• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.519-523
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• 2013

When atomic layer deposition (ALD) is performed on a porous material by using an organometallic precursor, minimum exposure time of the precursor for complete coverage becomes much longer since the ALD is limited by Knudsen diffusion in the pores. In the previous report by Min et al. (Ref. 23), shrinking core model (SCM) was proposed to predict the minimum exposure time of diethylzinc for ZnO ALD on a porous cylindrical alumina monolith. According to the SCM, the minimum exposure time of the precursor is influenced by volumetric density of adsorption sites, effective diffusion coefficient, precursor concentration in gas phase and size of the porous monolith. Here we modify the SCM in order to consider undesirable adsorption of byproduct molecules. $TiO_2$ ALD was performed on the cylindrical alumina monolith by using titanium tetrachloride ($TiCl_4$) and water. We observed that the byproduct (i.e., HCl) of $TiO_2$ ALD can chemically adsorb on adsorption sites, unlike the behavior of the byproduct (i.e., ethane) of ZnO ALD. Consequently, the minimum exposure time of $TiCl_4$ (~16 min) was significantly much shorter than that (~71 min) of DEZ. The predicted minimum exposure time by the modified SCM well agrees with the observed time. In addition, the modified SCM gives an effective diffusion coefficient of $TiCl_4$ of ${\sim}1.78{\times}10^{-2}\;cm^2/s$ in the porous alumina monolith.

• Journal of the Korean Society of Combustion
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• v.15 no.1
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• pp.22-29
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• 2010

In this study, carbon conversion was measured using an electronic mass balance. In a lab scale furnace, each coal sample was pyrolyzed in a nitrogen environment and became coal char, which was then gasified with steam under isothermal conditions. The reactivity of coal char was investigated at various temperatures and steam concentrations. The VRM(volume reaction model), SCM(shrinking core model), and RPM(random pore model) were used to interpret experimental data. For each model the activation energy(Ea), pre-exponential factor (A), and reaction order(n) of the coal char-steam reaction were determined by applying the Arrhenius equation into the data obtained with thermo-gravimetric analysis(TGA). According to this study, it was found that experimental data agreed better with the VRM and SCM for 1,000 and $1,100^{\circ}C$, and the RPM for 1,200 and $1,300^{\circ}C$. The reactivity of chars increased with the increase of gasification temperature. The structure parameter(${\psi}$) of the surface area for the RPM was obtained.

• Journal of the Korean Society of Combustion
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• v.15 no.2
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• pp.41-49
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• 2010

Various coals from many countries around the world have been used for pulverized coal boiler in power plants in Korea. In this study, the gasification reactivities of various coal chars with $CO_2$ were investigated. Carbon conversion was measured using a real time gas analyzer with NDIR CO/$CO_2$ sensor. In a lab scale furnace, each coal sample was devolatilized at $950^{\circ}C$ in nitrogen atmosphere and became coal char and then further heated up to reach to a desired temperature. Each char was then gasified with $CO_2$ under isothermal conditions. The reactivities of coal chars were investigated at different temperatures. The shrinking core model (SCM) and volume reaction model(VRM) were used to interpret the experiment data. It was found that the SCM and VRM could describe well the experimental results within the carbon conversion of 0-0.98. The gasification rates for various coals were very different. The gasification rate for any coal increased as the volatile matter content increased.

• Clean Technology
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• v.19 no.3
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• pp.306-312
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• 2013

We investigated the effects of the concentration of carbon dioxide on the char-$CO_2$ gasification reaction under isothermal conditions of $850^{\circ}C$ using the Drayton coal. Potassium carbonate was used to improve the low-temperature gasification reactivity. The enhancement of carbon dioxide concentration increased the gasification rate of char, while gasification rate reached a saturated value at the concentration of 70%. The best $CO_2$ concentration for gasification is determined to be 70%. We compared the shrinking core model (SCM), volumetric reaction model (VRM) and modified volumetric reaction model (MVRM) of the gas-solid reaction models. The correlation coefficient values, by linear regression, of SCM are higher than that of VRM at low concentration. While the correlation coefficients values of VRM are higher than that of SCM at high concentration. The correlation coefficient values of MVRM are the highest than other models at all concentration.

• Nuclear Engineering and Technology
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• v.29 no.3
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• pp.260-268
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• 1997

The effects of three mechanisms, calcium depletion, sulphate and carbonate penetration, on the concrete degradation have been studied. The shrinking core model (SCM) and the HYDROGEOC. HEM (HGC) model have been applied to evaluate how fast the mechanisms proceed. The SCM is an analytical approximation model and the HGC is a numerical mass transport model coupled with chemical reaction. The SCM leads to more conservative results than the HGC, and turns out to be very useful in the viewpoint of simplicity and conservatism. During 300 years, calcium has been depleted within 10 cm from the concrete outer surface, and sulphate has penetrated less than 13.5 cm into the concrete. Carbonate has not penetrated own 7 cm into the concrete in contact with the bentonite, and, furthermore, its penetration into the concrete with the groundwater is negligible. Conclusively, the concrete is expected to maintain its integrity for at least 300 years that are regarded as institutional control period of intermediate and low-level radioactive waste repository.

• Korean Chemical Engineering Research
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• v.53 no.6
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• pp.746-754
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• 2015

In this study, we investigated the effects of the temperature on the coal/biomass $char-CO_2$ gasification reaction under isothermal conditions of $700{\sim}900^{\circ}C$ using the lignite(Indonesia Eco coal) with biomass (korea cypress). Ni catalysts were impregnated on the coal by the ion-exchange method. Four kinetic models which are shrinking core model (SCM), volumetric reaction model (VRM), random pore model (RPM) and modified volumetric reaction model (MVRM) for gas-solid reaction were applied to the experimental data against the measured kinetic data. The Activation energy of Ni-coal/biomass, non-catalyst coal/biomass $Char-CO_2$ gasification was calculated from the Arrhenius equation.

• Korean Chemical Engineering Research
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• v.55 no.1
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• pp.99-106
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• 2017

In this study, mixed catalytic char gasification of Indonesia low-rank coal Kideco was investigated under nitrogen atmosphere and isothermal conditions at a fixed reactor. The effects of the temperature were investigated at various temperature (700, 750, 800, $850^{\circ}C$). The effects of blend ratio of catalysts ($K_2CO_3$, Ni) were investigated with different blend ratios (1:9, 3:7, 5:5, 7:3 and 9:1). The sample was prepared by mixing with $K_2CO_3$ physically and by ionexchange method with Ni. The data from thermogravimetric analyzer and gas chromatography were applied to four gassolid reaction kinetic models including shrinking core model, volumetric reaction model, random pore model and modified volumetric reaction model.

• 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.

• Applied Chemistry for Engineering
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• v.27 no.1
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• pp.56-61
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• 2016

In this study, the effect of natural minerals on the reaction kinetics for lignite-$CO_2$ gasification was investigated. After physical mixing of lignite from Meng Tai area with 5 wt% of each natural mineral catalysts among Dolomite, Silica sand, Olivine and Kaolin, $CO_2$ gasification was performed using TGA at each 800, $850^{\circ}C$ and $900^{\circ}C$. The experimental data was analyzed with volumetric reaction model (VRM), shrinking core model (SCM) and modified volumetric reaction model (MVRM). MVRM was the most suitable among three models. As increasing the reaction temperature, the reaction rate constant became higher. With natural mineral catalysts, the reaction rate constant was higher and activation energy was lower than that of without catalysts. The lowest activation energy, 114.90 kJ/mol was obtained with silica sand. The highest reaction rate constant at $850^{\circ}C$ and $900^{\circ}C$ and lower reaction rate constant at $800^{\circ}C$ were obtained with Kaolin. Conclusively, the better catalytic performance could be observed with Kaolin than that of using other catalysts when the reaction temperature increased.

• 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.