• Korean Chemical Engineering Research
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• v.57 no.5
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• pp.714-722
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• 2019

Catalysts were prepared by using incipient wetness impregnation method with 17 wt% Ni on a support ($SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, $SiO_2$, $TiO_2$, MgO) and the catalytic activity in the reductive amination of ethanol with ammonia in the presence of hydrogen was compared and evaluated. The catalysts used before and after the reaction were characterized using X-ray diffraction, nitrogen adsorption, ethanol-temperature programmed desorption (EtOH-TPD), isopropanol-temperature programmed desorption (IPA-TPD), and hydrogen chemisorption etc. In the case of preparing $ZrO_2$ and $Y_2O_3$ supports, the small amount of Si dissolution from the Pyrex reactor surface provoked the formation of mixed oxides $SiO_2-ZrO_2$ and $SiO_2-Y_2O_3$. Among the catalysts used, $Ni/SiO_2-Y_2O_3$ catalyst showed the best activity, and this good activity was closely related to the highest nickel dispersion, and low desorption temperature in EtOH-TPD and IPA-TPD. The low catalytic activity on Ni/MgO catalysts showed low activity due to the formation of NiO-MgO solid-solutions. In the case of $Ni/TiO_2$, the reactivity was low due to the low nickel metal phase due to strong metal-support interaction. In the case of using a support as $SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, and $SiO_2$, the selectivities of ethylamines and acetonitrile were not significantly different at similar ethanol conversion.

• 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.

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.461-468
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• 1991

The cationic polymerizations of substituted oxiranes which have pendant energetic groups such as azido, and nitrato, are investigated theoretically using the semiempirical MNDO, and $AM_1$ methods. The nucleophilicity and basicity of substituted oxiranes can be explained by the negative charge on oxygen atom of oxiranes. The reactivity of propagation in the polymerization of oxiranes can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxiranes. Ring opening of the complexed cyclic oxonium ion to the open chain carbenium ion is expected computational stability of the oxonium and carbenium ion by 30∼40 kcal/mol favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium and open carbenium ions will be a major determinant of mechanism. The chain growth $SN_1$, mechanism will be at least as fast as that for $SN_2$ mechanism.

• Applied Chemistry for Engineering
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• v.21 no.3
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• pp.278-283
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• 2010

The cationic polymerization of oxolane high explosives which have pendant explosive groups such as azido, nitrato and hydrazino is investigated theoretically using the semiempirical MINDO/3, MNDO and AM1 methods. The nucleophilicity and basicity of oxolane high explosives can be explained by the negative charge on oxygen atom of oxolane. The reactivity of propagation in the polymerization of oxolane can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxolane. The reaction of the oxolane high explosives in oxonium ion form to the open chain carbenium ion form is expected by computational stability energy (17.950~30.197 kcal/mol) of the oxonium ion and carbenium ion favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium ion and carbenium ion is found to be a major determinant of mechanism, owing to the rapid equilibrium of these catoinic forms. Based on calculation, in the prepolymer propagation step, $S_N1$ mechanism will be at least as fast as that for $S_N2$ mechanism.

• Applied Biological Chemistry
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• v.51 no.3
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• pp.177-182
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• 2008

This study was carried out to investigate the reaction of lipase-catalyst transesterification using animal fat recovered from fleshing scrap generated during leather making process. Transesterification reaction between fat and primary or secondary alcohol was carried out under the condition of immobilized enzyme catalyst. The conversion rate was the highest when 1.5 mole of methanol was injected by 4 times. As for lipase, Candida antarctica showed the highest conversion rate of 82.2% among the 4 different lipases. It was found that water contained in the fat causes lower conversion rate. The condition of 1.2wt. % of water in the fat decreased the conversion rate by 40%. It was considered that the resulted reactant, fatty acid ester could be used as raw material for biodiesel with the characteristics of not generating SOx and diminishing smoke.

• Applied Chemistry for Engineering
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• v.7 no.5
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• pp.925-937
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• 1996

Three types of mordenites treated by steaming($SM_{6.5}$), HF solution for $SM_{6.5}(FM_a)$ and HF solutlon+steaming for $SM_{6.5}(FM_b)$ were prepared and used as cracking catalysts of vacuum gas oil. These samples were analysed by XRF and XPS for average and surface Si/Al atomic ratio, XRD for unit cell constants, nitrogen adsorption/desorption for porosity, pyridine-IR for acidic properties. In comparison with three type samples, $SM_{6.5}$ had a lot of acid amount and showed micropore volume mostly(>85% to total volume). Dealuminated $FM_a$, compared with $SM_{6.5}$, was decreased a little in acid amount and improved for porosity. Also, $FM_b$ was decreased further in acid amount and developed in mesopore dramatically. The catalytic activity and the yield of gasoline, kerosine+diesel and branched aromatic over the modified mordenites which have developed mesopore were improved. This is due to limited access of diffusion of large molecules within pore of the modified mordenites.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.113.1-113.1
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• 2011

미세조류 내의 엽록소는 바이오디젤 전환 반응에서 산 촉매의 활성을 억제 할 뿐만 아니라, 짙은 색상을 띄게하여 바이오디젤 품질규격으로부터 벗어나게 한다. 미세조류의 엽록소 분석은 용매에 의해 엽록소를 추출한 후, 흡광도를 측정하여 그 함량을 계산하는 방법을 널리 사용하고 있다. 건조된 미세조류의 분석은 선택되는 용매에 따라 최대 추출량이 달라지는 것을 제외하고 큰 문제가 없지만 미세조류를 lipid 오일로 변환하면, 용매에 녹지 않아 추출이 되지않는 문제가 발생하여 흡광도 측정을 어렵게 한다. 따라서 미세조류의 형태가 powder일 때와 오일인 경우를 구분하여 용매를 선택해야 하며, 오일 또는 powder 형태 구분 없이 사용할 수 있는 분석법을 적용하여 서로 다른 엽록소 함량을 비교한 후 분석법 간의 상호 장단점을 파악해야한다. 본 연구에서는 메탄올을 용매로 사용하는 분석법(porra et al.)과 아세톤을 용매로 사용하는 분석법(Humphrey and Jeffrey)을 적용하여 엽록소 함량을 비교하였고, AAS(Atomic Absorption Spectrometer)를 통한 Mg 함량 측정을 통해 엽록소 함량을 계산하는 분석법간의 차이를 확인하였다.

• Korean Chemical Engineering Research
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• v.48 no.3
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• pp.316-321
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• 2010

The $SO_2$ catalytic reduction was carried out under the condition of high pressure in this study. Sn-Zr based oxide and CO were used as the catalyst and reducing agent for the reduction of $SO_2$ to element sulfur, respectively. In order to compare the reactivity with the pressure on the catalytic process, the reactivity tests were performed under the conditions of atmospheric pressure and 20 atm. $SO_2$ conversion, the element sulfur yield and COS selectivity were also compared with changing the reaction temperature, $CO/SO_2$ mole ratio and the space velocity(GHSV). $SO_2$ conversion increased with increasing temperature and $CO/SO_2$ mole ratio under the condition of atmospheric pressure and element sulfur yield decreased due to the production of COS by the series reaction of CO and the produced sulfur. However, high $SO_2$ conversion and high element sulfur were obtained under the condition of 20 atm. It was concluded that COS decreased due to the condensation of the produced element sulfur under the condition of high pressure. Therefore, the high sulfur yield for $SO_2$ catalytic reduction could be profitably obtained under the condition of high pressure.

• Applied Chemistry for Engineering
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• v.17 no.3
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• pp.321-326
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• 2006

Thermal degradation of styrene dimer fraction (SDF, main compound: 47 wt% of 1,3-diphenylpropane), 5~15% of total products produced during decomposition of waste expanded polystyrene (WEPS) was investigated. Reaction condition of $360^{\circ}C$, and 152 kPa to 202 kPa was an optimum for high pressure degradation. Under this operating condition, the yield of oil was 73.8% and the selectivities to Ben, Tol, EB, SM, and AMS were 0.4, 30.9, 15.0, 19.6, and 4.2%, respectively. Non-catalytic fixed bed continuous degradation was conducted at reaction temperatures of $510{\sim}610^{\circ}C$ and contact time ranges of 2~24 min, where the yield was increased by increasing of reaction temperature and contact time. A $Cr_2O_3$ catalyst showed the highest activity and SM yield among acid, base, and redox catalysts. The conversion of 74.6% and the yield of Ben, Tol, EB, SM, and AMS were 0.4, 21.6, 9.7, 17.9, and 3.5%, respectively at $560^{\circ}C$ and contact time of 24 min. It is thought that styrene is converted to EB and other secondary products throughout the formation of diradicals of styrene.

• Applied Chemistry for Engineering
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• v.20 no.2
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• pp.159-164
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• 2009

Monomers of oxetane high explosives were theoretically examined in terms of reactivity, reaction mechanism and process of polymerization substituted by azido $(-CH_2N_3)$, nitrato $(-CH_2ONO_2)$ and hydrazino $(-CH_2N_2H_3)$ which belong to the 5th class hazardous materials and have explosiveness under acid catalyst using MINDO/3, MNDO, and AMI methods for formal charge, heat of formation, and energy level. Nucleophilicity and base of oxetane high explosives could be explained by negative charge size of oxetane oxygen atom and reactivity of oxetane in the growth stage of polymerization under acid catalyzer could be expected to be governed by positive charge size of axial carbon atom and low LUMO energy of electrophile. It could be estimated that carbenium ion was more beneficial in the conversion process of oxetane high explosives than that of stabilization energy (13.90~31.02 kcal/mole) of oxonium ion. In addition, concentration of oxonium ion and carbenium ion in equilibrium state influenced mechanism and it was also estimated that $S_N1$ mechanism reacts faster than that of $S_N2$ in prepolymer growth stage considering quick equilibrium based on form and calculation of polymerization under acid catalyzer.