• Journal of the Korean Chemical Society
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• v.55 no.1
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• pp.14-18
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• 2011

Esterification of methacrylic acid with ethylene glycol was carried out over Heteropolyacids [HPA: $H_4SiW_{12}O_{40}$ (STA) and $H_3PW_{12}O_{40}$ (PTA)] supported on ZSM-5. For comparison, the same reaction was carried out over unsupported HPA, $H_2SO_4$, $BF_3$ and PTSA. Among the catalysts studied, HPA showed better activity compared to $H_2SO_4$, $BF_3$ and PTSA. Catalytic activity was compared with HPA supported ZSM-5 catalysts. Typical results indicated that 30 wt% PTA supported on ZSM-5 showed nearly the same activity as that of bulk PTA. It was found that the reaction follows first order kinetics with respect to methacrylic acid. The reaction products were identified by $^1H$-NMR and FT-IR.

• Applied Chemistry for Engineering
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• v.23 no.6
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• pp.604-607
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• 2012

Solid base catalysts for biodiesel production were synthesized by impregnating basic metal species on two support materials with large specific surface area : zeolite and pyrolysis char. KL zeolite and Undaria pinnatifida char were impregnated with KOH aqueous solution and calcium nitrate solution, respectively, to enhance the basic strength. The catalysts synthesized were characterized using Hammett indicators and $CO_2$-TPD analysis. Biodiesel was produced using soybean oil and methanol over the catalysts synthesized. The content of fatty acid methyl esters was measured to evaluate the catalytic activity. Generally, the catalytic activity increased with increasing quantity of basic metal impregnated but impregnation of excessive amount of metal could cause reduction in the activity.

• Korean Journal of Chemical Engineering
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• v.35 no.11
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• pp.2185-2190
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• 2018

Methane activation through oxychlorination is in the spotlight due to the relatively mild reaction conditions at atmospheric pressure and in the temperature range of $450-550^{\circ}C$. Although $CeO_2$ is known to exhibit good activity for methane oxychlorination, significant amounts of by-products such as $CO_2$, CO and carbon deposits are produced during the reaction over $CeO_2$. We investigated the effect of iron in $FeO_x/CeO_2$ catalysts on methane oxychlorination. $FeO_x/CeO_2$ with 3 wt% iron shows the maximum yield at $510^{\circ}C$ with 23% conversion of methane and 65% selectivity of chloromethane. XRD and $H_2$ TPR results indicate that iron-cerium solid solution was formed, resulting in the production of more easily reduced cerium oxide and the suppression of catalysts sintering during the reaction. Furthermore, the selectivity of by-products decreased more significantly over $FeO_x/CeO_2$ than cerium oxide, which can be attributed to the facilitation of HCl oxidation arising from the enhanced reducibility of the former sample.

• Clean Technology
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• v.16 no.1
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• pp.12-18
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• 2010

The object of the present study is to apply KF/MgO catalysts to remove sulfur dioxide from dibenzothiophene sulfone, a by-product of oxidative desulfurization. Potassium fluoride was deposited via an impregnation method on MgO. The effects KF loading and calcination on the characteristics of the KF/MgO catalysts were investigated through the BET surface area, XRF, XRD, and temperature-programmed desorption of $CO_2$. The catalytic performances of the samples were investigated during the decomposition of dibenzothiophene sulfone to biphenyl and sulfur dioxide gas. KF loaded on MgO prepared by the impregnation method showed high catalytic activities for the decomposition of dibenzothiophene sulfone. The higher activity of KF/MgO just dried at 373 K, avoiding the usual activation at high temperature, than that over the calcined catalyst is ascribed to increase of the amount of basic sites. The high basicity probably may be due to the coordinately unsaturated $F^-$. The simply dried 10 % KF/MgO catalyst, without the usual activation at high temperature, showed the optimal catalytic properties.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.963-968
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• 1999

The global environmental problems have been caused by the release of CFCs. Therefore, methods for safe destruction of recoverd CFCs will be eventually needed. The objective of this study was to develop and test a catalyst operating at a mild condition for the decomposition of CFC-113. In this work, catalytic oxidative decomposition of CFC-113 was carried out over aerosol $TiO_2/SiO_2(ATS)$ catalysts prepared by the sol-gel method. All ATS catalysts(Ti/Si mol ratio=1, 2, 2.33, 4) showed high initial activity. However, the deactivation of ATS catalysts was found that more remarkable due to an attack of fluorine and the destruction of ATS structure(Si-F reaction) from analyses of SEM-EDX, XRD than $TiO_2/SiO_2(ATS)$ catalyst prepared by the precipitation method. ATS catalysts prepared by more acidic prehydrolysis condition were found to have still more activity and longer life-time by increasing of acidity. The activity of ATS catalyst also depend on the content of $TiO_2$. There was reason that the acidity of the ATS catalyst was increased with the increased content of $TiO_2$ from 50 to 80 mol %. Solid superacid catalyst ($ATX/SO_4{^{2-}}$) modified with $H_2SO_4$ solution was prepared for high activity and lower deactivation. The reaction of $ATS/SO_4{^{2-}}$ catalyst also exhibited even higher activity and lower deactivation than the original ATS catalyst. It is suggested that the addition of the sulphate species clearly inhibit the deactivation.

• 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.

• Korean Chemical Engineering Research
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• v.48 no.5
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• pp.583-588
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• 2010

Esterification of free fatty acid with methanol to biodiesel was investigated in a batch reactor using various solid acid catalysts, such as polymer cation-exchanged resins with sulfuric acid functional group(Amberlyst-15, Dowex 50Wx8), acidic ionic liquids (ILs)-modified silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-[ASBI][HSO_4]$, $SiO_2-[ASCBI][HSO_4]$) and grafted silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-R-SO_3H$, $SiO_2-R-SO_2Cl$). The effects of reaction time, temperature, reactant concentration(molar ratio of methanol to oleic acid), and catalyst amount were studied. Allylimidazolium-based ILs on modified silica gels were superior to other tested solid acid catalysts. Especially, the performance of $SiO_2-[ASBI][HSO_4]$ (immobilized by grafting of 3-allyl-1-(4-sulfobutyl)imidazolium hydrogen sulfate on silica gel) was better than that of a widely known Amberlyst-15 catalyst at the same reaction conditions. A high conversion yield of 96% was achieved in the esterification reaction of the simulated cooking oil at 353 K for 2 h. The high catalytic activity of $SiO_2-[ASBI][HSO_4]$ was attributed to the presence of strong Brønsted acid sites from the immobilized functional groups. The catalyst was recovered and the biodiesel product was separated by simple processes such as decantation and filtration.

• Korean Chemical Engineering Research
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• v.53 no.5
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• pp.653-662
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• 2015

In general, the coal gasification has to be operated under high temperature ($1300{\sim}1400^{\circ}C$) and pressure (30~40 bar). However, to keep this conditions, it needs unnecessary and excessive energy. In this work, to reduce the temperature of process, alkali catalysts such as $K_2CO_3$ and $Na_2CO_3$ were added into Cyprus coal. We investigated the kinetic of Cyprus char-$CO_2$ gasification. To determine the gasification conditions, the coal (with and without catalysts) gasified with fixed variables (catalyst loading, catalytic effects of $Na_2CO_3$ and $K_2CO_3$, temperatures) by using TGA. When catalysts are added by physical mixing method into Cyprus coal the reaction rate of coal added 7 wt% $Na_2CO_3$ is faster than raw coal for Cyprus char-$CO_2$ gasification. The activation energy of coal added 7 wt% $Na_2CO_3$ was calculated as 63 kJ/mol which was lower than raw char. It indicates that $Na_2CO_3$ can improve the reactivity of char-$CO_2$ gasification.

• Journal of Korean Society of Environmental Engineers
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• v.39 no.4
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• pp.186-193
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• 2017

Microwave (MW) is an effective method for solubilizing organic solids because it has thermal, non-thermal and ionic conduction effects by dielectric heating and high energy efficiency. In this study, we evaluated the application of MW to the solubilization of cattle manure and investigated the solubilization ratio of cattle manure by solid concentration, MW power and target temperature. And $H_2SO_4$ and NaCl were added to investigated the effects on the MW-assisted solubilization. Also, we evaluated the solubilization efficiency by biochemical methane potential(BMP) test according to the solubilization conditions. Maximum SCOD increment per energy supply was 70.5 mg $SCOD_{increased}/kJ$ at 12% of the solid concentration, MW power of 800 W and the target temperature of $40^{\circ}C$. And SCOD concentration went up 153.2% compared to the initial concentration. In the MW-assisted solubilization with $H_2SO_4$ and NaCl as chemical catalysts, SCOD concentration was increased by 36% and 22.7%, respectively, compared to the result of MW. The methane production was increased by 13.3% and 11.3% with the addition of $H_2SO_4$ and NaCl. Therefore, MW is an effective method for solubilization of cattle manure, and it is necessary to use chemical catalysts to increase the solubilzation efficiency.

• Applied Chemistry for Engineering
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• v.25 no.3
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• pp.254-261
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• 2014

The transformer is a static electrical device that transfers energy by inductive coupling. Then, heat is occurred at coils, inner transformer was filled with insulating oils for cooling and insulation. Although mineral oil as insulating oil has been widely used, it does not meet health and current environmental laws because it is not biodegradable. Therefore, in this study, the diglycerol ester was synthesized with diglycerol and fatty acids (oleic acid and caprylic acid) over various catalysts for insulating oil having biodegradability, high flash points and low pour points. The sulfated zirconia ($SO_4{^{2-}}/ZrO_2$) catalyst prepared at different calcination temperature shows the highest conversion of fatty acids at $600^{\circ}C$ due to crystallinity and high density of acid sites per surface area. When the molar ratio of oleic acid and caprylic acid is 1:3, the diglycerol ester shows superior insulation properties that are the flash point of $306^{\circ}C$ and pour point of $-50^{\circ}C$. The insulation properties of synthesized diglycerol ester shows the pour point of $-50^{\circ}C$ and the flash point of over $300^{\circ}C$. Therefore, diglycerol ester is superior to the vegetable oils in insulation properties.