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The Reaction of 4,4′-Dihydroxydiphenyl Methane with Glycidyl Methacrylate

  • Pyun, Hyung-Chick;Park, Wan-Bin;Sung, Ki-Woung;Choi, Kyu-Suck
    • Nuclear Engineering and Technology
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    • v.11 no.2
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    • pp.119-126
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    • 1979
  • The reaction of 4,4'-dihydroxydiphenl methane (4,4'-DPM) with glycidyl methacrylate (GMA) catalyzed by triethylbenzyl ammonium chloride (TEBAC) has been studied for the purpose of synthesis of electron beam curable prepolymer. The reaction was in good agreement with third-order kinetics. according to -d[GMA]/dt=k[TEBAC][DPM][GMA] and the apparent activation energy was about 33.4kca1/mole. However, the reaction rates were increased if tile reaction proceeded after the mixtures exposed to air for 24 hrs at room temperature. The effects of the catalyst and the difference in the reactivity between 2.2'-DPM to GMA were discussed. The plausible reaction mechanism was proposed on basis of experimental data obtained.

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Optimization of Organosolv Pretreatment of Waste Wood for Lignin Extraction (폐목재로부터 리그닌 추출을 위한 Organosolv 전처리공정의 최적화)

  • Lee, Hyunsu;Kim, Young Mo
    • Journal of Korean Society of Environmental Engineers
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    • v.39 no.10
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    • pp.568-574
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    • 2017
  • The purpose of this study was to optimize experimental conditions (time ($X_1$) (ranging of 26.36 - 93.64 min), concentration of sulfuric acid ($X_2$) (ranging of 0-2.5%) and temperature ($X_3$) (ranging of $136.4-203.6^{\circ}C$) for an organosolv pretreatment process to extract lignin from waste wood. The resulting quadratic model equation using RSM (response surface methodology) represented y (lignin yield) = $-79.89+0.91X_1+9.8X_2-2.54{\times}10^{-3}X_1{^2}-2.11X_2{^2}$. The $R^2$ (coefficient of determination) value of 0.8531 for a model indicates this model has statistically significant predictors at the 10% levels. The predictive results optimized by quadratic model produced a lignin yield of 12.46 g/100 g of dry wood under conditions of $178.2^{\circ}C$ and 2.32% $H_2SO_4$. The lignin yield was more affected by the acid catalyst concentrations than the reaction temperature, but the reaction time was not an influential factor for improving lignin extraction from waste wood in this organosolv pretreatment. According to ANOVA (analysis of variance), the significance probability (p-value) of model was smaller than 0.001 and simulation of obtained model equations showed a good reproducibility based on actual organosolv tests under optimal conditions.

Equilibrium, Kinetic and Thermodynamic Parameter Studies on Adsorption of Acid Black 1 Using Coconut Shell-Based Granular Activated Carbon (야자각계 입상 활성탄의 Acid Black 1 염료 흡착에 대한 평형, 동역학 및 열역학 파라미터의 연구)

  • Lee, Dong-Chang;Lee, Jong-Jib
    • Applied Chemistry for Engineering
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    • v.27 no.6
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    • pp.590-598
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    • 2016
  • In this study, the adsorption behavior from aqueous solution as well as kinetic and thermodynamic parameters of Acid Black 1 were investigated through batch reaction using coconut shell based granular steam activated carbon. The effects of various adsorption parameters such as pH, initial concentration, contact time, temperature were studied. To confirm the effect of pH, pHpzc measurements were analyzed followed by measuring removal efficiencies of Acid Black 1 at the pH range from 3 to 11. Experimental equilibrium adsorption data were fitted using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich adsorption isotherm. The conformity of adsorption reaction for pseudo first and second order model were evaluated through kinetic analysis. Values of enthalpy change and activation energy were also investigated through thermodynamic analysis and it was confirmed that the adsorption process was endothermic. The spontaneity of adsorption process was evaluated using the values of entropy and Gibbs free energy changes.

Biosorption and Flotation of Lead and Chromium using Waste Activated Sludge (폐 활성슬러지를 이용한 납과 크롬의 생체흡착 및 부상)

  • Lee, Chang-Han
    • The Journal of the Korea Contents Association
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    • v.9 no.10
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    • pp.444-450
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    • 2009
  • We have investigated biosorption kinetics and equilibrium of $Pb^2+$ and $Cr^2+$ using waste sludge, and separation efficiency of waste sludge by dissolved air flotation was evaluated in the various A/S ratio. The biosorption capacity and contact time were shown as a simulation of biosorption equilibrium and kinetics models. Biosorption equilibrium of the $Pb^2+$ and $Cr^2+$ onto the waste sludge could be fitted by the Langmuir, Freundlich, Redlich-Peterson, and Koble-Corrigan equation. The kinetics could be fitted by a pseudo-second-order rate equation more than a pseudo-first-order rate equation. The separation efficiency of waste sludge using DAF was kept above 90%.

에이 : 오.티 -이소옥탄 역미셀계에서의 리파제의 특성과 이 효소에 의한 유지의 가수분해

  • 한대석
    • Proceedings of the Korean Society for Applied Microbiology Conference
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    • 1986.12a
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    • pp.508-508
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    • 1986
  • 이온성 계면활성제 존재하에서 유기용매에 물을 첨가하면 물이 계면활성제에 약해 둘러싸이면서 유기용매에 용해되어 의사 이상계가 형성된다. 이러한 계를 역미셀 또는 W/O microemulsion이라고 하며 계면활성제로 둘러 쌓인 물분자 집하체를 water pool이라고 한다. 그런데, 10여년 전 water pool에 bipolymer를 용해시킬 수 있다는 사실이 밟혀짐에 따라 이러한 체계를 생체막을 단순화시킨 모형막으로서 막을 통해 일어나는 여러 가지 현상의 규명에 이용하거나 물에 불용성인 기질의 효소 촉매반응의 반응계로 이용하는 연구가 꾸준히 이루어져 있다. 본 강연은 역미셀계에 리파제를 용해시켜 유지의 가수분해를 유도함으로써 지방산을 생산하는 방법에 관한 연구이다. 역미셀계에서 리파제의 특성은 에멀전계와 비교했을 때 큰 차이가 없었으며 물과 계면활성제의 몰 비율(R값)은 효소의 초기반응 속도에 커다란 영향을 끼치는 인자로 나타났다. 올리브유 농도가 5%(v/v), AOT농도가 0.1M, 초기 물 농도가 1.0M의 조건에서 유지의 회분식 가수분해 실험을 행한 결과 이 기질은 거의 완전히 가수분해되었으며, 이 반응계에서 R값과 초기 물 농도는 반응의 평형에 커다란 영향을 끼치는 것으로 나타났는데 초기 물 농도가 증가할수록 평형 가수분해율은 증가하였단 이러한 결과를 반응속도론 측면에서 분석한 결과 역미셀계에서 리파제 반응은 에멀전계에서와는 달리 2차 반응을 따르는 것으로 나타났다. 물 농도가 평형 가수 분해율과 속도 변수에 끼치는 영향을 수학적으로 표시하기 위하여 2차 가역적 반응 속도론에 근거하여 가수분해율, 평형상수, 속도상수 둥을 나타내는 식을 유도하였고 이를 바탕으로 여러 가지 실험 조건 하에서 리파제 반응의 반응 시간에 따른 가수분해율을 예측한 결과는 실제 실험 결과와 잘 일치하였다(편차는 5%). 또한 속도상수와 R값과의 관계식 및 유도한 방정식을 이용하여 추정한 초기속도와 평형 가수분해율을 최대화하는 R값은 각각 10.4 와 11.4 였다.

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Solvent Effects on the Nucleophilc Addition (I) Effect of Solvent Polarity on the Nucleophilic Addition of Amine to Phenylvinylketone (친핵성 첨가반응에 대한 용매효과 (I) Phenylvinylketone에 대한 아민의 첨가반응속도에 미치는 용매의 극성효과)

  • Gap-Cheol Shin;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.287-292
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    • 1992
  • The rate constants of the nucleophilic addition reaction of amines (piperidine and diethylamine) to phenylvinylketone in various solvents have been determined by UV spectrophotometry at $25^{\circ}C$. On the basis of the high sensitivity of the rate to the polarity of the medium, it may be concluded that the reaction intermediate has zwitterionic character. The effect of the solvents on the rate of the bimolecular nucleophilic addition reaction is described well by the Kirkwood equation: The transition state of the reaction has a cyclic structure formed through an intramolecular hydrogen bond. The addition reaction of primary and secondary amines to phenylvinylketone in all solvents take place considerably faster than that of tertiary amine and this results also can be explained by the intermediate products in the reaction have a cyclic structure formed through an intramolecular hydrogen bond for the primary and secondary amines but not for the tertiary amine.

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Adsorption Characteristics of Cobalt Ion with Zeolite Synthesized by Coal Fly Ash (석탄계 비산재로 합성한 제올라이트를 이용한 코발트 이온의 흡착특성)

  • Lee, Chang-Han;Suh, Jung-Ho
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.11
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    • pp.941-946
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    • 2009
  • Two types of synthetic zeolites, commercially used (Z-WK) and synthesized by coal fly ash (Z-C1), and raw coal fly ash(F-C1) were examined for its kinetics and adsorption capacities of cobalt. Experimental data are fitted with kinetic models, Lagergen $1^{st}$ and $2^{nd}$ order models, and four types of adsorption isotherm models, Langmuir, Freundlich, Redlich-Peterson, and Koble-Corrigan. Synthesized zeolite (Z-C1) which had 1.51 of Si/Al ratio was synthesized by raw coal fly ash from a thermal power plant. Adsorption capacities with three types of adsorbents, Z-WK, Z-C1, and F-C1, were in the order of Z-C1 (94.15 mg/g) > F-C1 (92.94 mg/g) > Z-WK (88.56mg/g). The adsorption kinetics of Z-WK and Z-C1 with cobalt could be accurately described by a pseudo-second-order rate equation. The adsorption isotherms of Z-WK and Z-C1 with cobalt were well fitted by the Langmuir and Redlich-Peterson equation. Z-C1 will be used to remove cobalt in water as a more efficient absorbent.

Multiphysics analysis of Hydrodynamics and Electrodeposition for Rotating Disk Electrode and Rotating Cylinder Hull Cell (회전원판전극(RDE) 및 회전헐셀(RCHC)에서의 유동 및 전기도금 다중물리 해석연구)

  • Lee, Gyu-Hwan;Hwang, Yang-Jin;Im, Jae-Hong;Jeon, Sang-Hyeon
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2015.11a
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    • pp.156-156
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    • 2015
  • 도금 시뮬레이션의 목적은 실제 도금 상황에서의 전류밀도 및 도금두께 분포를 정확히 예측하여 최상의 품질과 최적의 공정조건을 확립하는데 있다. 제품에 부착된 도금 두께는 기하학적 배치에 의한 저항 (1차 전류밀도), 전기화학적 전하교환 반응에 의한 분극 (2차 전류밀도) 및 확산, 유동 등 도금물질의 공급에 의한 분극(3차 전류밀도)에 의해 결정이 된다. 현재까지 도금 시뮬레이션은 1차 전류밀도 예측에 대한 전자기학적 해석과 Butler-Volmer 식에 근거한 동력학적 전기화학 해석을 통해 2차 전류밀도 분포 해석만 이루어졌다. 즉, 도금 반응에 있어서 물질공급은 항상 일정하게 유지되는 것을 가정하고 해석을 하였다. 이는 3차 전류밀도 분포에 있어서 전극반응 계면에서의 유동에 의한 물질공급이 전기화학과는 다른 물리(physics) 영역이어서 이를 전기화학과 coupling 하는데 기술적으로 어렵기 때문이었다. 그러므로, 물질공급반응이 속도결정단계가 되는 고속도금이나 저농도 도금, gap, tranch, via hole, through hole 등의 도금의 경우에는 해석결과에 큰 오차를 야기하게 된다. 본 발표에서는 그동안 접근하지 못했던 전기도금 해석에 있어서 유동해석을 커플링하여 다중물리해석을 한 결과를 발표한다. 시편으로는 회전원판전극과 회전 헐셀을 이용하여 회전속도 (rpm)에 따른 전류밀도 및 도금두께 분포의 변화 거동을 예측하였다.

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Enhancement of ${\beta}$-1,3-Glucan Functionality by Batch and Semi-continuous Typed Specific Carboxylation (회분식 및 반연속식 특이적 카르복실화 반응에 의한 ${\beta}$-1,3-glucan의 기능성 향상)

  • Jeong, Suk-Yun;Kim, Sang-Woo;Lee, Yong-Hwan;Lee, Jae-Hwan;Chang, Pahn-Shick
    • Korean Journal of Food Science and Technology
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    • v.40 no.2
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    • pp.146-151
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    • 2008
  • In this study, batch or semi-continuous reactions, introducing site-specific carboxylic acids in ${\beta}$-1,3-glucan structures, were performed to increase water solubility and gel forming ability, using TEMPO/hypobromite with or without NaBr as catalysts. Regio-selective carboxylic acid formations were determined with infrared (IR) and $^{13}C$ nuclear magnetic resonance (NMR) spectroscopic analyses. The regio-selective reactions with and without NaBr gave oxidation yields of 92.5 and 85.6%, respectively, in the batch type, and yields of 93.9 and 86.4%, respectively, in the semi-continuous type. The reaction times in the batch and semi-continuous reactions without NaBr were delayed by 100 and 150%, respectively, as compared to those with NaBr. A combination of IR and $^{13}C$ NMR analyses were used to confirm the formation of carboxylic acids in ${\beta}$-1,3-glucan. From the batch reactions with and without NaBr, the water solubilities of oxidized products were 50.0 and 55.6%, respectively, and in the semi-continuous reactions they were 52.6 and 53.5%, respectively; while the water solubility of the native ${\beta}$-1,3-glucan was less than 1.0%. Finally, as compared to the native ${\beta}$-1,3-glucan, the gel forming ability of the reaction products was greatly increased irrespective of the presence of NaBr or the reaction type.

Characteristics in Oxidation of Korean Corn Starch with Sodium Hypochlorite (Hypochlorite에 의한 한국산 옥수수 전분의 산화특성)

  • Han, Jin-Suk;Ahn, Seung-Yo
    • Korean Journal of Food Science and Technology
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    • v.29 no.6
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    • pp.1094-1100
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    • 1997
  • Effects of sodium hypochlorite (NaOCl) concentration, temperature and pH on oxidation mechanism of corn starch were investigated. The rate of oxidation was dependent on the concentration of hypochlorite, pH and temperature of oxidation. The reaction was either first or second order depending on the concentration of NaOCl. At oxidant concentration of $0.75{\sim}3.0%$ active Cl/g starch, the reaction was first-order and it was second-order at $3.75{\sim}4.5%$ active Cl/g starch. The first-order rate constants were increased with increasing oxidant concentration. The rate of oxidation of starch was highest at pH 7 and decreased with increasing acidity or alkalinity of the medium. As the reaction temperature increased, the rate of oxidation was increased.

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