model represents nucleation, growth and oxidation with gas-phase chemistry. This represented unsteady flamelet soot model has been tested and compared using well verified reference calculation result obtained solving the Full Transport Equations method.

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Experimental Study on the Partial Oxidation Reforming of CH4/O2 Mixture in Two-Section Porous Media at High Pressure Conditions (고압 분위기에서 CH4/O2 혼합기의 2단 다공체 내 부분산화 개질에 관한 실험적 연구)

  • Guahk, Young Tae;Lee, Dae Keun;Kim, Seung Gon;Ko, Chang-Bog;Park, Jong-Ho
    • 한국연소학회:학술대회논문집
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    • 2015.12a
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    • pp.73-74
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    • 2015
  • Synthesis gas such as hydrogen and carbon monoxide was produced from $CH_4/oxygen$ mixture using insulated pressurized porous media combustor. Experimentally, two cylindrical SiC foams with the different pore density were piled up in a quartz tube and fully premixed mixture was supplied in the axial direction. After stabilizing fuel-rich flame at the interface of the two foams at several pressure conditions, mole fractions of synthesis gases were measured by gas chromatography. Heat recirculation through the inner foam structure could extend the flow velocity of stable region over the laminar burning velocity. As the pressure increased, the rich flammability limit, $H_2/CO$ ratio, and module M increased.

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Research on Improvement of CH4 Reduction Performance of NGOC for CNG Bus (CNG 버스용 NGOC의 CH4 저감 성능 향상을 위한 연구)

  • Seo, Choong-Kil
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.18 no.5
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    • pp.708-715
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    • 2017
  • Recently, in order to meet the stricter emission regulations, the proportion of after-treatments for vehicles and vessels has been increasing gradually. The objective of this study is to investigate the improvement of $CH_4$ reduction ability of natural gas oxidation catalyst (NGOC), which reduces toxic gases emitted from CNG buses. Thirteen NGOCs were prepared, and the conversion performance of noxious gases according to the type of supports, the loading amount of noble metal, and surfactant and aging were determined. Support Zeolite supported on No. 3 $NGOC(1Pt-1Pd-3MgO-3CeO_2/(46TiO_2+23Al_2O_3+23Zeolite)$ is an anionic alkali metal/earth metal component that improved the oxidation reactivity between CO and NO and noble metal dispersion, and thus enhanced the $CH_4$ reduction ability. As the loading amount of Pd, a noble metal with a high selectivity to $CH_4$, was increased, the number of reaction sites was increased and the ability to reduce $CH_4$ was improved. No. 11 $NGOC(1Pt-1Pd-3MgO-3CeO_2/(Z20+Al80)$(pH=8.5), to which nitrate surfactant had been added, exhibited well dispersed catalyst particles with no agglomeration and improved the $CH_4$ reduction ability by 5-15%. The $NGOC(2Pt-2Pd-3Cr-3MgO/90Al_2O_3)$(48h aging), which was mildly thermal aged for 48h, increased the $CH_4$ reduction ability to about 10% or less as compared with No. 12 NGOC(Fresh).

Characterization of CH4-oxidizing and N2O-reducing Bacterial Consortia Enriched from the Rhizospheres of Maize and Tall Fescue (옥수수와 톨페스큐 근권 유래의 메탄 산화 및 아산화질소 환원 세균 컨소시움 특성)

  • Lee, Soojung;Kim, Seoyoung;Kim, Ye Ji;Lee, Yun-Yeong;Cho, Kyung-Suk
    • Microbiology and Biotechnology Letters
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    • v.49 no.2
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    • pp.225-238
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    • 2021
  • CH4-oxidizing and N2O-reducing bacterial consortia were enriched from the rhizosphere soils of maize (Zea mays) and tall fescue (Festuca arundinacea). Illumina MiSeq sequencing analysis was performed to comparatively analyze the bacterial communities of the consortia with those of the rhizosphere soils. Additionally, the effect of root exudate on CH4 oxidation and N2O reduction activities of the microbes was evaluated. Although the inoculum sources varied, the CH4-oxidizing and N2O-reducing consortia derived from maize and tall fescue were similar. The predominant methanotrophs in the CH4-oxidizing consortia were Methylosarcina, Methylococcus, and Methylocystis. Among the N2O-reducing consortia, the representative N2O-reducing bacteria were Cloacibacterium, Azonexus, and Klebsiella. The N2O reduction rate of the N2O-reducing consortium from maize rhizosphere and tall fescue rhizosphere increased by 1.6 and 2.7 times with the addition of maize and tall fescue root exudates, respectively. The CH4 oxidization activity of the CH4-oxidizing consortia did not increase with the addition of root exudates. The CH4-oxidizing and N2O-reducing consortia can be used as promising bioresources to mitigate non-CO2 greenhouse gas emissions during remediation of oil-contaminated soils.