• Journal of the Korean Chemical Society
• /
• v.37 no.8
• /
• pp.695-701
• /
• 1993

Rate constants of solvolysis of 2-thiophenesulfonyl chloride were determined in aqueous binary mixtures with methanol, ethanol, acetone in water and in methanol. These data are interpreted using the equation of Grunwald-Winstein and Kivinen relationship. Also, kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures were determined. Kinetic solvent isotope effect for hydrolysis of 2-thiopenesulfonyl chloride was 2.24 and 1.47 for methanol and water, respectively. Selectivity values for formation of ester relative to acid in ethanol-water mixtures show maximum S value. From kinetic solvent isotope effect in methanol and water, selectivity data in aqueous alcoholic solvents and solvent effects, it is proposed that the reaction channel favoured in low polarity solvents is general-base catalysis and/or is possibly addition elimination (S$_A$N) reaction pathway and in high polarity solvents iS S$_N$2 reaction mechanism.

• Advances in Energy Research
• /
• v.8 no.4
• /
• pp.223-231
• /
• 2022

An ex-situ gravitational fixed bed pyrolysis reactor was used over Al₂O₃ supported Ni₂P based catalyst with various Ni/P molar ratios (0.5-2.0) and constant nickel loading of 5.37 mmol/g Al₂O₃ to determine the hydrodeoxygenation of rubberwood sawdust (RWS) at atmospheric pressure. The 3D catalysts formed were characterized structurally as well as acidic properties were determined by hydrogen-temperature programmed reduction (TPR). The Ni₂P phase formed completely on Al₂O₃ for 1.5 Ni/P ratio, although lesser crystallite sizes of Ni₂P were seen at Ni/P ratios less than 1.5. Additionally, it was shown that when nickel loading level increased, acidity increased and specific surface area dropped, probably because nickel phosphate is not easily converted to Ni₂P. When Ni/P ratio was 1.5, Ni₂P phase fully formed on Al₂O₃. The catalytic activity was explained in terms of impacts of reaction temperature and Ni/P molar ratio. At relatively high temperature of 450℃, the high-value deoxygenated produce was predominantly composed of n-alkanes. Based on the findings, it was suggested that hydrogenolysis, hydrodeoxygenation, dehydration, decarbonylation, and hydrogenation are all part of mechanism underlying hydrotreatment of RWS. In conclusion, the synthesized Ni₂P/ Al₂O₃ catalyst was capable of deoxygenating RWS with ease at atmospheric pressure, primarily resulting in long chained (C₉-C₂₄) hydrocarbons and acetic acid.

• Journal of the Korean Institute of Gas
• /
• v.16 no.4
• /
• pp.52-58
• /
• 2012

Recently, waste gas incineration is increasing due to strong environmental regulatory system in Korea. These incinerating facilities are usually connected with the top of the storage tank through pipeline and incinerate off gas with the flame. Therefore, the flame originated from these facilities is likely to move back into pipeline and might cause an explosion of the storage tank. Accordingly, the purpose of this study is to suggest the preventive measures and the way to improve the safety of these incineration systems through the cause analysis of a major industrial accident occurred in a acrylic acid manufacturing process in Korea. As a result of the study, the preventive measures are suggested as follows. (1) Air or inert gas inflow facilities should be well designed to dilute flammable gases into air or inert gas sufficiently before the blower is restarted in order to prevent the explosion (2) It is needed for the detonation-type flame arresters to be installed on the top of the storage tanks. (3) In case of using the deflagration-type flame arresters, it is necessary to install a rupture disk before the arresters, or blow off the flame outside tanks by connecting the tank top and the incinerator with hood-type pipe. (4) TDR should be installed to be restarted automatically after the momentary power failure.

• Applied Chemistry for Engineering
• /
• v.5 no.2
• /
• pp.327-336
• /
• 1994

The synergistic effects in mechanical mixture catalysts of Mo-V-O and metal oxide were investigated for the selective oxidation of acrolein. The metal oxides used are $SnO_2$, ${\alpha}-Sb_2O_4$, $WO_3$, ${\alpha}-Al_2O_3$, CuO, $MnO_2$, $Cu_2O$, MgO, CoO, and ZnO. Mechanical mixtures of Mo-V-O plus $SnO_2$ or ${\alpha}-Sb_2O_4$ had resulted in higher conversion of acrolein and higher yield of acrylic acid than Mo-V-O. The origin of the synergy is attributed to the cooperation of Mo-V-O and $SnO_2$ or ${\alpha}-Sb_2O_4$, in which $SnO_2$ or ${\alpha}-Sb_2O_4$ forms dissociated oxygens at their oxygen vacancies and transports them to Mo-V-O. $Cu_2O$, MgO, CuO, and $MnO_2$, increased conversion of acrolein but decreased yield of acrylic acid. CoO and ZnO inhibited the catalytic performance of Mo-V-O. The different role of these metal oxides is explained in terms of their oxidation-reduction properties.

• Journal of the Korean Electrochemical Society
• /
• v.2 no.1
• /
• pp.31-37
• /
• 1999

Copper-containig enzyme, laccase (Rhus vernicifera) was immobilized onto gold electrode using self-assembly technique and its surface properties and catalytic activities were examined. Laccase is an oxidoreductase capable to oxidize diphenols or diamines by 4-electron reduction of molecular oxygen without superoxide or peroxide intermediates. The electrode surface were modified by $\beta-mercaptopropionate$ to have a net negative charge in neutral solution and positively charged laccase (pI=9) was immobilized by electrostatic interaction. The successful immobilization was confirmed by cyclic voltammograms which showed typical surface-confined shapes and behaviors. The amount of charge to reduce the surface was similar to the charge calculated assuming the surface being covered by monolayer. The activity of the immobilized enzyme was tested by the capbility of oxidizing a substrate, ABTS (2,2-azine-bis-(3-ethylbenzthioline-6-sulfonic acid) and it was maintained for $2\~3$ days at $4^{\circ}C$. The immobilzed laccase showed about $10\~15\%$ activity compared to that in solution. The laccase-modified electrode showed the activity of elefoocatalytic reduction of oxygen in the presence of mediator, $Fe(CN)_6^{3-}$ The addtion of azide which is an inhibitor of laccase compeletly eliminated the catalytic current.

• Applied Chemistry for Engineering
• /
• v.8 no.5
• /
• pp.777-783
• /
• 1997

$TiO_2$ powders were synthesized via hydrolysis reaction of titanium n-propoxide in n-propanol solvent and the reaction rates were studied by use of UV-vis spectroscopic method. Concentration of water, reaction temperature, reaction time and acid-base effects of the solution were investigated to determine the optimum conditions for $TiO_2$ powder synthesis. The reaction were controlled to proceed to pseudo-first orders reaction in the presence of excess water in n-propanol solvent. The rate constants which varied with temperature and concentration of water were calculated by Guggenheim method. Reaction using $D_2O$ was also carried out to determine the catalytic character of water. $TiO_2$ powders were synthesized only in the neutral and basic solution and those were almost spheric forms having average particle size of $0.4-0.7{\mu}m$ diameter. Particle size decreased with increasing concentration of water and reaction temperature, however, increased with increasing reaction time. Associative $S_N2$ mechanism for the hydrolysis was proposed from the data of n-value in the transition state and thermodynamic parameter. $D_2O$ solvent isotope effect showed that $H_2O$ molecules reacted as nucleophilic catalysis.

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

• Journal of Life Science
• /
• v.17 no.1 s.81
• /
• pp.6-11
• /
• 2007

[ $\beta$ ]-Fructofuranosidases, a family 32 of glycoside hydrolases (GH32), share three conserved domains including the W(L/M)(C/N)DP(Q/N), FRDPK, and ECP(D/G) motifs. The functional role of the conserved acidic residues within three domains of levan fructotransferase, one of the $\beta-fructofuranosidases$, from Microbacterium sp. AL-210 was studied by site-directed mutagenesis. Each mutant was overexpressed in E. coli BL21(DE3) and purified by using Hi-Trap chelating affinity chromatography and fast performance liquid chromatography. Substitution of Asp-63 by Ala, Asp-195 by Asn, and Glu-245 by Ala and Asp decreased the enzyme activity by approximately 100-fold compared to the wild-type enzyme. This result indicates that three acidic residues Asp-63, Asp-195, and Glu-245 play a major role in catalysis. Since the three acidic residues are present in a conserved position in inulinase, levanase, levanfructotransferase, and invertase, they are likely to have a common functional role as nucleophile, transition state stabilizer, and general acid in $\beta-fructofuranosidases$.

• Journal of Korean Society of Environmental Engineers
• /
• v.34 no.6
• /
• pp.397-405
• /
• 2012

In this study, performance evaluation of newly developed technology for the economical and safe removal of volatile organic compounds (VOCs) coming out from electronic devices washing operation and offensive odor induction materials was made. Metal oxidization catalyst has shown 50% of removal efficiency at the temperature of $220^{\circ}C$. Composite metal oxidization catalyst applied in this study has shown that the actual catalysis has started at the temperature of $100^{\circ}C$. Comprehensive analysis on the catalyst property using Mn-Cu metal oxidization catalyst in the pilot-scale unit was made and the removal efficiency was variable with temperature and space velocity. Full-scale unit developed based on the pilot-scale unit operation has shown 95% of removal efficiency at the temperature of $160^{\circ}C$. Optimum elimination effective rates for the space velocity was found to be $6,000hr^{-1}$. The most appropriate processing treatment range for the inflow concentration of VOCs was between 200 ppm to 4,000 ppm. Catalyst control temperature showed high destruction efficiency at $150{\sim}200^{\circ}C$ degrees Celsius in 90~99%. External heat source was not necessary due to the self-heat reaction incase of VOCs inflow concentration is more than 1,000 ppm. Equipment and fuel costs compared to the conventional RTO/RCO method can be reduced by 50% and 75% respectively. And it was checked when there was poisoning for sulfide and acid gas.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.22 no.6
• /
• pp.274-278
• /
• 2012

$TiO_2$ can be used optically and is applied on many areas such as gas sensor, solar cell and photocatalysis. Electrospun nanofibers have received great interest for development and utilization in some novel applications, such as chemical sensors, dye-sensitized solar cell and photo catalysis. In this study, pure $TiO_2$ and Ga-doped $TiO_2$ nanofibers synthesized by a modified electrospinning method. The Ga doped $TiO_2$ solution is prepared by mixing poly vinyl pyrrolidone, ethyl alcohol, and titanium (IV) isopropoxide. By electrospinning these sols, nanofibers were fabricated. These fibers are heat-treated at $800^{\circ}C$ in air. The prepared pure $TiO_2$ and Ga-doped $TiO_2$ nanofibers samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy.