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Noble metal catalysts for water gas shift reaction and their effectiveness factor (귀금속 계열 촉매의 수성가스전환반응특성과 유효인자)

  • Lim, Sung-Kwang;Bae, Joong-Myeon;Kim, Ki-Hyun
    • 한국신재생에너지학회:학술대회논문집
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    • 2008.05a
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    • pp.514-517
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    • 2008
  • Water gas shift(WGS) is an important step in fuel process for fuel cells, and improperness of commercial WGS catalysts for use in fuel cell systems has prompted numerous researches on noble metal catalysts. A selected noble metal catalyst for water gas shift reaction(WGS) was prepared with various metal loadings. The prepared catalysts were tested under two feeding conditions. At moderate residence time, carbon monoxide conversion was much higher on the noble metal catalysts as compared to commercial high-temperature shift catalyst. Effects of metal loading were examined by activity tests at short residence time. Higher metal loading effected higher reaction rate. The kinetic data was fitted to simple reaction equations and effectiveness factor was estimated. The results suggest the necessity of a structural design for the highly active noble metal catalysts.

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PM3 Studies on the Acid-Catalyzed Hydrolysis of 1-Phenoxyethyl Propionate

  • 김찬경;이인영;정동수;이본수;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.993-999
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    • 1998
  • Acid catalyzed hydrolysis of 1-phenoxyethyl propionate, Ⅰ, has been studied using the PM3 method in the gas phase. The first step of the reaction is the protonation of basic sites, three different oxygens in Ⅰ, producing three protonated species Ⅱ, Ⅲ and Ⅳ. All possible reaction pathways have been studied from each protonated structure. Changes in the reaction mechanisms have also been discussed from the results obtained by varying a nucleophile from a water monomer to a water dimer to a complex between one water molecule and an intermediate product (propionic acid or phenol) produced in the preceding unimolecular dissociation processes. Minimum energy reaction pathway is 2-W among the possible pathways, in which water dimer acts as an active catalyst and therefore facilitates the formation of a six-membered cyclic transition state. Lower barrier of 2-W is ascribed to an efficient bifunctional catalytic effect of water molecules. PM3-SM3.1 single point calculations have been done at the gas-phase optimized structure (SM3.1/PM3//PM3) to compare theoretical results to those of experimental work.

The Risk Assessment of Runway Reaction in the Process of Fridel-Crafts Acylation for Synthesis Reaction (화합물 합성반응 중 Fridel - Crafts Acylation 공정에서의 폭주반응 위험성평가)

  • Lee, Kwangho;Kim, Wonsung;Jun, Jinwoo;Joo, Youngjong;Park, Kyoshik
    • Journal of the Korean Society of Safety
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    • v.36 no.3
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    • pp.24-30
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    • 2021
  • Heat is generated during the synthesis and mixing process of chemical compounds due to a change in activation energy during the reaction. A runaway reaction occurs when sufficient heat is not removed during the heat control process within a reactor, rapidly increasing the temperature, reaction speed, and rate of heat generation inside the reactor. A risk assessment was executed using an RC-1 (Reaction Calorimeter) during Friedel-Crafts acylation. Friedel-Crafts acylation runs the risk of rapid heat generation during Active Pharmaceutical Ingredient (API) manufacturing; it was used to confirm the risk of a runaway reaction at each synthesis stage and during the mixing process. This study used experimental data to develop a safety efficiency improvement plan to control the risks of runaway and other exothermic reactions, which was implemented at the production site of a chemical plant.

Catalytic Combustion System Stability : Active Centre with High Temperature Heat Exchanger (촉매연소 시스템 안정화 : 고온용 열교환기를 이용한 능동제어)

  • 유상필;송광섭;류인수
    • Proceedings of the Korea Society for Energy Engineering kosee Conference
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    • 2002.11a
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    • pp.133-140
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    • 2002
  • Catalytic combustion known as one of the traditional oxidation methods of VOC gas is restricted to its applicable fields because of its reaction characteristics. But recently innovative improvement of catalytic endurance makes its applicable range broader from MEMs to industrial power generation. Therefore, control technologies based on the catalytic combustion characteristics are researched and developed dynamically. Especially, the stable control of catalytic combustion is an essential factor in a view of maximizing its efficiency. In this research, the fuel equivalence ratio and the preheating temperature of mixture gas is controlled by catalytic combustion system enhanced in heat transfer with high temperature heat exchanger. As a result the combustion characteristics of system was investigated, and both passive and active control type were compared and analyzed.

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Ammonia Decomposition Over Tantalum Carbides of Hydrogen Fuel Cell (수소연료전지용 탄탈륨 탄화물에 대한 암모니아 분해반응)

  • Choi, Jeong-Gil
    • New & Renewable Energy
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    • v.9 no.1
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    • pp.51-59
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    • 2013
  • Tantalum carbide crystallites which is to be used for $H_2$ fuel cell has been synthesized via a temperature-programmed reduction of $Ta_2O_5$ with pure $CH_4$. The resultant Ta carbide crystallites prepared using two different heating rates and space velocity exhibit the different surface areas. The $O_2$ uptake has a linear relation with surface area, corresponding to an oxygen capacity of $1.36{\times}10^{13}\;O\;cm^{-2}$. Tantalum carbide crystallites are very active for hydrogen production form ammonia decomposition reaction. Tantalum carbides are as much as two orders of magnitude more active than Pt/C catalyst (Engelhard). The highest activity has been observed at a ratio of $C_1/Ta^{{\delta}+}=0.85$, suggesting the presence of electron transfer between metals and carbon in metal carbides.

The Analysis on the Activation Procedure of Polymer Electrolyte Fuel Cells

  • Jang, Jong-Mun;Park, Gu-Gon;Sohn, Young-Jun;Yim, Sung-Dae;Kim, Chang-Soo;Yang, Tae-Hyun
    • Journal of Electrochemical Science and Technology
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    • v.2 no.3
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    • pp.131-135
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    • 2011
  • It is, in general, believed that during the activation process, the proton conductivity increases due to wetting effect and the electrochemical resistance reduction, resulting in an increase in the fuel cell performance with time. However, until now, very scant information is available on the understanding of activation processes. In this study, dominant variables that effect on the performance increase of membrane electrode assemblies (MEAs) during the activation process were investigated. Wetting, pore restructuring and active metal utilization were analyzed systematically. Unexpectedly, the changes for both ohmic and reaction resistance characterized by the electrochemical impedance spectroscopy (EIS) after initial wetting process were much smaller when considering the degree of cell performance increases. However, the EIS spectra represents that the pore opening of electrode turns into gas transportable structure more easily. The increase in the performance with activation cycles was also investigated in a view of active metals. Though the particle size was grown, the number of effective active sites might be exposed more. The impurity removal and catalytic activity enhancement measured by cyclic voltammetry (CV) could be a strong evident. The results and analysis revealed that, not merely wetting of membrane but also restructuring of electrodeand catalytic activity increase are important factors for the fast and efficient activation of the polymer electrolyte fuel cells.

Various Temperatures Affecting Characteristics of Pt/C Cathode Catalysts for Polymer Electrolyte Membrane Fuel Cells (Polymer Electrolyte Membrane Fuel Cells용 Pt/C 캐소드 전극촉매 특성에 미치는 반응 온도)

  • Yoo, Sung-Yeol;Kang, Suk-Min;Lee, Jin-A;Rhee, Choong-Kyun;Ryu, Ho-Jin
    • Korean Journal of Materials Research
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    • v.21 no.3
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    • pp.180-185
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    • 2011
  • This study is aimed to increase the activity of cathodic catalysts for PEMFCs(Polymer Electrolyte Membrane Fuel Cells). we investigated the temperature effect of 20wt% Pt/C catalysts at five different temperatures. The catalysts were synthesized by using chemical reduction method. Before adding the formaldehyde as reducing agent, process was undergone for 2 hours at the room temperature (RT), $40^{\circ}C$, $60^{\circ}C$, $80^{\circ}C$ and $100^{\circ}C$, respectively. The performances of synthesize catalysts are compared. The electrochemical oxygen reduction reaction (ORR) was studied on 20wt% Pt/C catalysts by using a glassy carbon electrode through cyclic voltammetric curves (CV) in a 1M H2SO4 solution. The ORR specific activities of 20wt% Pt/C catalysts increased to give a relative ORR catalytic activity ordering of $80^{\circ}C$ > $100^{\circ}C$ > $60^{\circ}C$ > $40^{\circ}C$ > RT. Electrochemical active surface area (EAS) was calculated with cyclic voltammetry analysis. Prepared Pt/C (at $80^{\circ}C$, $100^{\circ}C$) catalysts has higher ESA than other catalysts. Physical characterization was made by using X-ray diffraction (XRD) and transmission electron microscope (TEM). The TEM images of the carbon supported platinum electrocatalysts ($80^{\circ}C$, $100^{\circ}C$) showed homogenous particle distribution with particle size of about 2~3.5 nm. We found that a higher reaction temperature resulted in more uniform particle distribution than lower reaction temperature and then the XRD results showed that the crystalline structure of the synthesized catalysts are seen FCC structure.

An Optimization of Synthesis Method for High-temperature Water-gas Shift Reaction over Cu-CeO2-MgO Catalyst (고온수성가스전이반응 적용을 위한 Cu-CeO2-MgO 촉매의 제조방법 최적화)

  • I-Jeong Jeon;Chang-Hyeon Kim;Jae-Oh Shim
    • Clean Technology
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    • v.29 no.4
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    • pp.321-326
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    • 2023
  • Recently, there has been a growing interest in clean hydrogen energy that does not emit carbon dioxide during combustion due to the increasing focus on carbon neutral. Research related to hydrogen production continues, and in this study, we applied waste-derived synthesis gas to the water-gas shift reaction to simultaneously treat waste and produce high-purity hydrogen. To enhance catalytic activity in the high-temperature water-gas shift (HT-WGS) reaction, magnesium was used as a support material alongside cerium. Cu-CeO2-MgO catalysts were synthesized, with copper acting as the active component for the HT-WGS reaction. A study on the catalytic activity based on the preparation method was conducted, and the Cu-CeO2-MgO catalyst prepared by impregnation method exhibited the highest activity in the HT-WGS reaction. The observed superior performance of the Cu-CeO2-MgO catalyst prepared through the impregnation method can be attributed to its significantly higher oxygen storage capacity and amount of active Cu species.

Li:Al cathode layer and its influence on interfacial energy level and efficiency in polymer-based photovoltaics

  • Park, Sun-Mi;Jeon, Ji-Hye;Park, O-Ok;Kim, Jeong-Won
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.08a
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    • pp.72-72
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    • 2010
  • Recent development of organic solar cell approaches the level of 8% power conversion efficiency by the introduction of new materials, improved material engineering, and more sophisticated device structures. As for interface engineering, various interlayer materials such as LiF, CaO, NaF, and KF have been utilized between Al electrode and active layer. Those materials lower the work function of cathode and interface barrier, protect the active layer, enhance charge collection efficiency, and induce active layer doping. However, the addition of another step of thin layer deposition could be a little complicated. Thus, on a typical solar cell structure of Al/P3HT:PCBM/PEDOT:PSS/ITO glass, we used Li:Al alloy electrode instead of Al to render a simple process. J-V measurement under dark and light illumination on the polymer solar cell using Li:Al cathode shows the improvement in electric properties such as decrease in leakage current and series resistance, and increase in circuit current density. This effective charge collection and electron transport correspond to lowered energy barrier for electron transport at the interface, which is measured by ultraviolet photoelectron spectroscopy. Indeed, through the measurement of secondary ion mass spectroscopy, the Li atoms turn out to be located mainly at the interface between polymer and Al metal. In addition, the chemical reaction between polymer and metal electrodes are measured by X-ray photoelectron spectroscopy.

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Packed Bed Reactor Simulation for the Water Gas Shift Reaction in the Steam Reforming of Natural Gas (천연가스의 수증기 개질에서 수성가스 전환용 충진층 반응기의 전산모사)

  • LEE, DEUKKI
    • Transactions of the Korean hydrogen and new energy society
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    • v.27 no.5
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    • pp.494-502
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    • 2016
  • A 1-dimensional heterogeneous reactor model with the gas-solid interfacial phase gradients was developed for the simulation of the packed bed reactor where the exothermic reversible water gas shift reaction for the natural gas steam reformed gas was proceeding in adiabatic mode. Experimental results obtained over the WGS catalyst, C18-HA, were best simulated when the frequency factor of the reaction rate constant was adjusted to a half the value reported over another WGS catalyst, EX-2248, having the same kinds of active components as the C18-HA. For the reactor of the inside diameter 158.4 mm and the bed length 650 mm, the optimum feeding temperature of the reformed gas was simulated to be $194^{\circ}C$, giving the lowest CO content in the product gas by 1.68 mol% on the basis of dried gas. For reactors more extended in the bed length, the possible lowest CO content in the product gas with the optimum feeding temperature of the reformed gas were suggested.