• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.135-142
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• 1989

Methyl tert-butyl ether(MTBE) was synthesized from vapor phase reaction of methanol with iso-butylene over HZSM-5 catalysts, and effects of SiO$_2/Al_2O_3$ ratio in the HZSM-5 catalysts and reaction conditions on products distribution have been examined. Acid strength and acid type of each catalyst with different SiO$_2/Al_2O_3$ ratio were measured using pyridine adsorption followed by temperature programmed desorption(TPD) and IR analysis. Reactants and products adsorption characteristics on different acid sites have also been examined. As the SiO$_2/Al_2O_3$ ratio of HZSM-5 catalyst was increased, selectivity to MTBE was improved as a result of decrease in dimethylether(DME) formation at the strong acid sites. Conversion and selectivity to MTBE were also greatly enhanced as $i-C_4H_8/CH_3OH$ reactant ratio was increased, and overall about 80$^{\circ}$C was adequate for the MTBE synthesis. The properties of deposited coke on spent catalysts were examined by TG, DTA and IR spectrum analysis, indicating the amount of the coke deposit in the order of HY > H-Mordenite > HZSM-5. Even if the coke deposited on H-Mordenite was little more in amount than to that on HZSM-5, the former deactivated quickly due to its non-interconnected channel structure. For HY, owing to its lange pore size, significant $i-C_4H_8$ polymerization was occured, and rapid deactivation and severe coke formation has resulted within few hours.

• Clean Technology
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• v.22 no.1
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• pp.53-61
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• 2016

Steam reforming of tar produced from biomass gasification was conducted using several Ni-based catalysts. In labscale, the catalytic steam reforming of toluene which is a major component of biomass tar was studied. A fixed bed reactor was used at various temperatures of 400-800 ℃. Ru (0.6 wt%) and Mn or K (1 wt%) were applied as a promoter in Ni based catalysts. Generally, Ni/Ru-K/Al₂O₃ catalyst shows higher performance on steam reforming of toluene than Ni/Ru-Mn/Al₂O₃ catalyst. Used catalysts were analyzed by XRD and TGA to detect sintering and carbon deposition. Base on the lab-scale studies, the monolith and pellet type catalysts were tested in 1 ton/day scale biomass gasification system. Ni/Ru-K/Al₂O₃ monolith catalyst shows high tar reforming performance at high temperature. In addition, Ni/Ru-Mn/Al₂O₃ monolith catalyst was showed deactivation with operation time. Reforming performance of Ni/Ru-K/Al₂O₃ pellet catalyst which showed 66.7% tar conversion at 587 ℃ was compared to regenerated one. Overall, Ni/Ru-K/Al₂O₃ pellet catalyst shows higher stability and performance than other used catalysts.

• Journal of Hydrogen and New Energy
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• v.24 no.5
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• pp.359-366
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• 2013

This work is investigated for the catalytic decomposition of hydrogen iodide (HI). Platinum was used as active material by loading on $ZrO_2-SiO_2$ mixed oxide in HI decomposition reaction. To obtain high and stable conversion of hydrogen iodide in severe condition, it was required to improve catalytic activity. For this reason, a method increasing dispersion of platinum was proposed in this study. In order to get high dispersion of platinum, zirconia was incorporated in silica by sol-gel synthesis. Incorporating zirconia influence increasing platinum dispersion and BET surface area as well as decreasing deactivation of catalysts. It should be able to stably product hydrogen for a long time because of inhibitive deactivation. HI decomposition reaction was carried out under the condition of $450^{\circ}C$ and 1 atm in a fixed bed reactor. Catalysts analysis methods such as $N_2$ adsorption/desorption analysis, X-ray diffraction, X-ray fluorescence, ICP-AES and CO gas chemisorption were used to measurement of their physico-chemical properties.

• Clean Technology
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• v.25 no.1
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• pp.91-97
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• 2019

Oxidative desulfurization (ODS) has received much attention in recent years because refractory sulfur compounds such as dibenzothiophenes can be oxidized selectively to their corresponding sulfoxides and sulfones, and these products can be removed by extraction and adsorption. In this work, The oxidative desulfurization of marine diesel fuel was performed in a batch reactor with hydrogen peroxide ($H_2O_2$) in the presence of various supported heteropoly acid catalysts. The catalysts were characterized by XRD, XRF, XPS and nitrogen adsorption isotherm techniques. Based on the sulfur removal efficiency of promising silica supported heteropoly acid catalysts, the ranking of catalytic activity was: $30\;H_3PW_{12}/SiO_2$ > $30\;H_3PMo_{12}/SiO_2$ > $30\;H_4SiW_{12}/SiO_2$, which appears to be related with their intrinsic acid strength. The $30\;H_3PW_{12}/SiO_2$ catalyst showed the highest initial sulfur removal efficiency of about 66% under reaction conditions of $30^{\circ}C$, $0.025g\;mL^{-1}$ (cat./oil), 1 h reaction time. However, through the recycle test of the $H_3PW_{12}/SiO_2$ catalyst, significant deactivation was observed, which was attributed to the elution of the active component $H_3PW_{12}$. By introducing cesium cation ($Cs^+$) into the $H_3PW_{12}/SiO_2$ catalyst, the stability of the catalyst was improved with changing the solubility, and the $Cs^+$ ion exchanged catalyst could be recycled for at least five times without severe elution.

• Korean Chemical Engineering Research
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• v.48 no.1
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• pp.10-15
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• 2010

Intensive works have been carried out to develop more efficient solid catalysts for biodiesel production from various feedstocks including refined oils and waste fats. Among many catalysts, metal oxides and ion exchange resins are the most intensively studied ones. With regard to metal oxide catalysts, major research activities have focused on the identification of the active compounds and their immobilizing methods on the supports. As metal oxide catalysts have strong thermal stability, they may be used in simultaneous transesterification and esterification of waste fats. However, ion exchange resin catalysts were mainly applied in the esterification of the free fatty acids in waste fats because of their lower thermal stability. For both solid catalysts, further works are needed to make them to be used in commercial process. Especially fast deactivation of the solid catalyst would be the most challenging problem.

• Clean Technology
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• v.19 no.3
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• pp.327-332
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• 2013

Space- and time-resolved in-situ optical and fluorescence microspectroscopy techniques have been applied to investigate the coke formation during aromatization of C5 paraffin and olefin over H-ZSM-5 crystal. In-situ UV/vis absorption measurement offers space- and time-resolved information for the coke formation. Different coking trends have been observed with respect to the location of a crystal as well as the reactant types. From in-situ confocal fluorescence microspectroscopy study, it is revealed that the concentration of certain species photo-excited at 488 nm becomes high at the central region, whereas the compounds emitting fluorescence by 561 nm laser move towards the boundary region of the crystal. The different fluorescence patterns obtained varying excitation lasers suggest the existence of distinct fluorescence emitting species having different degree of coke growth.

• Applied Chemistry for Engineering
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• v.23 no.1
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• pp.23-27
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• 2012

To make synthetic liquid fuel from biomass such as wood pellet, energy crop and so on, a biomass to liquid (BTL) process by using a biomass gasifier with Fisher-Tropsch (FT) reaction was developed. However $H_2S$, COS and $CO_2$ in syngas from biomass gasifiers resulted in a decrease of the conversion efficiency and the deactivation of the catalyst. To remove acid gases in syngas, a lab-scale methanol absorption tower was developed and the removal characteristics of acid gases were investigated. The methanol absorption tower efficiently removed $H_2S$ and COS with a removal of $CO_2$, so it could be useful process for the BTL process.

• Bulletin of the Korean Chemical Society
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• v.30 no.5
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• pp.1047-1053
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• 2009

The future use of hydrogen as an energy source is expected to increase on account of its environmentally friendliness. In order to enhance the production of hydrogen, Pd ions (0.01, 0.05, 0.1, and 0.5 mol%) were incorporated $TiO_2$ (Pd-$TiO_2$) and used as a photocatalyst. The UV-visible absorbance decreased with increasing level of palladium incorporation without a wavelength shift. Although all the absorption plots showed excitation characteristics, there was an asymmetric tail observed towards a higher wavelength caused by scattering. However, the intensity of the photoluminescence (PL) curves of Pd-$TiO_2$ was smaller, with the smallest case being observed at 0.1 and 0.5 mol% Pd-$TiO_2$, which was attributedto recombination between the excited electrons and holes. Based on these optical characteristics, the evolution of $H_2$ from methanol/water (1:1) photo-splitting over Pd-$TiO_2$ in the liquid system was enhanced, compared with that over pure $TiO_2$. In particular, 2.4 mL of $H_2$ gas was produced after 8 h when 0.5 g of a 1.0 mol% Pd-$TiO_2$ catalyst was used. $H_2$ was stably evolved even after 28 h without catalytic deactivation, and the amount of $H_2$ produced reached 14.5 mL after 28 h. This is in contrast to the case of the Pd 0.1 mol% impregnated $TiO_2$ of $H_2$ evolution of 17.5 mL due to the more decreasedelectron-hole recombination.

• Journal of Hydrogen and New Energy
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• v.25 no.3
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• pp.219-226
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• 2014

In HI decomposition, $Pt/Al_2O_3$ has been studied by several researchers. However, after HI decomposition, it could be seen that metal dispersion of $Pt/Al_2O_3$ was greatly decreased. This reason was expected of platinum loss and sintering, which platinum was aggregated. Also, this decrease of metal dispersion caused catalytic deactivation. This study was conducted to find the condition to minimize platinum sintering and loss. In particular, heat treatment atmosphere and temperature were examined to improve the activity of HI decomposition reaction. First of all, although $Pt/Al_2O_3$ treated in hydrogen atmosphere had low platinum dispersion between 13 and 18%, it was shown to suitable platinum form that played an important role in improving HI decomposition reaction. Oxygen in the air atmosphere made $Pt/Al_2O_3$ have high platinum dispersion even 61.52% at $500^{\circ}C$. Therefore, in order to get high platinum dispersion and suitable platinum form in HI decomposition reaction, air heat treatment at $500^{\circ}C$ was needed to add before hydrogen heat treatment. In case of 5A3H, it had 51.13% platinum dispersion and improved HI decomposition reaction activity. Also, after HI decomposition reaction it had considerable platinum dispersion of 23.89%.

• Applied Chemistry for Engineering
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• v.10 no.3
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• pp.407-414
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• 1999

We have studied the reduction of NO by CO over perovskite-type oxides prepared by malic and method. The catalysts were modified to enhance the activity by substitution of metal into A or B site of perovskite oxides. In the $LaCoO_3$ type catalyst, the partial substitution of Sr into A site enhanced the catalytic activity on the conversion of NO at less than $350^{\circ}C$. In the $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3$ catalyst, the partial substitution of Fe or Mn into B site enhanced the conversion of NO, but excess amount of Fe decreased the conversion of NO. In addition, $La_{0.6}Sr_{0.4}Co_{0.8}Fe_{0.2}O_3$ mixed with $SnO_2$ or $MnO_2$ showed the synergy effect on the reduction of NO. The introduction of water into reactants feed decreased the catalytic activity but the deactivation was shown to be reversible. The introduction of $SO_2$ into reactants feed also decreased the catalytic activity.