• Title/Summary/Keyword: Kinetic Parameters

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Chemical Reactions in Surfactant Solution (I). Substituent Effects of 2-Alkylbenzimidazolide ions on Dephosphorylation in CTABr Solutions (계면활성제 용액속에서의 화학반응 (제1보). 미셀용액속에서의 탈인산화 반응에 미치는 2-알킬벤즈이미다졸음이온들의 치환기효과)

  • Young-Seuk Hong;Chan-Sik Park;Jung-Bae Kim
    • Journal of the Korean Chemical Society
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    • v.29 no.5
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    • pp.522-532
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    • 1985
  • The reactions of p-nitrophenyldiphenylphosphate (p-NPDPP) with anions of benzimidazole (BI) and its 2-alkyl derivatives (R-BI) are strongly catalyzed by the micelles of cetyltrimethyl ammonium bromide (CTABr). On the other hand, the first order rate constants $(k'_{R-BI^-})$ and the second order rate constants $(k_{m(R-BI^-)})$ of the reactions mediated by R-$BI^-$in the micellar pseudophase are much smaller than those mediated by $BI^-$. In order to explain the slower rates of the micellar reactions mediated by R-$BI^-$, we compared the concentration-ratios ([R-$BI^-$]/[$BI^-$]) with the first order rate constant-ratios $(k'_{R-BI^-}/k'_{BI^-})$ and the second order constant-ratios $(k_{m(R-BI^-)}/k_{m(BI^-)})$ for the reactions taking place in the micellar pseudophase. The rate constant-ratios were much smaller than the concentration-ratios. For example in a 5 ${\times}10^{-4}$M butyl-BI solution, the two ratios were 0.089 and 0.430 (for the first order) respectively, and in a $10^{-4}$M butyl-BI solution the former was 0.100 (for the second order). This predicts that the reactivities of R-$BI^-$ in the micellar pseudophase are much smaller than that of $BI^-$. Based on the values of several kinetic parameters measured for dephosphorylation of p-NPDPP mediated by R-$BI^-$, a schemetic model is proposed. Due to the hydrophobicity and the steric effect of the alkyl substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long cetyl groups of CTABr. Consequently, the movements of R-$BI^-$ bound to the micelle should be restricted, leading to decreased collison frequencies between the nucleophiles and p-NPDPP. We refer this as an "anchor effect". This effect became more predominent when a larger alky group in R-BI was employed and when a greater concentration of R-BI was used.

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The Analysis of Kinetic Parameters for BNR Process Simulation in Domestic Wastewater (국내하수에 적합한 BNR 공정 시뮬레이션을 위한 최적 동력학적 계수 산출)

  • Kim, Dae-Sung;Park, Myung-Gyun;Ahn, Ho-Chul;Ahn, Won-Sik;Lee, Eui-Sin
    • Proceedings of the Korea Water Resources Association Conference
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    • 2006.05a
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    • pp.1385-1390
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    • 2006
  • 외국에서 ASM 모델의 BNR 적용 연구결과를 국내 하수에 적용하기에는 하수농도, 온도, 슬러지농도 등이 국내와는 달라 적용상 무리가 있다. 본 연구에서 BNR 시뮬레이션을 위한 입력 자료로 활용되는 인자들은 IAWPRC task group에서 제안하는 값들을 사용하되 국내 하수성상에서 필요로 하는 인자들은 직접 실험을 통하여 부분적으로 구해냄으로써 모델 시뮬레이션의 신뢰도를 높이고자 하였다. F/M비의 변화량과 1/SRT과의 관계로부터, 종속영양미생물 생산계수 $Y_H$값을 구한결과, 0.40mg VSS/mg COD였다. 이것을 ASM No.2d에 적용하기 위하여 mg cell COD formed/mg COD oxidized 단위로 환산한 결과 0.58을 나타냈다. H 하수처리장의 1차 침전지 하수를 이용하여 호기성상태에서 OUR Test를 통한 미생물에 의한 유기물 섭취시 산소섭취율 변화를 측정하였다. 호기성상태와 무산소상태에서 구한 쉽게 분해되는 용존성유기물(Ss)값을 비교해보면 각각 35.5mg/L와 39.9mg/L로 약간의 차이는 있으나 유사한 값을 보여주고 있다. 시뮬레이션을 위한 동력학적 계수 중 무산소 상태에서 종속영양미생물의 ${\mu}_{max,H}$$3.56d^{-1}$로 나타났고, 호기성상태에서는 구하면 ${\mu}_{max,H}$$4.2d^{-1}$로 산출되었다. 종속영양미생물의 사멸계수 $b_H$를 구하기 위한 실험에서 초기 OUR의 10%이내가 될 때까지 걸린 시간은 7일정도가 걸렸으며, 사멸률 $b_H$$0.043hr^{-1}$로 나타났다. 독립영양미생물의 최대비성장률 ${\mu}_{max,A}$는 최대암모니아 섭취률을 이용하여 구한 결과 $0.65d^{-1}$로 나타났다.EX>$60%{\sim}87%$가 수심 10m 이내에 분포하였고, 녹조강과 남조강이 우점하는 하절기에는 5m 이내에 주로 분포하였다. 취수탑 지점의 수심이 연중 $25{\sim}35m$를 유지하는 H호의 경우 간헐식 폭기장치를 가동하는 기간은 물론 그 외 기간에도 취수구의 심도를 표층 10m 이하로 유지 할 경우 전체 조류 유입량을 60% 이상 저감할 수 있을 것으로 조사되었다.심볼 및 색채 디자인 등의 작업이 수반되어야 하며, 이들을 고려한 인터넷용 GIS기본도를 신규 제작한다. 상습침수지구와 관련된 각종 GIS데이타와 각 기관이 보유하고 있는 공공정보 가운데 공간정보와 연계되어야 하는 자료를 인터넷 GIS를 이용하여 효율적으로 관리하기 위해서는 단계별 구축전략이 필요하다. 따라서 본 논문에서는 인터넷 GIS를 이용하여 상습침수구역관련 정보를 검색, 처리 및 분석할 수 있는 상습침수 구역 종합정보화 시스템을 구축토록 하였다.N, 항목에서 보 상류가 높게 나타났으나, 철거되지 않은 검전보나 안양대교보에 비해 그 차이가 크지 않은 것으로 나타났다.의 기상변화가 자발성 기흉 발생에 영향을 미친다고 추론할 수 있었다. 향후 본 연구에서 추론된 기상변화와 기흉 발생과의 인과관계를 확인하고 좀 더 구체화하기 위한 연구가 필요할 것이다.게 이루어질 수 있을 것으로 기대된다.는 초과수익률이 상승하지만, 이후로는 감소하므로, 반전거래전략을 활용하는 경우 주식투자기간은 24개월이하의 중단기가 적합함을 발견하였다. 이상의 행태적 측면과 투자성과측면의 실증결과를 통하여 한국주식시장에 있어서 시장수익률을 평균적으로 초과할 수 있는 거래전략은 존재하므로 이러한 전략을 개발 및 활용할 수 있으며, 특히, 한국주식시장에 적합한 거래전략은 반전거래전략이고, 이 전략의 유용성은 투자자가 설정한 투자기간보다 더욱 긴 분석기간의 주식가격정보에 의하여 최대한 발휘될 수 있음을 확인하였다.(M1), 무역적자의 폭, 산업의 생산

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Kinetics of esterification of food waste oil by solid acid catalyst and reaction optimization (고체 산 촉매를 이용한 고산가 음폐유의 에스테르화 반응 동역학 연구 및 반응 최적화)

  • Lee, Hwa-Sung;Lee, Joon-Pyo;Lee, Jin-Suk;Kim, Deog-Keun
    • Journal of the Korean Applied Science and Technology
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    • v.34 no.3
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    • pp.683-693
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    • 2017
  • Transport biofuels have been recognized as a promising means to resolve the following issues like global warming, oil depletion and environmental pollutions. Among various biofuels, biodiesel has several advantages such as less emission of air pollutants and higher cetane values compared to diesel oil. Demand for biodiesel in Korea is increasing that leads to higher dependence on the imported feedstocks. Therefore, it is important to utilize the waste materials collected domestically for biodiesel production. Food waste oil collected in waste treatment facility has not been used for biodiesel production due to high free fatty contents in the oil. In this work, biodiesel conversion of food waste oil by Amberlyst 15 was studied. Synthetic and actual food waste oils have been used in the study. First, the effects of the major operating parameters including reaction temperature, methanol to oil molar ratio and catalyst loading on the conversion rates and yields were determined with synthetic waste oil. Kinetic modelling work was also done to determine the activation energy of the reaction. From the work, optimization reaction conditions were determined to be 383K, 1: 26.1 for methanol molar ratio to oil, 10 wt.% for catalyst loading and 360 min for reaction time. Activation energy of the reaction is determined to be 29.75 kJ/mol, lower than those reported in the previous works. So the solid catalyst, Amberlyst 15, was more efficient for esterification than the solid catalysts employed in the other works. Agitation rates have the negligible effects on the conversion rates and yields. With the identified optimization conditions, conversion of the actual food waste oil was also carried out. The esterification yield of actual food waste oil in 60 min was 13% lower than that of synthetic waste oil but the final yields in 240 min were similar each other, 98.12% for synthetic oil and 97.62% for actual waste oil.

Roles of Monoamine Neurotransmitters in Regulation of Hypothalamic PITUITITARY-ADRENAL AXIS(HPA) (III) - Role of 5-hydroxytryptamine in Controlling the Stress-Induced Elevation of Corticosterone in Rat - (시상하부-뇌하수체-부신계 조절에 대한 Monoamine 신경전달물질의 역할에 관한 연구(III)-뇌 5-hydroxytyptamine(Serotonin)이 Stress 시 Corticosteroid 변동에 미치는 영향)

  • Suh, Yoo-Hun;Lim, Jung-Kyoo;Park, Chan-Woong
    • The Korean Journal of Pharmacology
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    • v.19 no.2
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    • pp.45-55
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    • 1983
  • A role for brain serotonin(5-HT) in regulation of the HPA axis has been suggested but remains contoversial and poorly defined. The present experiments were designed to check kinetic parameters of 5-HT turnover in rat hypothalamus and remainder brain areas before and after stress and to test whether using various different pharmacologic approaches to stimulate or eliminate the control serotonergic system have any consistent effect on the stress-induced activation of HPA system. Steady state brain serotonin and 5-HIAA concentrations during 1 min ether stress were significantly elevated without significant rise in the levels of plasma corticosterone, which highly increased 2 minutes after stress. This suggests that the increase in serotonergic neuron activity precede that in HPA activity. Furthermore, during 1 ruin-ether stress or 30 min immobilization stress there is a marked increase in hypothalamic and remainder brain serotonin (5-HT) turnover or synthesis rates assessed by both the pargline/5-HT method and pargyline/5-HIAA method. The stress-induced corticosterone levels were increased by serotonin precursors and serotonin agonist in a dose-related fashion. The stress- induced corticosterone levels were highly elevated by L-tryptophan (100 mg/kg) and Potentiated by monoamine oxidase inhibitor, pargyline or serotonin agonist, 5-MeoDMT. The stress-induced elevation of corticosterone and 5-HT levels in rat brain were not significantly decreased by the administration of 5-HT synthesis inhibitor, PCPA and 5-HT neurotoxin, 5,7-DHT. However, the stress-induced elevation of corticosterone and 5-HT levels were decreased by the destruction of midline raphe nuclei. There was a strong positive correlation between plasma corticosterone and 5-HT concentrations changed by drugs which mainly manipulating 5-HT system in the hyhothalamus and in the remainder of the brain. In conclusion, our present data stongly suggest that 5-HT is an important key neurotransmitter involved in the stress-induced activation of the HPA system.

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Determination of Adsorption Isotherms of Hydrogen at an Ir Electrode Interface Using the Phase-Shift Method and Correlation Constants (Ir 전극 계면에서 위상이동 방법 및 상관계수를 이용한 수소의 흡착동온식 결정)

  • Jeon, Sang-K.
    • Journal of the Korean Electrochemical Society
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    • v.10 no.2
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    • pp.132-140
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    • 2007
  • The phase-shift method and correlation constants for studying a linear relationship between the behavior ($-{\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and that (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}\theta{\geq}0$) have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) at noble metal/aqueous electrolyte interfaces. At an Ir/0.1 M KOH aqueous electrolyte interface, the Langmuir and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=3.3{\times}10^{-4}\;mol^{-1}$ for the Langmuir and $K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}$ for the Temkin adsorption isotherm), interaction parameter (g = 4.6 for the Temkin adsorption isotherm), and standard free energies (${\Delta}G_{ads}^0=19.9kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-4}\;mol^{-1}$ and $16.5<{\Delta}G_{\theta}^0<23.3\;kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}\;and\;0.2<\theta<0.8$) of H for the cathodic $H_2$ evolution reaction are determined using the phase-shift method and correlation constants. The inhomogeneous and lateral interaction effects on the adsorption of H are negligible. At the intermediate values of ${\theta},\;i.e,\;0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms (${\theta}\;vs.\;E$) and related electrode kinetic and thermodynamic parameters(K, g, ${\Delta}G_{ads}^0, {\Delta}G_{\theta}^0$).

Kinetic Studies on the Reaction of the Homobimetallic Anion, M+5-MeCp)Mn(CO)2Mn(CO)5-(M+=Na+, PPN+) with Allyl Chloride (동종이핵착물인 M+5-MeCp)Mn(CO)2Mn(CO)5-(M+=Na+, PPN+)와 염화알릴간의 반응에 대한 반응속도론적 연구)

  • Park, Yong-Kwang;Yun, Dong-Shin
    • Journal of the Korean Chemical Society
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    • v.48 no.5
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    • pp.473-482
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    • 2004
  • The homobimetallic anion, $M^+({\eta}^5-MeCp)Mn(CO)_2Mn(CO)_5^-(M^+=Na^+,\;PPN^+)$was disrupted by CH2CHCH2Cl in THF at various temperatures ($20^{\circ}C~50^{\circ}C$) under the pseudo 1st order reaction conditions where excess of allyl chloride was employed under a nitrogen atmosphere. This homobimetallic anion seems to be involved in a concerted reaction mechanism in which a four-centered transition state is proposed. After undergoing the transition state, this reaction eventually leads to (MeCp)Mn$(CO)_3$ on addition of CO and $({\eta}^1-allyl)Mn(CO)_5$, respectively. However, in case of $Na^+$ analog, $Na^+$ may play a novel counter ion effect on the disruption reaction either by transferring one terminal CO from the $Mn(CO)_5$ moiety on to the $({\eta}^5-MeCp)Mn(CO)_2$of the corresponding homobimetallic complex, eventually resulting in $({\eta}^5-MeCp)Mn(CO)_3$ or through the interaction between $Na^+$ and the leaving group (Cl) of allyl chloride. This reaction is of overall second order with respect to homobimetallic complex with the activation parameters (${\Delta}H^{\neq}=17.15{\pm}0.17kcal/mol,\;{\Delta}S^{\neq}=-9.63{\pm}0.10$ e.u. for $Na^+$ analog; ${\Delta}H^{\neq}=22.13{\pm}0.21 kcal/mol,\;{\Delta}S^{\neq}=9.74{\pm}0.19$ e.u. for $PPN^+$ analog reaction).

Effect of Sodium ion on the Anaerobic Degradation of Food Waste : Quantitative Evaluation, Inhibition Model (주방폐기물의 혐기성분해에 대한 나트륨이온의 영향: 저해 특성평가, 저해모델)

  • Shin, Hang-Sik;Song, Young-Chae;Paik, Byeong-Cheon
    • Journal of the Korea Organic Resources Recycling Association
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    • v.2 no.2
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    • pp.3-17
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    • 1994
  • The inhibitory effect of sodium ion on the anaerobic degradation of food waste was studied by an anaerobic batch toxicity assay and inhibition model. The anaerobic degradation activity of food waste spiked with over $2g\;Na^+/L$ of sodium ion was severely inhibited at the initial stage of the exposure. The inhibition response of anaerobic microorganisms on the sodium ion estimated from the methane production was differed according to the concentration of sodium ion. The relative acclimation time(RAT) and methanation rate(RMR), defined as the ratios of initial lag time and maximum methane production rate of the sample spiked with sodium ion to the control. respectively, were used to evaluate the acclimation and inhibitory effects quantitatively on the anaerobic microorganisms. When sodium ion was increased from $2g\;Na^+/L$ to $20g\;Na^+/L$, the RAT was exponentially increased from 18.9 to 90. but the RMR was linearly decreased from 0.97 to 0.02. The effects of sodium ion for the maximum methanation rate, first order kinetic constant and ultimate methane production were well evaluated by a generalized nonlinear expression model. it could be described by the uncompetitive inhibition mode. The sodium ion concentration causing 50% inhibition of methanation activity was about $11g\;Na^+/L$, and the critical sodium ion beyond to compelete inhibition was 20 to $21g\;Na^+/L$. The presented results could be used to obtain the design or operation parameters of the anaerobic process treating food waste of high salt.

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Development of Mixed-bed Ion Exchange Resin Capsule for Water Quality Monitoring (수질 중 질소와 인 모니터링을 위한 혼합이온교환수지 캡슐의 개발)

  • Park, Chang-Jin;Kim, Dong-Kuk;Ok, Yong-Sik;Ryu, Kyung-Ryul;Lee, Ju-Young;Zhang, Yong-Seon;Yang, Jae-E
    • Applied Biological Chemistry
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    • v.47 no.3
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    • pp.344-350
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    • 2004
  • This study was conducted to develop and assess the applicability of mixed-bed ion exchange resin capsules for water quality monitoring in small agricultural watershed. Recoveries of resin capsules for inorganic N and P ranged from 96 to 102%. The net activation energies and pseudo-thermodynamic parameters, such as ${\Delta}G^{o\ddag},\;{\Delta}H^{o\ddag},\;and\;{\Delta}S^{o\ddag}$ for ion adsorption by resin capsules, exhibited relatively low values, indicating the process might be governed by chemical reactions such as diffusion. However, those values increased with temperature coinciding with the theory. The reaction reached pseudo-equilibrium within 24 hours for $NH_4-N\;and\;NO_3-N$, and only 8 hours for $PO_4-P$, respectively. The selectivity of resin capsules were in the order of $NO_3\;^-\;>\;NH_4\;^+\;>\;PO_4\;^{3-}$, coinciding with that of encapsulated Amberlite IRN-150 resin. At the initial state of equilibrium, the resin adsorption quantity was linearly proportional to the mass of ions in the streams, but the rate of movement leveled off, following Langmuir-type sorption isotherm. The overall results demonstrated that the resin capsule system was suitable for water quality monitoring in small agricultural watershed, judging from the reaction mechanism(s) of the resin capsule and the significance of model in field calibration.

The Grazing Rates and Community Dynamics of Zooplankton in the Continuous River Stretch Ecosystem Include with Brackish Zone (기수 지역을 포함한 연속적인 강 구획 생태계 내에서의 동물플랑크톤의 군집 동태와 섭식율)

  • Kim, Hyun-Woo
    • Korean Journal of Ecology and Environment
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    • v.39 no.4 s.118
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    • pp.462-470
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    • 2006
  • The zooplankton community dynamics and grazing experiments was evaluated along a 40 km section of the lower Seomjin river system. Zooplankton was sampled twice a month from January 2005 to June 2006 at three sites (River mouth; RKO, Seomjin bridge: RK12 and Gurae bridge: RK36) in the main river channel. During the study period, the values of most limnological parameters in the three sites were fairly similar, except for conductivity. Annual variation of conductivity in River mouth and Seomjin bridge was more dramatic than which of the other site. There were statistically significant spatial and seasonal differences in zooplankton abundance (ANOVA, P<0.01). Total abundance of major zooplankton groups at both stations was much higher than in Gurae bridge. Among the macrozooplankton, cladocerans abundance was negligible in study sites during study periods. Community filtering rates (CFRs) for phytoplankton and bacteria varied from 0 to 50 mL $L^{-1}\;D^{-1}$ and from 0 to 45 mL $L^{-1}\;D^{-1}$, respectively. The spatial variation of CFRs for phytoplankton was significant (ANOVA, P<0.05). The CFRs of copepods for phytoplankton and bacteria was much higher than that of cladocerans at study sites. Total zooplankton filtering rates on bacteria were slightly lower than filtering rates on phytoplankton. The CFRs of microzooplankton (MICZ) for bacteria were much higher than for macrozooplankton (MACZ) at all sites. Considering the total zooplankton community, MICZ generally were more important than MACZ as grazers of bacteria and phytoplankton in freshwater zone, while MACZ were more important than MICZ as grazers of phytoplankton in brackish zone.

A Study of Nitrous Oxide Decomposition using Calcium Oxide (Calcium Oxide를 이용한 N2O 분해에 관한 CO2의 영향 연구)

  • Paek, Jin-Young;Park, Yeong-Sung;Shun, Dowon;Bae, Dal-Hee
    • Korean Chemical Engineering Research
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    • v.40 no.6
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    • pp.746-751
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    • 2002
  • Fluidized bed combustion is a coal combustion technology that can reduce both SOx and NOx emission; SOx is removed by limestone that is fed into the combustion chamber and the NOx is reduced by low temperature combustion in a fluidized bed combustor and air stepping, but $N_2O$ generation is quite high. $N_2O$ is not only a greenhouse gas but also an agent of ozone destruction in the stratosphere. The calcium oxide(CaO) is known to be a catalyst of $N_2O$ decomposition. This study of $N_2O$ decomposition reaction in fixed bed reactor packed over CaO bed has been conducted. Effects of parameters such as concentration of inlet $N_2O$ gas, reaction temperature, CaO bed height and effect of $CO_2$, NO, $O_2$ gas on the decomposition reaction have been investigated. As a result of the experiment, it has been shown that $N_2O$ decomposition reaction increased with the increasing fixed bed temperature. While conversion of the reaction was decreased with increasing $CO_2$ concentration. Also, under the present of NO, the conversion of $N_2O$ decomposition is decreased. From the result of kinetic study gained the heterogeneous reaction rate on $N_2O$ decomposition. In the case of $N_2O$ decomposition over CaO, heterogeneous reaction rate is. $\frac{d[N_2O]}{dt}=\frac{3.86{\times}10^9{\exp}(-15841/R)K_{N_2O}[N_2O]}{(1+K_{N_2O}[N_2O]+K_{CO_2}[CO_2])}$. In this study, it is found that the calcium oxide is a good catalyst of $N_2O$ decomposition.