• 수산해양기술연구
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• 제35권4호
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• pp.366-376
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• 1999

In order to examine the catching selectivity of the ark shell(Scapharca broughtonii) dredge, the various factors affecting the selective action of the dredge are analyzed, and the probabilities of the ark shell not shifting through the gaps between the teeth, and the mesh of the netting bag, are calculated for the various shell lengths, using the relation between the posture and the length when the shell passes through these parts.Considering that the probability of making catch is the product of the both probabilities described above, and that this probability is proportional to the relative catching efficiency, the selectivity curves for the ark shell dredge were estimated for various gaps between the teeth and for the various mesh sizes of the netting bag. The obtained results are summarized as follows :1. The ratios of the shell length of ark shell to the distance between teeth indicating the relative catching efficiency of 0%, 50, 100% respectively were 1.0, 1.26~1.28, 1.47~1.44, and that the selection ranges of selective shell length by the distance between teeth were 0.47~0.44, where the distances between teeth were 3.2cm, 3.6cm, 4.0cm, 4.4cm and 4.8cm. 2. The ratios of the shell length of ark shell to the mesh size indicating the relative catching efficiency of 0%, 50%, 100% respectively were 0.67, 0.84, 0.97 and that the selection range of shell length for catching, that in the range of selective shell length by the mesh size was 0.31, where the distance of 4.0cm between teeth, mesh size of 6.0 cm and the smaller mesh angle of $60^{\circ}$3. Where the distance between teeth is 4.0 cm and the smaller mesh angle is $60^{\circ}$, the selection range of shell length for catching of the ark shell dredge is decreased according to the mesh size, and it is minimized by 0.20 in the mesh size of 9.0~10.0 cm, but increased in the mesh size of over 11.0 cm. 4. Where the distance between teeth is 4.0 cm, the selective action by the mesh size of netting bag is begun with the mesh size of over 10.0 cm.

• Tribology and Lubricants
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• 제35권2호
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• pp.132-138
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• 2019

In this study, we demonstrate the effects of the acidic properties of montmorillonite (MMT), which is commonly used as a catalyst, on the conversion and selectivity of the dimer acid methyl ester (DAME) synthesis. We synthesize DAME by the dimerization of conjugated linoleic acid methyl ester (CLAME) and oleic acid methyl ester using MMT KSF. Incidentally, trimer acid methyl ester was formed as a by-product during the DAME synthesis. There is a necessity to adequately adjust the strength and quantity of the acid site to control the selectivity of DAME. Therefore, we vary the pH of the MMT acid by using various metal hydroxides. The purpose of this study is to increase the yield of monocyclic dimer acid methyl ester, which is a substance with adequate physical properties for industrial applications (e.g., lubricant and adhesive, etc.), using a heterogeneous catalyst. We report the dimerization of fatty acid methyl ester by using base treated-KSF, and apply it to conjugated soybean oil methyl ester. Then, we transmute the acid site properties of KSF, such as pH of 5 wt.% slurry KSF and various alkali metals (Li, Na, K, Ca). Characterization of base treated-KSF using a pH meter, x-ray diffraction, inductively coupled plasma-atomic emission spectrometer, Brunauer-Emmett-Teller surface analysis, and temperature-programmed desorption. We conduct an analysis of CLAME and DAME using nuclear magnetic resonance spectroscopy, gas chromatography, and gel permeation chromatography. Through these experiments, we demonstrate the effects of the acidic properties of KSF on the conversion and selectivity of the DAME synthesis, and evaluate its industrial potential by application to waste vegetable oil.

• Bulletin of the Korean Chemical Society
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• 제26권4호
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• pp.558-562
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• 2005

Crystallization of SAPO-5 and SAPO-34 molecular sieves with microwave and conventional electric heating of the same gel has been investigated in an alkaline condition using N,N,N’N’tetraethylethylenediamine as a template molecule. SAPO-5 structure can be selectively prepared with microwave heating because of the fast crystallization of the technique. On the other hand, SAPO-34 is the sole product with usual conventional electric heating because SAPO-5 can be gradually transformed into SAPO-34 structure with an increase in crystallization time. This phase selectivity is probably because of the relative stability of the two phases at the reaction conditions (kinetic effect). Crystallization with microwave heating can be suggested as a phase selective synthesis method for relatively unstable materials because of fast crystallization.

• Bulletin of the Korean Chemical Society
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• 제31권8호
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• pp.2361-2367
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• 2010

$TiO_2-ZrO_2$ was prepared with surfactant through a sol-gel method. Catalysts containing 5 - 35% $H_3PO_4$ were prepared using these oxides. Subsequently the catalytic performance of prepared catalysts was determined for liquid phase esterification of aromatic acids. $H_3PO_4/TiO_2-ZrO_2$ has been used as catalyst to synthesize various novel esters by esterification of some aromatic acids with aliphatic alcohols (2-propanol, 1-butanol, iso butanol, 3-pentanol, 1-hexanol, heptanol, cyclo heptanol, octanol and decanol). Under optimized conditions, maximum yields and selectivity (100%) to the corresponding ester, was obtained by using 25 wt % $H_3PO_4/TiO_2-ZrO_2$ as catalyst. The Catalyst can be easily recycled after reaction and can be reused without any significant loss of activity/selectivity performance. No by-product formation, high yields, short reaction times, mild reaction conditions, operational simplicity with reusability of the catalyst are the salient features of the present synthetic protocol. The reaction was carried out under solvent-free condition.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2618-2626
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• 2010

In this paper poly (4-methyl vinylpyridinium hydroxide)/SBA-15 composite was prepared as a highly efficient heterogeneous basic catalyst by in situ polymerization method for the first time. It was characterized by XRD, FT-IR, BET, TGA, SEM and back titration using NaOH. This catalyst exhibited the excellent catalytic activities for the Knoevenagel condensation of various aldehydes with ethyl cyanoacetate. Over this catalyst, ${\alpha},{\beta}$-unsaturated carbonyl compounds were obtained in the reasonable yield at $95^{\circ}C$ in 10 - 30 min in $H_2O$ as a solvent with a 100% selectivity to the condensation products. Catalyst could be easily recycled after the reaction and it could be reused without the significant loss of activity/selectivity performance. No by-product formation, high yields, short reaction times, mild reaction conditions and operational simplicity with reusability of the catalyst were the salient features of the present synthetic protocol. Presence of $H_2O$ as a solvent was also recognized as a "green method".

• Nuclear Engineering and Technology
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• 제44권7호
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• pp.767-772
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• 2012

In support of optimizing electrorefining technology for treating spent nuclear fuel, lithium drawdown has been investigated for separating actinides from molten salt electrolyte. Drawdown reaction selectivity is a major issue that requires investigation, since the goal is to remove actinides while leaving the fission products and other components in the salt. A series of lithium drawdown tests with surrogate fission product chlorides was run to obtain selectivity data with non-radioactive salts, develop a predictive model, and draw conclusions about the viability of using this process with actinide-loaded salt. Results of tests with CsCl, $LaCl_3$, $CeCl_3$, and $NdCl_3$ are reported here. Equilibrium was typically achieved in less than 10 hours of contact between lithium metal and molten salt under well-stirred conditions. Maintaining low oxygen and water impurity concentrations (<10 ppm) in the atmosphere was observed to be critical to minimize side reactions and maintain stable salt compositions. An equilibrium model has been formulated and fit to the experimental data. Good fits to the data were achieved. Based on analysis and results obtained to date, it is concluded that clean separation between minor actinides and lanthanides will be difficult to achieve using lithium drawdown.

• 대한화학회지
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• 제36권4호
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• pp.558-564
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• 1992

여러 가지 치환기를 가지는 망간 포피린착물을 촉매로 사용하여 CH$_2$Cl$_2$ 용매하에서 styrene과 NaOCl간의 반응에 대한 수율을 구하였다. ortho 위치에 치환기를 가지는 망간 포피린 착물과 전자받게성의 치환기를 가지는 망간 포피린착물일 때 반응속도와 에폭사이드에 대한 선택성이 증가했다. 또한 망간 포피린착물에 축상 리간드로서 이미다졸을 도입할 때 반응속도와 에폭사이드에 대한 선택성이 증가했다. Michealis-Menten식을 이용한 반응속도론적 연구에 의하면 착물의 촉매능에 더 큰 영향을 주는 요소는 $K_m$ 임을 알았다. $K_m$ 값이 작을수록 더 큰 결합친화도를 가진다. 이론적인 연구로 EHMO계산에 의해 나온 결과와 실험에 의해 나온 결과는 좋은 일치를 보여주었다.

• Bulletin of the Korean Chemical Society
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• 제24권4호
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• pp.431-436
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• 2003

Solvolytic rate constants at 25℃ are reported for solvolyses of cinnamyl bromide (1) in binary mixtures of water with acetone, ethanol, methanol, methanol-d, and 2,2,2-trifluoroethanol. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol. Rate ratios in solvents of the same $Y_{Br}$ value and different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance (e.g. $[k_{40EW}/k_{97TFE}]$Y = 2.88, EW = ethanol-water). With use of the extended Grunwald-Winstein equation, the l and m values are similar to the values of 0.43 and 0.88 obtained for the solvolyses of 1 using the equation (see below) which includes a parameter (I) for solvation of aromatic rings. The magnitude of l and m values associated with a change of solvent composition predicts the $S_{N1}$ reaction mechanism rather than an $S_{N2}$ channel. Product selectivities (S), defined by S = [ether product]/[alcohol product]×[water]/[alcohol solvent] are related to four rate constants for reactions involving one molecule of solvent as nucleophile and another molecule of solvent as general base catalyst. A linear relationship between 1/S and molar ratio of solvent is derived theoretically and validated experimentally for solvolyses of the above substrates from water up 75% 1/S = $(k_{wa}/k_{aw})$([alcohol solvent]/[water]) + $k_{ww}/k_{aw}$ alcohol-water. The results are best explained by product formation from a “free” carbocation intermediate rather than from a solvent-separated ion pair.

• Journal of Microbiology and Biotechnology
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• 제31권3호
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• pp.464-474
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• 2021

Bacterial cytochrome P450 (CYP) enzymes are responsible for the hydroxylation of diverse endogenous substances with a heme molecule used as a cofactor. This study characterized two CYP154C3 proteins from Streptomyces sp. W2061 (CYP154C3-1) and Streptomyces sp. KCCM40643 (CYP154C3-2). The enzymatic activity assays of both CYPs conducted using heterologous redox partners' putidaredoxin and putidaredoxin reductase showed substrate flexibility with different steroids and exhibited interesting product formation patterns. The enzymatic characterization revealed good activity over a pH range of 7.0 to 7.8 and the optimal temperature range for activity was 30 to 37℃. The major product was the C16-hydroxylated product and the kinetic profiles and patterns of the generated hydroxylated products differed between the two enzymes. Both enzymes showed a higher affinity toward progesterone, with CYP154C3-1 demonstrating slightly higher activity than CYP154C3-2 for most of the substrates. Oxidizing agents (diacetoxyiodo) benzene (PIDA) and hydrogen peroxide (H2O2) were also utilized to actively support the redox reactions, with optimum conversion achieved at concentrations of 3 mM and 65 mM, respectively. The oxidizing agents affected the product distribution, influencing the type and selectivity of the CYP-catalyzed reaction. Additionally, CYP154C3s also catalyzed the C-C bond cleavage of steroids. Therefore, CYP154C3s may be a good candidate for the production of modified steroids for various biological uses.

• 한국응용과학기술학회지
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• 제21권1호
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• pp.45-50
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• 2004

The effects of reaction temperature and flow rate of reactants on the methane conversion, product selectivity, product ratio, and carbon deposition were investigated with 13wt% Ni/MgO catalyst. Reaction temperatures were changed from 600 to $850^{\circ}C$, and reactants flow rates were changed from 100 to 200 mL/mim. There were no significant changes in the methane conversion observed in the range of temperatures used. It is possibly stemmed from the nearly total exhaustion of oxygen introduced. The selectiveties of hydrogen and carbon monoxide did not largely depend on the reaction temperature. The selectivities of hydrogen and carbon monoxide were 96 and 90%, respectively. Carbon deposition observed was the smallest at $750^{\circ}C$ and the largest at $850^{\circ}C$. It is found that the proper reaction temperature is $750^{\circ}C$. The best reactant flow rate was 150 ml/min.