• Title/Summary/Keyword: 불균일 촉매

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Synthesis of Enantiopure Epoxide Compounds Using Dimeric Chiral Salen Catalyst (이량체구조를 갖는 키랄 살렌 촉매를 이용한 고 광학순도의 에폭사이드 화합물 합성)

  • Kim, Geon-Joong;Kim, Seong-Jin;Li, Wenji;Chen, Shu-Wei;Shin, Chang-Kyo;Thakur, Santosh S.
    • Korean Chemical Engineering Research
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    • v.43 no.6
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    • pp.647-661
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    • 2005
  • The stereoselective synthesis of chiral terminal epoxide is of immense academic and industrial interest due to their utility as versatile starting materials as well as chiral intermediates. In this review, we investigate the research and development trend in the asymmetric ring opening reactions using cobalt salen catalysts. Hydrolytic kinetic resolution (HKR) technology is the very prominent way to prepare optically pure terminal epoxides among available methods. We have synthesized homogeneous and heterogeneous chiral dinuclear salen complexes and demonstrated their catalytic activity and selectivity for the asymmetric ring opening of terminal epoxides with variety of nucleophiles and for asymmetric cyclization to prepare optically pure terminal epoxides in one step. The resolved ring opened product combined with ring closing in the presence of base and catalyst afforded the enantioriched terminal epoxides in quantitaive yield. Potentially, these catalysts are using on an industrial scale to produce chiral intermediates. The experimental results of HKR technology applied to the synthesis of various chiral compounds are presented in this paper.

A Study on Heterogeneous Catalysts for Transesterification of Nepalese Jatropha Oil (네팔산 Jatropha 오일의 전이에스테르화 반응용 불균일계 촉매 연구)

  • Youngbin Kim;Seunghee Lee;Minseok Sim;Yehee Kim;Rajendra Joshi;Jong-Ki Jeon
    • Clean Technology
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    • v.30 no.1
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    • pp.47-54
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    • 2024
  • Jatropha oil extracted from the seeds of Nepalese Jatropha curcas, a non-edible crop, was used as a raw material and converted to biodiesel through a two-step process consisting of an esterification reaction and a transesterification reaction. Amberlyst-15 catalyst was applied to the esterification reaction between the free fatty acids contained in the Jatropha oil and methanol. The acid value of the Jatropha oil could be lowered from 11.0 to 0.26 mgKOH/g through esterification. Biodiesel was synthesized through a transesterification reaction between Jatropha oil with an acid value of 0.26 mgKOH/g and methanol over NaOH/γ-Al2O3 catalysts. As the loading amount of NaOH increased from 3 to 25 wt%, the specific surface area decreased from 129 to 28 m2/g and the pore volume decreased from 0.249 to 0.129 cm3/g. The amount and intensity of base sites over the NaOH/γ-Al2O3 catalysts increased simultaneously with the NaOH loading amount. It was confirmed that the optimal NaOH loading amount for the NaOH/γ-Al2O3 catalyst was 12 wt%. The optimal temperature for the transesterification reaction of Jatropha oil using the NaOH/γ-Al2O3 catalyst was selected to be 65 ℃. In the transesterification reaction of Jatropha oil using the NaOH/γ-Al2O3 catalyst, the reaction rate was affected by external diffusion limitation when the stirring speed was below 150 RPM, however the external diffusion limitation was negligible at higher stirring speeds.

A Study on the Hydrolysis of Sarin and Soman by Merrifield-Type Diaminatedpolystyrene-Cu (II) Heterogeneous Polymers (Merrifield-Type Diaminatedpolystyrene-Cu (II) 불균일 촉매에 의한 Sarin과 Soman 분해반응 연구)

  • 정우영;계영식
    • Journal of the Korea Institute of Military Science and Technology
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    • v.3 no.1
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    • pp.164-175
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    • 2000
  • Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

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Formation Mechanism of Pores in Ni-P Coated Carbon Fiber Prepared by Electroless Plating Upon Annealing (무전해 니켈-인 도금법을 이용하여 도금된 탄소 섬유의 열처리 과정에서 나타나는 다공성 구조 생성 메커니즘 분석)

  • Ham, Seung Woo;Sim, Jong Ki;Kim, Young Dok
    • Applied Chemistry for Engineering
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    • v.24 no.4
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    • pp.438-442
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    • 2013
  • In the present work, electroless plating was used for coating thin films consisting mainly of Ni and P on carbon fiber. Structural changes appeared upon the post-annealing at various temperatures of the Ni-P film on carbon fiber was studied using various analysis methods. Scanning, a flat surface structure of Ni-P film on carbon fiber was found after electroless plating of Ni-P film on carbon fiber without post-annealing, whereas annealing at $350^{\circ}C$ resulted the formation of porous structures. With increasing the annealing temperature to $650^{\circ}C$ with an interval of $50^{\circ}C$, the pore size increased, but the density decreased. X-ray diffraction (XRD) showed the existence of metallic Ni, and Ni-P compounds before post-annealing, whereas the post-annealing resulted in the appearance of NiO peaks, and the decrease in the intensity of the peak of metallic Ni. Using X-ray photoelectron spectroscopy (XPS), phosphorous oxides were detected on the surface upon annealing at $650^{\circ}C$, and $700^{\circ}C$, which can be attributed to the phosphorous compounds originally existing in the deeper layers of the Ni films, which undergo sublimation and escape from the film upon annealing. Escape of phosphorous species from the bulk of Ni-P film upon annealing could leave a porous structure in the Ni films. Porous materials can be of potential applications in diverse fields due to their interesting physical properties such as high surface area, and methods for fabricating porous Ni films introduced here could be easily applied to a large-scale production, and therefore applicable in diverse fields such as environmental filters.

Numerical Investigation of the Spray Behavior and Flow Characteristics of Urea-Water Solution Injected into Diesel Exhaust Pipe (디젤 배기관에 분사된 우레아 수용액의 분무 거동 및 유동 특성에 관한 연구)

  • An, Tae Hyun;Kim, Man Young
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.38 no.1
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    • pp.41-48
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    • 2014
  • A urea-SCR system suffers from some issues associated with the ammonia slip phenomenon, which mainly occurs because of the shortage of evaporation and thermolysis time, and this makes it difficult to achieve an uniform distribution of injected urea. A numerical study was therefore performed by changing such various parameters as installed injector angle and application and angle of mixer to enhance evaporation and the mixing of urea water solution with exhaust gases. As a result, various parameters were found to affect the evaporation and mixing characteristics between exhaust gas and urea water solution, and their optimization is required. Finally, useful guidelines were suggested to achieve the optimum design of a urea-SCR injection system for improving the DeNOx performance and reducing ammonia slip.

결정질 실리콘 태양전지 표면 조직화 형상과 효율의 상관관계 분석

  • Kim, Min-Yeong;Kim, Jun-Hui;Park, Ju-Eok;Jo, Hae-Seong;Kim, Dae-Seong;Byeon, Seong-Gyun;Im, Dong-Geon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.445.2-445.2
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    • 2014
  • 표면 조직화의 목적은 태양전지 표면에서의 입사되는 빛의 반사율을 감소 시키고, 웨이퍼 내에서 빛의 통과 길이를 길게 하며, 흡수되는 빛의 양을 증가시키는 것이다. 본 연구에서는 여러 가지 표면 조직화 공정 기술을 이용하여 표면 형상에 따른 광 변환 효율에 대해 연구하였으며, 셀을 제작하여 전기적 특성과 광학적 특성의 상관관계를 분석하였다. KOH를 이용한 표면 조직화, 산 증기를 이용한 표면 조직화, 반응성 이온 식각을 이용한 표면 조직화, 금속 촉매 반응을 이용한 표면 조직화 공정 기술을 이용하여 표면 조직화 공정을 진행하였다. 셀 제작 결과, 반사도 결과와는 상반되는 결과를 얻을 수 있었다. 표면 조직화 형상에 따른 셀 효율의 변화는 도핑 프로파일과 표면 재결합 속도의 변화 때문이라 생각되며 더 명확한 분석을 위해 양자 효율을 측정하여 분석을 시도하였다. 표면 조직화 공정 기술별 도핑 프로파일을 보면 KOH를 이용한 표면 조직화 공정을 제외한 나머지 표면 조직화 공정들의 도핑 프로파일은 불균일하게 형성되어 있는 것을 확인 할 수 있다. 양자 효율 측정 결과 단파장 대역에서 낮은 응답특성을 가지는 것을 확인 할 수 있었다. 그 이유는 낮은 반사도를 가지는 표면 조직화 공정의 경우 나노사이즈의 구조를 갖기 때문에 균일한 도핑 프로파일을 얻지 못해 전자, 정공의 분리가 제대로 이루어지지 못하였고 표면 재결합 속도증가의 원인으로 단락전류와 개방전압이 낮아져 효율이 떨어진 것으로 판단된다. 결과적으로 낮은 반사율을 갖는 표면 조직화 공정도 중요하지만 표면 조직화 공정 기술에 따른 균일한 도핑 프로파일을 갖는 공정을 개발한다면 단파장 응답도가 향상되어 단락전류밀도와 개방전압 상승효과를 얻을 수 있을 것이라 판단된다.

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The Effect of Comonomer Type and Content on the Properties of Ziegler-Natta Bimodal High-Density Polyethylene (공단량체의 종류 및 조성이 지글러-나타 중합된 이중 분자량 분포 고밀도 폴리에틸렌의 물성에 미치는 영향)

  • Meng, Weijuan;Li, Hongbo;Li, Jianwei;Chen, Biaohua
    • Journal of the Korean Chemical Society
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    • v.55 no.4
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    • pp.673-679
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    • 2011
  • Bimodal high-density polyethylenes with different comonomer type and content were synthesized by polymerization of ethylene using Ziegler-Natta catalyst. Their structure and properties were studied using GPC, NMR, DSC and tensile test. It was found that ethylene/1-hexene copolymer exhibits higher tensile strength and elongation at break than that of ethylene/1-butylene copolymer with similar comonomer content. The molecular weight decreases as the comonomer content of the polymer increases. Short chain branching affects the crystallinity and thus the morphology and consequently the mechanical properties of the corresponding bimodal high-density polyethylenes. After SSA treated, the multiple endothermic peaks were observed. Multiple endothermic peaks are mainly attributed to the heterogeneity of ethylene sequence length and lamellar thickness. The difference of broadness index indicates that SCB distribution of polyethylene containing higher comonomer content has improved uniformity.

Tubular Type Direct Methanol Fuel Cell for in situ NMR Diagnosis (In Situ NMR 진단용 원통형 직접 메탄올 연료전지)

  • Joh, Han-Ik;Um, Myung-Sup;Han, Kee-Sung;Han, Oc-Hee;Ha, Heung-Yong;Kim, Soo-Kil
    • Journal of the Korean Electrochemical Society
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    • v.12 no.4
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    • pp.329-334
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    • 2009
  • This study is to develop a fuel cell system applicable to an in situ NMR (Nuclear magnetic resonance) diagnosis. The in situ NMR can be used in real time monitoring of various reactions occurring in the fuel cell, such as oxidation of fuel, reduction of oxygen, transport phenomena, and component degradation. The fuel cell for this purpose is, however, to be operated in a specifically designed tubular shape toroid cavity detector (TCD), which constrains the fuel cell to have a tubular shape. This may cause difficulties in effective mass transport of reactants/products and uniform distribution of assembly pressure. Therefore, a new flow field designed in a particular way is necessary to enhance the mass transport in the tubular fuel cell. In this study, a tubular-shaped close-type flow field made of non-magnetic material is developed. With this flow field, oxygen is effectively delivered to the cathode surface and the produced water is readily removed from the membrane-electrode assembly to prevent flooding. The resulting DMFC (direct methanol fuel cell) outperforms the open-type flow field and exhibits $36\;mW/cm^2$ even at room temperature.