• Clean Technology
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• v.21 no.1
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• pp.53-61
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• 2015

In this study, we have investigated the kinetics on the char-CO₂ catalytic gasification reaction. Thermogravimetric analysis (TGA) experiments were carried out for char-CO₂ catalytic gasification of an Indonesian Kideco sub-bituminous. Na₂CO₃ and K₂CO₃ were selected as catalysts which were physically mixed with coal. The char-CO₂ catalytic gasification reaction showed a rapid increase of carbon conversion rate at 850 ℃, 60 vol% CO₂, and 7 wt% Na₂CO₃. At the isothermal conditions ranging from 750 ℃ to 900 ℃, the carbon conversion rates increased as the temperature increased. Four kinetic models for gas-solid reaction including the shrinking core model (SCM), random pore model (RPM), volumetric reaction model (VRM), and modified volumetric reaction model (MVRM) were applied to the experimental data against the measured kinetic data. The gasification kinetics were suitably described by the MVRM for the Kideco sub-bituminous. The activation energies for each char mixed with Na₂CO₃ and K₂CO₃ were found 55-71 kJ/mol and 69-87 kJ/mol.

• Bulletin of the Korean Chemical Society
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• v.26 no.1
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• pp.139-145
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• 2005

Artificial neural networks (ANNs), for a first time, were successfully developed for the modeling and prediction of solvent effects on rate constant of [2+2] cycloaddition reaction of diethyl azodicarboxylate with ethyl vinyl ether in various solvents with diverse chemical structures using quantitative structure-activity relationship. The most positive charge of hydrogen atom (q$^+$), dipole moment ($\mu$), the Hildebrand solubility parameter (${\delta}_H^2$) and total charges in molecule (q$_t$) are inputs and output of ANN is log k$_2$ . For evaluation of the predictive power of the generated ANN, the optimized network with 68 various solvents as training set was used to predict log k$_2$ of the reaction in 16 solvents in the prediction set. The results obtained using ANN was compared with the experimental values as well as with those obtained using multi-parameter linear regression (MLR) model and showed superiority of the ANN model over the regression model. Mean square error (MSE) of 0.0806 for the prediction set by MLR model should be compared with the value of 0.0275 for ANN model. These improvements are due to the fact that the reaction rate constant shows non-linear correlations with the descriptors.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.3
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• pp.357-362
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• 2011

Complete mixture preparation of reactants prior to catalytic reforming is an enormously important step for successful operation of a fuel reformer. Incomplete mixing between fuel and reforming agents such as air and steam can cause temperature overshoot and deposit formation which can lead the failure of operation. For that purpose it is required to apply computational models describing coupled kinetics and transport phenomena in the mixing region, which are computationally expensive. Therefore, it is advantageous to analyze the gas-phase reaction kinetics prior to application of the coupled model. This study suggests one of the important design constraints, the required residence time in the mixing chamber to avoid substantial gas-phase reactions which can lead serious deposit formation on the downstream catalyst. The reactivity of various gaseous and liquid fuels were compared, then liquid fuels are far more reactive than gaseous fuels. n-Octane was used as a surrogate among the various hydrocarbons, which is one of the traditional liquid fuel surrogates. The conversion was slighted effected by reactants composition described by O/C and S/C. Finally, threshold residence times in the mixing region of a hydrocarbon reformer were studied and the mixing chamber is required to be designed to make complete mixture of reactants by tens of milliseconds at the temperature lower than $400^{\circ}C$.

• Korean Chemical Engineering Research
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• v.52 no.4
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• pp.544-552
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• 2014

In this study, We have investigated the kinetics on the char-$CO_2$ gasification reaction. Thermogravimetric analysis (TGA) experiments were carried out for char-$CO_2$ catalytic gasification of an Indonesian Roto lignite. $Na_2CO_3$, $K_2CO_3$, $CaCO_3$ and dolomite were selected as catalyst which was physical mixed with coal. The char-$CO_2$ gasification reaction showed rapid an increase of carbon conversion rate at 60 vol% $CO_2$ and 7 wt% $Na_2CO_3$ mixed with coal. At the isothermal conditions range from $750^{\circ}C$ to $900^{\circ}C$, the carbon conversion rates increased as the temperature increased. Three kinetic models for gas-solid reaction including the shrinking core model (SCM), volumetric reaction model (VRM) and modified volumetric reaction model (MVRM) were applied to the experimental data against the measured kinetic data. The gasification kinetics were suitably described by the MVRM model for the Roto lignite. The activation energies for each char mixed with $Na_2CO_3$ and $K_2CO_3$ were found a 67.03~77.09 kJ/mol and 53.14~67.99 kJ/mol.

• Composites Research
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• v.28 no.3
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• pp.99-103
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• 2015

This paper presents the cure kinetics studies on the cure reaction of thermosetting resin. Above all, change in degree of cure and specific heat capacity according to temperature are observed using DSC and MDSC. The results are analyzed by cure kinetics and specific heat capacity model. Glass transition temperature was also measured to apply to the specific heat capacity model. Model parameters were gained from the modeling result. As a result, behavior of specific heat capacity can be calculated mathematically.

• KSBB Journal
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• v.5 no.2
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• pp.133-139
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• 1990

A simple and convenient method was introduced to determine the kinetic parameters for various enzymatic reaction kinetics. The method based on integrated formular can be applied to the parameter estimations from a single experiment. A modified three-parameter model was applied for the parameter estimation in reversible reaction and the equilibrium substrate concentration could be also estimated. It is possible to identify the enzymatic reaction pattern by inspecting the parameter values and the square of the correlation coefficient.

• Membrane Journal
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• v.17 no.2
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• pp.146-160
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• 2007

A parametric study on pervaporation-facilitated esterification was performed by using a practical model based on non-perfect separation through membrane which is not perfectly permselective to water. Thus, membrane selectivity as well as membrane capability to remove water should be taken into account in establishing the simulation model to explain how the membrane separation influence the esterification reaction process. It was shown by simulation that in the reaction systems with non-perfect separation, the permeation of reactants which are acid or/and alcohol retards the reaction by inducing the backward reaction so that reaction conversion curve is located between a reaction system coupled with pervaporation process having a perfect permselectivity to water and a reaction system without pervaporation process. The volume change of reaction system occurs as a result of the permeation through the membrane. The reaction volume change which can be characterized by the reaction ratio of $r_{\Psi}\;to\;r_{{\Psi}=1}$ affects reaction kinetics by concentrating reactants and products, respectively, with different extent with time; reactant-concentrating effect is dominant during the initial stage of reaction, resulting in facilitating the reaction, and then product-concentrating effect is exerted more on reaction, causing to slow down the reaction. When pervaporative dehydration is applied to the reaction system plays an important role in the reaction as well. The effect of timing to impose pervaporation on reaction system affected the reaction kinetics in terms of reaction rate and reaction conversion. A relationship was derived to explain membrane unit capacity and reaction parameters that will be used as a design tool to determine membrane unit capacity at a given reaction conditions or reaction parameters at a membrane unit capacity.

• Composites Research
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• v.33 no.2
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• pp.44-49
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• 2020

The cure kinetics of carbon fiber-reinforced prepreg for Vacuum Bag Only(VBO) process was studied by differential scanning calorimetry (DSC). The total heat of reaction (ΔH_total = 537.1 J/g) was defined by the dynamic scanning test using prepregs and isothermal scanning tests were performed at 130℃~180℃. The test results of isothermal scanning were observed that the heat of reaction was increased as the temperature elevated. The Kratz model was applied to analyze the cure kinetics of resin based on the test results. To verify the simulation model, the degree of cure from panels using different cure cycles were compared with the measurement. The simulation model showed that the error against the experimental value was less than 3.4%.

• Journal of Environmental Science International
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• v.6 no.4
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• pp.399-407
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• 1997

The pyrolysis reactions of atomic hydrogen with chloroform were studied In a 4 cm 1.6. tubular flow reactor with low flow velocity 1518 cm/sec and a 2.6 cm 1.4. tubular flow reactor with high flow velocity (1227 cm/sec). The hydrogen atom concentration was measured by chemiluminescence titration with nitrogen dioxide, and the chloroform concentrations were determined using a gas chromatography. The chloroform conversion efficiency depended on both the chloroform flow rate and linear flow velocity, but 416 not depend on the flow rate of hydrogen atom. A computer model was employed to estimate a rate constant for the initial reaction of atomic hydrogen with chloroform. The model consisted of a scheme for chloroform-hydrogen atom reaction, Runge-Kutta 4th-order method for Integration of first-order differential equations describing the time dependence of the concentrations of various chemical species, and Rosenbrock method for optimization to match model and experimental results. The scheme for chloroform-hydrogen atom reaction Included 22 elementary reactions. The rate constant estimated using the data obtained from the 2.6 cm 1.4. reactor was to be 8.1 $\times$ $10^{-14}$ $cm^3$/molecule-sec and 3.8 $\times$ $10^{-15}$ cms/molecule-sec, and the deviations of computer model from experimental results were 9% and 12% , for the each reaction time of 0.028 sec and 0.072 sec, respectively.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.7
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• pp.746-752
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• 2005

In this study, the effect of reaction parameters including reaction temperature, time, and pressure on sludge degradation and conversion to intermediates such as organic acids were investigated at low critical wet air oxidation(LC-WAO) conditions. Degradation pathways and a modified kinetic model in LC-WAO were proposed and the kinetics model predictions were compared with experimental data under various conditions. Results in the batch experiments showed that reaction temperature directly affected the thermal hydrolysis reaction rather than oxidation reaction. The efficiencies of sludge degradation and organic acid formation increased with the increase of the reaction temperature and time. The removal of SS at $180^{\circ}C$, $200^{\circ}C$, $220^{\circ}C$ and $240^{\circ}C$ of reaction temperatures and 10 min of reaction time were 52.6%, 68.3%, 72.6%, and 74.4%, respectively, indicating that most organic suspended solids were liquified at early stage of reaction. At $180^{\circ}C$, $200^{\circ}C$, $220^{\circ}C$ and $240^{\circ}C$ of reaction temperatures and 40 min of reaction time, the amounts of organic acids formed from 1 g of sludge were 93.5 mg/g SS, 116.4 mg/g SS, 113.6 mg/g SS, and 123.8 mg/g SS, respectively, and the amounts of acetic acid from 1 g of sludge were 24.5 mg/g SS, 65.5 mg/g SS, 88.1 mg/g SS, and 121.5 mg/g SS, respectively. This suggested that the formation of sludge to organic acids as well as the conversion of organic acids to acetic acid increased with reaction temperature. Based on the experimental results, a modified kinetic model was suggested for the liquefaction reaction of sludge and the formation of organic acids. The kinetic model predicted an increase in kinetic parameters $k_1$ (liquefaction of organic compounds), $k_2$ (formation of organic acids to intermediate), $k_3$ (final degradation of intermediate), and $k_4$ (final degradation of organic acids) with reaction temperature. This indicated that the liquefaction of organic solid materials and the formation of organic acids increase according to reaction temperature. The calculated activation energy for reaction kinetic constants were 20.7 kJ/mol, 12.3 kJ/mol, 28.4 kJ/mol, and 54.4 kJ/mol, respectively, leading to a conclusion that not thermal hydrolysis but oxidation reaction is the rate-limiting step.