• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.16 no.4
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• pp.411-420
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• 2018

This study presents a revised crackling core model for the description of $UO_2$ sphere oxidation in air atmosphere. For close reproduction of the sigmoid behavior exhibited in $UO_2$ to $U_3O_8$ conversion, the fragmentation effect contributing to the increased reactive surface area and the concept of variable grain conversion time were considered in the model development. Under the assumptions of two-step successive reaction of $UO_2{\rightarrow}U_3O_7{\rightarrow}U_3O_8$ and final grain conversion time equivalent to ten times the initial grain conversion time, the revised model showed good agreement with the experimental data measured at 599 - 674 K and a lowest deviation when compared with Nucleation and Growth model and AutoCatalytic Reaction model. The evaluated activation energy at 100% conversion to $U_3O_8$, $57.6kJ{\cdot}mol^{-1}$, was found to be closer to the experimentally extrapolated value than to the value determined in AutoCatalytic Reaction model, $48.6kJ{\cdot}mol^{-1}$.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.5
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• pp.819-825
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• 2000

The physico-chemical characteristics and the combustion activities of a waste automotive catalyst were carried out in this study. The physico-chemical characteristics of waste automotive catalyst was examined by EA(Elemental analysis), ICP-AES (Inductively coupled plasma-atomic emission spectrophotometer), and XRD(X-ray diffraction) analysis. Carbon deposit amount was higher in front brick than rear brick of catalyst, and increased with mileage. The content of Pt. Pd and Rh in waste automotive catalyst was different from the car manufacturing company. The combustion activities of waste automotive catalyst were investigated for acetaldehyde as a model VOC in a fixed bed reactor at atmospheric pressure. The catalytic activity of rear brick for acetaldehyde combustion was better than front brick of waste automotive catalyst. The catalytic activity of waste automotive catalyst for acetaldehyde combustion decreased with mileage. The linear relationship between catalytic activity and mileage was negative and has a very excellent correlation. Finally, the waste automotive catalyst has a good catalytic activity for acetaldehyde combustion. and can be used to control of small emission source.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.837-845
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• 2002

Based on ab initio calculations at the MP2(FULL)/6-31+G**//RHF/6-31G** level, we compare the energetic and mechanistic features of a model reaction for catalytic action of Δ?-3-ketosteroid isomerase (KSL,E.C.5.3,3.1) with those of a corresponding nonenzymatic reaction in aqueous solution. The results show that the two catalytic acid residues,Tyr14 and Asp99, can lower the free energy of activation by 8.6kcal/mol, which is in good agreement with the experimentally predicted~9 kcal/mol,contribution of electrophilic catalyses to the whole enzymatic rate enhancement. The dienolate intermediate formed by proton transfer from the substrate carbon acid to the catalytic base residue (Asp38) ins predicted to be stabilized by 12.0 kcal/mol in the enzymatic reaction, making its formation thermodynamically favorable. It has been argued that enzymes catalyzing the reactions of carbon acids should resolve the thermodynamic problem of stabilizing the enolate intermediate as well as the kinetic porblem of lowering the free energy of activation for porton abstraction. We find that KSI can successfully overcome the thermodynamic difficulty ingerent in the nonenzymatic reaction through the electrophilic catalyses of the two acid residues. Owing to the stabilization of dienolate intermediate, the reketonization step could influence the overall reaction rate more significantly in the KSI- catalyzed reaction than in the nonenzymatic reaction, further supporting the previous experimental findings. However, the electrophilic catalyses alone cannot account for the whole catalygic capability (12-13 kcal/mol), confiming the earlier experimental implications for the invement of additional catalytic components. The present computational study indicates clearly how catalytic residues of KSI resolve the fundamental problems associated with the entropic penalty for forming the rate-limiting transition state and its destabilization in the bulk solvation environment.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.38 no.3
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• pp.197-202
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• 2014

The efficiency of a catalytic converter depends on the flow distribution across a system's chemically active substrate. If irregularities or non-uniform flow patterns exist, the system's conversion efficiency decreases, whereas the manufacturing cost increases. Therefore, it is important to analyze the internal flow of a catalytic converter. In this study, flow pattern measurements along the minor axis were recorded at the mid and exit planes of a ceramic honeycomb catalytic converter at flow rates of 37.8 l/s and 94.4 l/s. Flow distributions of the measurement plans were compared with an automotive company's computed velocity profiles. Measurements along the minor axis showed uneven velocity profiles. The ${\upsilon}$-velocity components between the honeycomb bricks were small but somewhat erratic opposite the intake side of the converter, however, they became flatter in measurements recorded near the intake entrance. For almost all velocity values, the computer model suggested velocities greater than the measured values.

• Applied Chemistry for Engineering
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• v.10 no.1
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• pp.85-92
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• 1999

The complete catalytic oxidation of vinyl chloride was investigated over chromium oxide supported ${\gamma}$-alumina using a fixed bed micro-reactor at temperature between 240 and $300^{\circ}C$ and concentration between 600 and 3500 ppm. The oxidation of vinyl chloride was nonlinear in the concentration of vinyl chloride and zeroth order in the concentration of oxygen. The addition of HCl and $H_2O$ as products to the feed stream didn't influence the conversion of vinyl chloride. Several kinetic rate model were tested to describe the data over the range of condition investigated, and developed a model which provide the best correlation of experimental data. The resulting model of kinetic rate was derived by assuming that the reacting occurred via adsorption and subsequent decomposition of the vinyl chloride onto the oxygen covered chromium oxide surface, with the reaction being inhibited by the adsorption of vinyl chloride. The percent standard deviation between the predicted and experimental was about 5.2%, and the activation energy was 18.9 kcal/mol.

• Korean Chemical Engineering Research
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• v.46 no.5
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• pp.922-930
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• 2008

The selective non-catalytic reduction(SNCR) performance is sensitive to the process parameters such as flow velocity, reaction temperature and mixing of reagent(ammonia or urea) with the flue gases. Therefore, the knowledge of the velocity field, temperature field and species concentration distribution is crucial for the design and operation of an effective SNCR injection system. In this work, a full-scale two-dimensional computational fluid dynamics(CFD)-based reacting model involving a droplet model is built and validated with the data obtained from a pilot-scale urea-based SNCR reactor installed with a 150 kW LPG burner. The kinetic mechanism with seven reactions for nitrogen oxides($NO_x$) reduction by urea-water solution is used to predict $NO_x$ reduction and ammonia slip. Using the turbulent reacting flow CFD model involving the discrete droplet phase, the CFD simulation results show maximum 20% difference from the experimental data for NO reduction. For $NH_3$ slip, the simulation results have a similar tendency with the experimental data with regard to the temperature and the normalized stoichiometric ratio(NSR).

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.156.1-156.1
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• 2011

It is of great importance to predict operating parameter characteristics of an integrated fuel processor by the increased life-time and system performance. In this study, computational analysis is performed to gain fundamental insights on transport phenomena and chemical reactions in reformer which consists of preheating, steam reforming, and water gas shift reaction beds. Also, a top-fired burner locates inside of the reforming system. The combustor is providing thermal energy necessary for the steam reforming bed which is a endothermic catalytic reactor. Two-dimensional numerical model of the integrated fuel processing system is introduced for the analysis of heat and mass transport phenomena as well as surface kinetics and catalytic process. A kinetic model was developed and then computational results were compared with the experimental data available in the literature. Subsequently, parameter study using the validated steam methane reforming model was conducted by considering operating parameters, i.e. steam to carbon ratio and temperature.

• Environmental Engineering Research
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• v.25 no.2
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• pp.186-196
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• 2020

Pillared clays with Zr and Fe/Cu/Zr polycations have been prepared from natural clays found in large deposits of Kazakhstan and assessed as catalysts for the catalytic wet peroxide oxidation (CWPO), using 4-nitrophenol (4-NP) as model compound. The performance of the catalysts was followed by measuring the concentration of 4-NP, H₂O₂ and the total organic carbon (TOC), considering C_4-NP = 5 g L^-1, $C_{H_2O_2}$ = 17.8 g L^-1, C_cat = 2.5 g L^-1, initial pH = 3.0 and T = 50℃. At those selected conditions, the pillared clays showed higher activity than natural clays in the CWPO of 4-NP. The conversion of the model pollutant was complete when Fe/Cu/Zr-PILCs were used, with the TOC removal reaching 78.4% after 24 h with the best Fe/Cu/Zr-PILC. The H₂O₂, 4-NP and TOC time-evolution was well described by a kinetic model based on TOC lumps in three blocks, considering the initial TOC (corresponding to 4-NP), the production of oxidizable intermediates and the formation of refractory products.

• Journal of Advanced Marine Engineering and Technology
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• v.28 no.5
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• pp.818-826
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• 2004

The spray-induced mixing characteristics and thermal decomposition of aqueous urea solution into ammonia have been studied to design optimum sizes and geometries of the mixing chamber in SCR(Selective Catalytic Reduction) system. The cold flow tests about the urea-injection nozzle were performed to clarify the parameters of spray mixing characteristics such as mean diameter and velocity of drops and spray width determined from the interactions between incoming air and injected drops. Discrete particle model in Fluent code was adopted to simulate spray-induced mixing process and the experimental results on the spray characteristics were used as input data of numerical calculations. The simulation results on the spray-induced mixing were verified by comparing the spray width extracted from the digital images with the simulated Particle tracks of injected drops. The single kinetic model was adopted to predict thermal decomposition of urea solution into ammonia and solved simultaneously along with the verified spray model. The hot air generator was designed to match the flow rate and temperature of the exhaust gas of the real engines The measured ammonia productions in the hot air generator were compared with the numerical predictions and the comparison results showed good agreements. Finally, we concluded that the design capabilities for sizing optimum mixing chamber were established.

• Computers and Concrete
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• v.25 no.1
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• pp.29-36
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• 2020

This work presents a numerical modeling procedure to simulate the refractory concrete lining in fluid catalytic cracking units of oil refineries. The model includes the simulation of the anchors that reinforce the contact between the refractory concrete and the steel casing. For this purpose, the constitutive relations of an interface finite element are set to values that represent the homogenized behavior of the anchored interface. The parameters of this constitutive relation can be obtained by experimental tests. The model includes also multi-surface plasticity, in order to represent the behavior of the refractory concrete lining. Since the complexity of real case applications leads to high computational costs, the models presented here were implemented in a high-performance parallelized finite element platform. A case study representing a riser similar to the ones used by the refinery industry demonstrates the potential of the model.