• Title/Summary/Keyword: heterogeneous reaction

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Kinetics and Mechanism of the Oxidation of Carbon Monoxide on H$_2$-Reduced NiO-Doped $\alpha$-Fe$_2O_3$

  • Kim, Don;Kim, Keu-Hong;Choi, Jae-Shi
    • Bulletin of the Korean Chemical Society
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    • v.9 no.2
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    • pp.81-84
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    • 1988
  • The CO oxidation was performed on $H_2$-reduced NiO-${\alpha}-Fe_2O_3$ in the temperature range 150-$250^{\circ}C$. The kinetic study and the conductivity measurements indicate the oxidation reaction follows Langmuir-Rideal type process that is uncommon in heterogeneous catalyst$^1$. No active site is found on the catalyst surface for CO adsorption, but an oxygen vacancy adsorbs an oxygen, and this step is rate initiation. The partial orders are half for $O_2$ and first for CO, respectively. Apparent activation energy for over-all reaction is 9.05 kcal/mol.

Quantitative Analysis of Grafted Methacrylate Groups by Michael Addition Reaction between Primary and Secondary Amino Groups on the Silica Nanoparticle Surface with 3-(Acryloyloxy)-2-Hydroxypropyl Methacrylate (실리카 나노 입자 표면에 결합된 1차 및 2차 아미노기와 3-(Acryloyloxy)-2-hydroxypropyl Methacrylate의 마이클 부가 반응에 의해 도입되는 메타크릴레이트기의 정량적 분석)

  • Lee, Sangmi;Ha, KiRyong
    • Polymer(Korea)
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    • v.39 no.2
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    • pp.300-310
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    • 2015
  • In this study, we modified silica nanoparticles with N-[3-(trimethoxysilyl)propyl]ethylenediamine (TPED) silane coupling agent, which has one primary and one secondary amino groups in a molecule, to introduce amino groups on the silica surface. After modification of silica, we used 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) to introduce methacrylate groups by Michael addition reaction. We found about 30% of N-H groups on the TPED modified silica surface reacted with acrylate groups of AHM compared to about 85% of reaction between N-H groups of pure TPED with acrylate groups of pure AHM. This lower degree of Michael addition reaction for heterogeneous reaction between N-H groups on the solid TPED modified silica and liquid AHM compared to homogeneous reaction between pure liquid TPED and pure liquid AHM may be caused by lower mobility of grafted amino groups of TPED moiety and higher steric hindrance caused by solid silica particles.

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 Catalysts for Hydrogen Generation Based on Ru-Incorporated Hydroxyapatite

  • Jaworski, Justyn Wayne;Kim, Dae-Hyun;Jung, Kyeong-Mun;Kim, So-Hue;Jeong, Jong-Ok;Jeon, Hyo-Sang;Min, Byoung-Koun;Kwon, Ki-Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.319-319
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    • 2011
  • Hydrolysis of sodium borohydride provides a safe and clean approach to hydrogen generation. Having the proper catalytic support for controlling this reaction is therefore a valuable technology. Here we demonstrate the capability of hydroxyapatite as a novel catalytic support material for hydrogen generation. Aside from being inexpensive and durable, we reveal that Ru ion exchange on the HAP surface provides a highly active support for sodium borohydride hydrolysis, exemplifying a high total turnover number of nearly 24,000 mol $H_2$/ mol Ru. Moreover, we observe that the RuHAP support exhibits a high catalytic lifetime of approximately one month upon repeated exposure to $NaBH_4$ solutions. In addition to examining surface area effects, we also identified the role of complex surface morphology in enhancing hydrolysis by the catalytic transition metal covered surface. Particularly, we found that a polycrystalline RuHAP catalytic support exhibits shorter induction times for the initial bubble formation as well as increased hydrogen generation rates as compared to a single crystal supports. The independent factor of a complex surface morphology is believed to provide enhanced sites for gas release during the initial stages of the reaction. By demonstrating the ability to shorten induction time and enhance catalytic activity through changes in surface morphology and Ru content, we find it feasible to further explore this catalyst support in the construction of a practical hydrogen generator.

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A Trial for Improvement of Energy Efficiency of Plasma Reactor by Superposing Two Heterogeneous Discharges - Characteristics of Surface and Corona Discharge Combined Plasma Reactor - (이종방전 중첩에 의한 방전 플라스마반응기의 효율개선의 시도 - 연면.직류코로나 방전 중첩형 반응기의 특성 -)

  • ;Mizuki Yamaguma
    • Journal of the Korean Society of Safety
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    • v.15 no.3
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    • pp.66-70
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    • 2000
  • In order to cope with environmental problems caused by harmful gases emitted from various industrial sources, a new technology which employs discharge plasma formed in ordinary atmospheric pressure has been intensively investigated in many industrialized nations. Although a plenty of useful outcomes and suggestions have been made public by scientists in this field, few commercial products which effectively decompose pollutant gases have appeared as yet. This is partly because that the energy efficiency of a most effective plasma reactor has not reached a satisfactory level in comparison with those of devices using conventional technologies. In an attempt to solve the problem mentioned above, we noticed to combine heterogeneous electrical discharges. This concepts is based on that each plasma reactor has its specific spatial region in which chemical reaction are active and by electrically affected with another reactor of different type, the activated region would increase - which may lead to cutting down the energy consumption. To prove this concept experimentally, two different discharge equipments, a plane ceramic-based surface discharge electrode and a corona electrode with tungsten needle may, are selected and combined to fabricate a hybrid plasma reactor. The results are summarized as follows; (1) Ozone concentration generated in the plasma region drastically increases when the positive corona discharge is added to the surface discharge. The rate of increase of ozone depends on the frequency of the surface discharge. The negative corona, however, does not contribute to the improvement of the ozone generation. (2) NO(nitrogen monoxide) decomposition rate also improves by simultaneously applying the surface and the positive corona discharges. The effect of the corona superposition is more evident when the level of the surface discharge is moderate. (3) By adjusting the corona level, the net energy efficiency during NO decomposition improves in comparison with the simple surface discharge reactor.

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Esterification of High Concentration Free Fatty Acid in Rice Bran Oil (미강유 중 고농도 자유지방산의 에스테르화)

  • Shin, Yong-Seop
    • Journal of Environmental Science International
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    • v.17 no.2
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    • pp.211-224
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    • 2008
  • Characteristics of the esterification reaction between free fatty acid in rice bran oil and methanol was investigated in the presence of catalysts, such as PTS(p-toluene sulfonic acid), Amberlyst 15 dry and SCX(silica gel based strong cation exchange resin). While reaction temperature was kept constant at $65^{\circ}C$, initial feed content of free fatty acid was varied from 100% to 1% by addition of pure free fatty acid which was previously made from rice bran oil. Also, the effect of mole ratio of methanol to fatty acid on the final conversion was examined. When esterification of pure free fatty acid was catalyzed by several acids, final conversions were increased in order of Amberlyst 15 dry, SCX and PTS. Using PTS catalyst, initially the reaction proceeded in homogeneous 2nd oder reaction mechanism. However, phase of reaction mixture changed from homogeneous to heterogeneous along the reaction time and then reaction rate was retarded by mass transfer resistance of methanol. Final conversion of free fatty acid in reaction mixture was depended on initial feed content of free fatty acid, and had maximum value at 30% of initial feed free fatty acid content for all kinds of catalysts used. And the final conversion was increased with mole ratio of methanol by the improvement of reaction rate. When initial feed free fatty acid content below 10% and the reaction was catalyzed by PTS, concentration of free fatty acid in reaction mixture was increased in the middle of reaction time by hydrolysis of triglyceride in reaction mixture. Also, if silica gel was added into the reaction mixture which had initial feed free fatty acid content below 50%, final conversion was increased by the adsorption of moisture produced. The SCX catalyst made the esterification reaction of free fatty acid to progress like in case of PTS catalyst. However, when initial feed free fatty acid content below 10%, concentration of free fatty acid in. reaction mixture was decreased monotonically and not increased in the middle of reaction time on the contrary to the case of PTS. Thus, SCX catalyst accomplished more high value of final conversion than PTS catalyst for the initial feed fatty acid content range from 50% to 5% In case of initial feed free fatty acid content of 1% and mole ratio of methanol was 2, concentration of free fatty acid in reaction mixture increased over the initial feed free fatty acid content for all kind of catalysts used. Although SCX catalyst was added into reaction mixture which had 1% of initial feed fatty acid content, final conversion was hardly raised by mole ratio of methanol.

Knoevenagel Reaction in Water Catalyzed by Mesoporous Silica Materials Synthesized from Industrial Waste Coal Fly Ash (석탄회 산업폐기물로부터 제조한 메조다공성 실리카소재를 촉매로 사용하는 Knoevenagel 수용액 반응)

  • Dhokte, Aashish O.;Khillare, Santosh L.;Lande, Machhindra K.;Arbad, Balasaheb R.
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.430-435
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    • 2011
  • Coal fly ash of thermal power plants converted into mesoporous materials MCM-41. The synthesized material was characterized by XRD, FT-IR, SEM, and EDS techniques. The catalytic activity of prepared material was studied for the synthesis of 5-arylindene malononitriles via Knoevenagel condensation of aromatic aldehydes and malonontrile is described. The features of present method are easy handling, stability, reusability, and eco-friendliness of catalyst, high yields, short reaction time, simple experimental and work up procedure.

Effects of coal devolatilization model and turbulent reaction rate in numerical simulations of a large-scale pulverized-coal-fired boiler (상용 미분탄 보일러 연소해석에서 석탄 탈휘발 모델 및 난류반응속도의 영향 평가)

  • Yang, JooHyang;Kim, Jung-en A.;Ryu, Changkook
    • 한국연소학회:학술대회논문집
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    • 2014.11a
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    • pp.59-62
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    • 2014
  • Predicting coal combustion by computational fluid dynamics (CFD) requires a combination of complicated flow and reaction models for turbulence, radiation, particle flows, heterogeneous combustion, and gaseous reactions. There are various levels of models available for each of the phenomena, but the use of advanced models are significantly restricted in a large-scale boiler due to the computational costs and the balance of accuracy between adopted models. In this study, the influence of coal devolatilization model and turbulent mixing rate was assessed in CFD for a commercial boiler at 500 MWe capacity. For coal devolatilization, two models were compared: i) a simple model assuming single volatile compound based on proximate analysis and ii) advanced model of FLASHCHAIN with multiple volatile species. It was found out that the influence of the model was observed near the flames but the overall gas temperature and heat transfer rate to the boiler were very similar. The devolatilization rate was found not significant since the difference in near-flame temperature became noticeable when it was multiplied by 10 or 0.1. In contrast, the influence of turbulent mixing rate (constant A in the Magnussen model) was found very large. Considering the heat transfer rate and flame temperature, a value of 1.0 was recommended for the rate constant.

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Lipid Peroxidation and Its Nutritional Significance (지방질의 과산화와 영양)

  • 최홍식
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.23 no.5
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    • pp.867-878
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    • 1994
  • A general overview of the lipid peroxidation and its nutritional significance are presented ,with emphasis on the reaction mechaisms, peroxidized products, further interaction and nutritional/biological deterioration in a series of oxidative process. Overall mechanism with various factors and elements for initiation , propagation and termination of free radical reaction is reviewed and the primary /secondary products of peroxidized lipids are defined. Since these products are potentially reactive substances that can cause deterioration of proteins /amino acids and vitamins (carotene, tocopherols and ascorbic acid etc), mechanism and actual damages of their deterioration in some foods and biological models are outlined. Especially , chemical changes caused by interaction of peroxidized products (related hydroperoxides, radicals and malonaldehye etc) and protein are emphasized here. And also, the detailed mechanisms on radical scavenging of the these vitamins which are the most prominent natural antioxidants are presented . Additionally , the possible roles of peroxidicaed lipids and their secondary products in the process of aging an carcinogenesis are briefly discussed . However, it is important to not that more detailed and integrated studies on the reaction kinetics, energetics of peroxidation, their decomposed products , biochemical interaction potential damaging/aging / carcinogenic effects, protection from their oxidative spoilage and novel antioxidants in food and heterogeneous biological systems will be essential in order to assessing the implication of lipid peroxidation to human nutrition and health.

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Properties of Silicon Carbide-Carbon Fiber Composites Prepared by Infiltrating Porous Carbon Fiber Composites with Liquid Silicon

  • Lee, Jae-Chun;Park, Min-Jin;Shin, Kyung-Sook;Lee, Jun-Seok;Kim, Byung-Gyun
    • The Korean Journal of Ceramics
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    • v.3 no.4
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    • pp.229-234
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    • 1997
  • Silicon carbide-carbon fiber composites have been prepared by partially Infiltrating porous carbon fiber composites with liquid silicon at a reaction temperature of $1670^{\circ}C$. Reaction between molten silicon and the fiber preform yielded silicon carbide-carbon fiber composites composed of aggregates of loosely bonded SiC crystallites of about 10$\mu\textrm{m}$ in size and preserved the appearance of a fiber. In addition, the SiC/C fiber composites had carbon fibers coated with a dense layer consisted of SiC particles of sizes smaller than 1$\mu\textrm{m}$. The physical and mechanical properties of SiC/C fiber composites were discussed in terms of infiltrated pore volume fraction of carbon preform occupied by liquid silicon at the beginning of reaction. Lower bending strength of the SiC/C fiber composites which had a heterogeneous structure in nature, was attributed to the disruption of geometric configuration of the original carbon fiber preform and the formation of the fibrous aggregates of the loosely bonded coarse SiC particles produced by solution-precipitation mechanism.

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