• Korean Chemical Engineering Research
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• 제50권2호
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• pp.217-222
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• 2012

이산화탄소를 이용하여 디메틸카보네이트(DMC)를 제조하는 반응은 지구온난화 현상의 주요 원인으로 지적되는 이산화탄소의 효율적 전환 방법의 하나로 주목 받고 있다. DMC는 유독한 포스겐과 디메틸슬페이트를 대체하는 반응 매개체, 가솔린 연료 첨가제, 폴리카보네이트 수지의 전구체 등으로 다양하게 활용되고 있다. 본 연구에서는 에틸렌카보네이트(EC)와 메탄올의 에스테르 교환반응에 의한 DMC의 제조 반응에 대하여 이온성 액체와 금속 촉매의 특성을 조사하였다. 촉매 스크리닝 실험 결과 [Choline][OH]와 [BMIm][OH]가 금속염인 MgO, ZnO, CaO보다 더 좋은 촉매 활성을 나타내었다. [Choline][OH] 촉매에 대해서 반응변수인 반응온도, MeOH/EC 몰비, 이산화탄소 압력이 반응에 미치는 영향을 고찰하였다. 반응온도가 높고 MeOH/EC 몰비가 클수록 EC의 전화율이 증가하였다. 그러나 이산화탄소 압력의 영향에서는 1.34 MPa에서 최고의 DMC 수율을 나타내었고 그 이상의 압력에서는 DMC 수율이 오히려 감소하였다. $ZnCl_2$를 조촉매로 사용한 경우 각각 촉매의 활성보다 더 높은 활성을 나타내어 시너지 효과가 관찰되었으며, 이것은 혼합촉매의 산-염기적 특성에 기인하는 것으로 판단된다.

• 한국응용과학기술학회지
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• 제7권1호
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• pp.93-105
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• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

• 폴리머
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• 제36권1호
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• pp.98-103
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• 2012

구리 계열의 $Cu(NO_2)_2{\cdot}3H_2O$와 CuCl을 중합촉매로 사용하고 다양한 용매, 리간드와 염기의 함량을 변화시켜 poly(2,6-dimethyl-1,4-phenylene ether)(PPE) 중합반응을 고찰하였다. 이 가운데 CuCl/1-methylimidazole/ammonium hydroxide 시스템에서 가장 높은 중합 수율을 나타내었다. 한편, 몇 가지 다른 유기용매와 메탄올의 혼합용매 시스템에서 용매의 성분비율을 변화시켜 용매의 조성이 중합반응에 미치는 영향을 조사하였으며 2,4,6-trimethylphenol (TMP)를 사용하여 TMP 함량에 따른 분자량 조절 효과를 조사하였다. 클로로포름/메탄올 9/1(v/v) 혼합용매를 사용했을 때 가장 높은 중합 수율과 높은 분자량을 갖는 중합체($\overline{M_n}$ : 55 K; $\overline{M_w}$ : 92 K; PDI: 1.7)를 얻었다. 구리 일가 촉매인 CuCl 과 CuI를 사용하여 서로다른 짝이온, 즉 $Ci^-$와 $I^-$ 이온이 중합결과에 미치는 영향을 조사하였다. 촉매의 활성 비교를 위하여 산소 흡수량(oxygen-uptake)을 측정하였으며, 중합반응의 부산물인 5,5'-tetramethyl-4,4'-diphenoquinone (DPQ)의 함량을 자외선 분광기(ultraviolet spectroscopy)를 통하여 분석하였다.

• 한국수산과학회지
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• 제19권5호
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• pp.436-445
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• 1986

As the second part of the studies on the utilization of polyunsaturated lipids in sardine oil as nutritional or medical supplement, the conditions of lipid extration and concentration, refining, and storage stability of EPA-condensed sardine oil were investigated. In extraction of lipids, solvent ratios of chloroform-methanol mixture(2:1 v/v) affected the final content of unsaturated lipid in extracted oil and recovery. Stepwise solvent fractionation method at various low temperatures was effective to concentrate polyenoic acids like EPA and DHA when acetone or acetone-methanol mixture, added in the ratio of 1:5 (v/v) was applied step by step to different temperatures at 0 to $-35^{\circ}C$. Addition of 1 to $5\%$ (v/v) of water to acetone was also benefit to raise EPA content but that resulted in reducing the yield of condensed oil from $65\%\;to\;28\%$. Concentration rate of polyenoic acids by solvent fractionation in lipid-actone solution (1:5, v/v) at 0 to $-30^{\circ}C$ seemed limited to $5{\sim}8\%$ in fatty acid composition depending on the initial content of those polyenoic acids in the sardine oil. During the extraction, concentration, and alkaline treatment, oxidation was rapidly induced but oxidation products could be thoroughly removed on the process of deceleration and peroxide elimination. To stabilize the reactive polyenoic acid condensed oil during the storage, stuffing nitrogen gas was essential to expel dissolved oxygen in oil or to seal the oil from open air, and the addition of antioxidative agents as BHA and tocopherols were greatly helpful to extend the storage life.

• 한국수소및신에너지학회논문집
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• 제25권2호
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• pp.105-113
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• 2014

Performance tests on $Ni/Ce-ZrO_2/Al_2O_3$ catalysts with additives (MgO, $La_2O_3$) were investigated in the combined reforming processes (SCR, ATR, TRM) in order to produce hydrogen and carbon monoxide (it is called "syngas".). The catalyst characterization was conducted using the BET surface analyzer, X-ray diffraction (XRD), SEM, TPR and TGA. The combined reforming process was developed to adjust the syngas ratio depending on the synthetic fuel (methanol, DME and GTL) manufacturing processes. Ni-based catalysts supported on alumina has been generally recommended as a combined reforming reaction catalyst. It was found that both free NiO and complexed NiO species were responsible for the catalytic activity in the combined reforming of methane conversion, and the $Ce-ZrO_2$ binary support employed had improved the oxygen storage capacity and thermal stability. The additives, MgO and $La_2O_3$, also seemed to play an important role to prevent the formation of the carbon deposition over the catalysts. The experimental results were compared with the equilibrium data using a commercial simulation tool (PRO/II).

• Bulletin of the Korean Chemical Society
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• 제14권6호
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• pp.687-691
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• 1993

Complexation of $Cd^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions with four cryptands were studied by potentiometry and solution calorimetry in various weight percent methanol-aqueous solvent at 25${\circ}$C under $CO_2$free nitrogen atmosphere. The stabilities of the complexes were dependent on the cavity size of macrocycles. The $Hg^{2+}$ ion stability constants are higher than those of $Cd^{2+}\;and\;Pb^{2+}$ ion. All the cryptands formed complexes having 1 : 1 (metal to ligand) mole-ratio except for $Hg^{2+}-L_1$ (cryptand 1,2b: 3,5-benzo-9,14,17-trioxa-1,7-diazabicyclo-(8,5,5) heptadecane) and $Cd^{2+}-L_2$ (cryptand 2,2b: 3,5-benzo-10,13,18,21-tetraoxa-1,7-diazabicyclo (8,5,5) eicosane) complexes. $Hg^{2+}-L_1$ complex was a sandwitch type, and the $Cd^{2+}-L_2$ complex showed two stepwise reactions. Thermodynamic parameters of the $Cd^{2+}-L_2$ complex were $6.08(log\;K_1)$, -7.28 Kcal/mol $({\Delta}H_1)$, and $4.78\;(log\;K_2)$, -4.62 Kcal/mol $({\Delta}H_2)$, respectively, for 1 : 1 and 2: 1 mole-ratio. The sequences of the selectivity were increased in the order of $Hg^{2+}\;>Pb^{2+}\;>Cd^{2+}$ ion for $L_3\;and\;L_4$ macrocycles, and the $L_2$-macrocycle has a selectivity for $Cd^{2+}$ ion relative to $Zn^{2+},\;Ni^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions. Thus, it is expected that the $L_2$ can be used as carrier for seperation of the post transition metals by macrocycles-mediated liquid membrane because $L_2$ is not soluble in water, and the difference of stability constants of the metal complexes with $L_2$ are large as compared with the other transition metal complexes. The $^1H\;and\;^{13}C-NMR studies indicated that the nitrogen atoms of cryptands have greater affinity to the post transition metal ions than the oxygen atoms, and that the planarities of the macrocycles were lost by complexation with the metal ions because of the perturbation of ring current of benzene molecule attached to macrocycles and counter-anions.