• Title/Summary/Keyword: heterogeneous chemical reaction

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Selective Oxidation of Amines to Imines or Nitriles by Manganese Dioxide in Air (공기 중에서 망간 다이옥사이드에 의한 아민에서 이민 또는 나이트릴로의 선택적 산화 반응)

  • Kim, Yo Han;Hwang, Seung Kyu;Lee, Yoon Sik;Kim, Jung Won
    • Applied Chemistry for Engineering
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    • v.25 no.2
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    • pp.215-221
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    • 2014
  • A simple heterogeneous system has been developed by using base treated manganese dioxide (B-$MnO_2$) for the aerobic oxidation of amines under mild reaction conditions of 1 atm of air and $50^{\circ}C$ in hexane. This system was highly efficient to oxidize various kinds of primary or secondary amines including aliphatic, aromatic, and hetero-atomic ones under the applied reaction conditions. Amines were oxidized to nitriles or diimines by the self-condensation or oxidative dehydrogenation through imine intermediate. The B-$MnO_2$ was reused for at least 5 times without any loss of its catalytic performance and showed its cost effectiveness, easy workup, and easy separation of the products for achieving the protocol of green chemistry.

P123-Templated Co3O4/Al2O3 Mesoporous Mixed Oxides for Epoxidation of Styrene

  • Jung, Mie-Won;Kim, Young-Sil
    • Korean Journal of Materials Research
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    • v.22 no.6
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    • pp.316-320
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    • 2012
  • $Co_3O_4$, $Al_2O_3$ and $Co_3O_4$/$Al_2O_3$ mesoporous powders were prepared by a sol-gel method with starting matierals of aluminum isopropoxide and cobalt (II) nitrate. A P123 template is employed as an active organic additive for improving the specific surface area of the mixed oxide by forming surfactant micelles. A transition metal cobalt oxide supported on alumina with and without P123 was tested to find the most active and selective conditions as a heterogeneous catalyst in the reaction of styrene epoxidation. A bBlock copolymer-P123 template was added to the staring materials to control physical and chemical properties. The properties of $Co_3O_4$/$Al_2O_3$ powder with and without P123 were characterized using an X-ray diffractometer (XRD), a Field-Emission Scanning Electron Microscope (FE-SEM), a Bruner-Emmertt-Teller (BET) surface analyzer, and $^{27}Al$ MAS NMR spectroscopy. Powders with and without P123 were compared in catalytic tests. The catalytic activity and selectivity were monitored by GC/MS, $^1H$, and $^{13}C$-NMR spectroscopy. The performance for the reaction of epoxidation of styrene was observed to be in the following order: [$Co_3O_4$/$Al_2O_3$ with P123-1173 K > $Co_3O_4$/$Al_2O_3$ with P123-973 K > $Co_3O_4$-973 K>$Co_3O_4$/$Al_2O_3$-973 K > $Co_3O_4$/$Al_2O_3$ with P123-1473 K > $Al_2O_3$-973 K]. The existence of ${\gamma}$-alumina and the nature of the surface morphology are related to catalytic activity.

Heterogeneous growth of the triploid Pacific oysters Crassostrea gigas created by chemical inhibition of polar body release

  • Jo, Qtae;Han, Jong-Chul;Hur, Yong-Baek;Byun, Soon Kyu;Moon, Tae-Seok
    • The Korean Journal of Malacology
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    • v.30 no.4
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    • pp.443-447
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    • 2014
  • Triploids have several potential advantages over diploids in aquaculture, drawing an elevated commercial reaction into the realistic application of the techniques despite we are still in the early stage of triploid industry for the Pacific oysters Crassostrea gigas. We traced the growth performance of the triploid C. gigas for over a year from hatchery spats, which was created by manipulations of chemicals (Cytochalasin B, CB or 6-Dimethylaminopurine, 6-DMAP). The growth was clearly marked by an initial longer dormancy and following a great magnitude of heterogeneity. The dormancy was almost 9 to 10-month long or even longer and was considered as a downside of the creation. The heterogeneity was magnified by appearance of extraordinarily growing oysters in part during summer season, which could be a representative upside of the triploids. Overall, however, the results were not as positive as were expected. The longer dormancy and following heterogeneity observed in our practice could be marked as an additional negative sign of the chemical use. The present study, thus, might be highly indicative in the introduction of biological cross between tetraploid and diploid to produce natural triploid embryos.

Micro-Chemical Structure of Polyaniline Synthesized by Self-Stabilized Dispersion Polymerization

  • NamGoong, Hyun;Woo, Dong-Jin;Lee, Suck-Hyun
    • Macromolecular Research
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    • v.15 no.7
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    • pp.633-639
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    • 2007
  • A variety of NMR techniques were applied to the micro-chemical structural characterization of polyanilines prepared via an efficient synthetic method in a self-stabilized dispersion medium in which the polymerization was conducted in a heterogeneous organic/aqueous biphasic system without any stabilizers. Here, the monomer and growing polymer chain were shown to function simultaneously as a stabilizer, imparting compatibility for the dispersion of the organic phase, and as a form of flexible template in an aqueous reaction medium. Polymerizations predicated on this concept generated polyanilines with a low defect content: solution state $^{13}C-NMR$ and solid $^{13}CDD/CP/MAS$ spectroscopy indicated that the synthesized HCPANi and its soluble derivative, HCPANi-t-BOC, evidenced distinctly different NMR spectra with fewer side peaks, as compared to conventionally prepared PANis, and the complete structural assignments of the observed NMR peaks could be determined via the combination of both 1D and 2D techniques. Ortho-linked defects in HCPANi were estimated to be as low as 7%, as shown by a comparison of the integration of the carbonyl carbon resonance peaks.

Microwave-mediated Asymmetric Hydrogen Transfer by SBA-15-supported Ruthenium Catalyst (SBA-15 실리카에 고정화된 ruthenium 촉매를 사용한 Microwave하에서의 비대칭 수소 전달반응)

  • Jin, Myung-Jong;Jun, In-Chul
    • Korean Chemical Engineering Research
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    • v.46 no.4
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    • pp.752-755
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    • 2008
  • Mesoporous SBA-15 silica-supported TsCHDA and TsDPEN ligands have been prepared by reaction of SBA-15 silica with (1R,2R)-N-(trimethoxysilylpropyl-N-sulfonyl)-1,2-cyclohaxanediamine or (1R,2R)-N-(trimethoxysilylpropyl-N-sulfonyl)-1,2-diphenylethylenediamine-1,2-diphenylethylenediamine, respectively. The Ru complexes exhibited excellent catalytic activity and satisfactory enantioselectivity in the asymmetric hydrogen transfer of ketones under microwave conditions. The heterogeneous Ru catalyst was reusable as well as air-stable to allow easy use. Microwave-assisted efficient procedure has been developed for asymmetric hydrogen transfer.

A Green Chemical Approach towards the 'One-Pot' Synthesis, Spectral Characterization and in Vitro Antibacterial and Antifungal Activities of Morpholino Pyrimidines (친환경적 One Pot 합성, In Vitro에서 Morpholino Pyrimidines의 분광학적 특성과 항균성 및 항진균성)

  • Kanagarajan, V.;Thanusu, J.;Gopalakrishnan, M.
    • Journal of the Korean Chemical Society
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    • v.53 no.6
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    • pp.731-741
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    • 2009
  • ‘One-pot’ reaction procedure for the synthesis of novel morpholino pyrimidines (10-18) under microwave irradiation in ‘dry media’ in the presence of heterogeneous $NaHSO_4.SiO_2$ catalyst was developed. All the synthesized compounds were screened for their in vitro antibacterial activities against clinically isolated bacterial strains namely Bacillus subtilis, Bacillus cerues, Micrococcus luteus and Salmonella typhii and antifungal activities against fungal strains namely Aspergillus niger, Candida 6 and Candida 51. Structure activity relationship of the synthesized compounds against microbiological results was discussed.

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.

Rigorous Modeling and Simulation of Multi-tubular Reactor for Water Gas Shift Reaction (Water Gas Shift Reaction을 위한 Multi-tubular Reactor 모델링 및 모사)

  • Park, Junyong;Choi, Youngjae;Kim, Kihyun;Oh, Min
    • Korean Chemical Engineering Research
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    • v.46 no.5
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    • pp.931-937
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    • 2008
  • Rigorous multiscale modelling and simulation of the MTR for WGSR was carried out to accurately predict the behavior of process variables and the reactor performance. The MTR consists of 4 fixed bed tube reactors packed with heterogeneous catalysts, as well as surrounding shell part for the cooling purpose. Considering that fluid flow field and reaction kinetics give a great influence on the reactor performance, employing multiscale methodology encompassing Computational Fluid Dynamics (CFD) and process modeling was natural and, in a sense, inevitable conclusion. Inlet and outlet temperature of the reactant fluid at the tube side was $345^{\circ}C$ and $390^{\circ}C$, respectively and the CO conversion at the exit of the tube side with these conditions approached to about 0.89. At the shell side, the inlet and outlet temperature of the cooling fluid, which flows counter-currently to tube flow, was $190^{\circ}C$ and $240^{\circ}C$. From this heat exchange, the energy saving was achieved for the flow at shell side and temperature of the tube side was properly controlled to obtain high CO conversion. The simulation results from this research were accurately comparable to the experimental data from various papers.

Study on the Gas Permeation Behaviors of Surface Fluorinated Polysulfone Membranes (표면불소화 폴리설폰 막의 기체 투과거동에 관한 연구)

  • Kim, Dae-Hoon;Im, Hyeon-Soo;Kim, Min-Sung;Lee, Byung-Seong;Lee, Bo-Sung;Yoon, Seok-Won;Kim, Beom-Sik;Park, You-In;Cheong, Seong-Ihl;Rhim, Ji-Won
    • Polymer(Korea)
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    • v.33 no.6
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    • pp.537-543
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    • 2009
  • The direct fluorination of polymers is a heterogeneous reaction using the mixture of $F_2$ and inert gas. In general, the resulting fluorinated polymers have good barrier property chemical stability similar to those of the fluoro-polymers, and could be prepared from the simple process. In this study, the polysulfone dense films were surface fluorinated using the direct fluorination technique and gas permeability and selectivity of the prepared membranes were measured with varying both $F_2$ concentration and reaction time. The introduction of $F_2$ was confirmed by X-ray photoelectron spectroscopy (XPS), water contact angles, and atomic force microscopy (AFM). As the $F_2$ increased, the permeability decreased while the selectivities for $O_2$, $CO_2$, and He gases relative to $N_2$ increased.

Preparation of the MnO2/Macroporous Carbon for PET Glycolysis

  • Choi, Bong Gill;Yang, MinHo
    • Journal of Powder Materials
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    • v.25 no.3
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    • pp.203-207
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    • 2018
  • Plastic pollution is threatening human health and ecosystems, resulting in one of the biggest challenges that humanity has ever faced. Therefore, this study focuses on the preparation of macroporous carbon from biowaste (MC)-supported manganese oxide ($MnO_2$) as an efficient, reusable, and robust catalyst for the recycling of poly(ethylene terephthalate) (PET) waste. As-prepared $MnO_2/MC$ composites have a hierarchical pore network and a large surface area ($376.16m^2/g$) with a narrow size distribution. $MnO_2/MC$ shows a maximum yield (98%) of bis(2-hydroxyethyl)terephthalate (BHET) after glycolysis reaction for 120 min. Furthermore, $MnO_2/MC$ can be reused at least nine times with a negligible decrease in BHET yield. Based on this remarkable catalytic performance, we expect that $MnO_2$-based heterogeneous catalysts have the potential to be introduced into the PET recycling industry.