• Korean Chemical Engineering Research
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• v.55 no.5
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• pp.704-710
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• 2017

Although the desalination technique using gas hydrate formation is at a development stage compared to the commercially well-established reverse osmosis (RO), it still draws attention because of its simplicity and moderate operational conditions especially when using refrigerants for guest gases. In this study, DFT (density functional theory)-based molecular modeling was employed to explain the energetics of the gas hydrate formation using HFC (hydrofluorocarbon) and HCFC (hydrochlorofluorocarbon) refrigerants. For guest gases, R-134a, R-227ea, R-236fa, and R-141b were selected and three cavity structures ($5^{12}$, $5^{12}6^2$, and $5^{12}6^4$) composed of water molecules were constructed. The geometries of guest gas, cavity, and cavity encapsulating guest gas were optimized by molecular modeling respectively and their located energies were then used for the calculation of binding energy between the guest gas and cavity. Finally, the comparison of binding energies was used to propose which refrigerant is more favorable for the gas hydrate formation energetically. In conclusion, R-236fa was the best choice in terms of thermodynamic spontaneity, less toxicity, and low solubility in water.

• Korean Chemical Engineering Research
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• v.55 no.5
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• pp.723-730
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• 2017

The batch experiments by response surface methodology (RSM) have been applied to investigate the influences of operating parameters such as temperature, initial concentration, contact time and adsorbent dosage on 2,4-dichlorophenol (2,4-DCP) adsorption with an activated carbon prepared from waste citrus peel (WCAC). Regression equation formulated for the 2,4-DCP adsorption was represented as a function of response variables. Adequacy of the model was tested by the correlation between experimental and predicted values of the response. A fairly high value of $R^2$ (0.9921) indicated that most of the data variation was explained by the regression model. The significance of independent variables and their interactions were tested by the analysis of variance (ANOVA) and t-test statistics. These results showed that the model used to fit response variables was significant and adequate to represent the relationship between the response and the independent variables. The kinetics and isotherm experiment data can be well described with the pseudo-second order model and the Langmuir isotherm model, respectively. The maximum adsorption capacity of 2,4-DCP on WCAC calculated from the Langmuir isotherm model was 345.49 mg/g. The rate controlling mechanism study revealed that film diffusion and intraparticle diffusion were simultaneously occurring during the adsorption process. The thermodynamic parameters indicated that the adsorption reaction of 2,4-DCP on WCAC was an endothermic and spontaneous process.

• Korean Chemical Engineering Research
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• v.52 no.6
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• pp.768-774
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• 2014

SI process is a thermochemical process producing hydrogen by decomposing water while recycling sulfur and iodine. Various technologies have been developed to improve the efficiency on Section III of SI process, where iodine is separated and recycled. EED(electro-electrodialysis) could increase the efficiency of Section III without additional chemical compounds but a substantial amount of $I_2$ from a process stream is loaded on EED. In order to reduce the load, a crystallization technology prior to EED is considered as an $I_2$ removal process. In this work, $I_2$ particle sinking behavior was modeled to secure basic data for designing an $I_2$ crystallizer applied to $I_2$-saturated $HI_x$ solutions. The composition of $HI_x$ solution was determined by thermodynamic UVa model and correlation equations and pure properties were used to evaluate the solution properties. A multiphysics computational tool was utilized to calculate particle sinking velocity changes with respect to $I_2$ particle radius and temperature. The terminal velocity of an $I_2$ particle was estimated around 0.5 m/s under considered radius (1.0 to 2.5 mm) and temperature (10 to $50^{\circ}C$) ranges and it was analyzed that the velocity is more dependent on the solution density than the solution viscosity.

• Korean Journal of Soil Science and Fertilizer
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• v.36 no.4
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• pp.210-217
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• 2003

An alternative method to the empirical approach such as Langmuir and Freundlich model, surface complexation model using thermodynamic database is used to simulate adsorption behavior of cadmium for oxide minerals. Sorption of cadmium onto amorphous silica ($SiO_2$) and synthetic goethite (${\alpha}$-FeOOH) at various conditions of pH, initial cadmium loading, oxide concentration, and ionic strength, were investigated. For both oxide minerals, increasing cadmium concentration resulted in right shifting of the sorption curve of cadmium as the function of pH. The $pH_{50}$, where 50% of cadmium sorbed, of goethite (pH 5.25) was much smaller than that of the silica (pH 7.83). The sorption of cadmium onto both minerals were not affected by the background ion strength from $10^{-1}$ to $10^{-2}$ M of $KNO_3$. It indicated that the binding affinity of goethite surface for cadmium is much stronger than that of silica. The strong affinity of oxide mineral for cadmium can be explained by the existence of coordination or covalent bond between cadmium and surface of it.

• Analytical Science and Technology
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• v.27 no.2
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• pp.79-91
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• 2014

Solubility data of carbon dioxide ($CO_2$) in 1-butyl-3-methylpiperidinium bis(trifluoromethylsulfonyl)imide ($[bmpip][Tf_2N]$) ionic liquid are presented at pressures up to about 30 MPa and at temperatures between 303 K and 343 K. As far as we know, the data on the $CO_2$ solubility in the $[bmpip][Tf_2N]$ ionic liquid have never been reported in the literature by other investigators. The solubilities of $CO_2$ were determined by measuring the bubble point or cloud point pressures of the $CO_2+[bmpip][Tf_2N]$ mixtures with various compositions using a high-pressure equilibrium apparatus equipped with a variable-volume view cell. To observe the effect of the cation composing the ionic liquid on the $CO_2$ solubility, the $CO_2$ solubilities in $[bmpip][Tf_2N]$ used in this study were compared with those in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide ($[bmim]Tf_2N]$). As the equilibrium pressure increased, the $CO_2$ solubility in $[bmpip][Tf_2N]$ increased sharply. On the other hand, the $CO_2$ solubility decreased with increasing temperature. The mole fraction-based $CO_2$ solubilities were almost the same for both $[bmpip][Tf_2N]$ and $[bmim][Tf_2N]$, regardless of temperature and pressure. The phase equilibrium data for the $CO_2+[bmpip][Tf_2N]$ systems have been correlated using the Peng-Robinson equation of state.

• Korean Chemical Engineering Research
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• v.48 no.4
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• pp.519-533
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• 2010

Activity oefficients and solubilities of L-Alanine in aqueous solutions containing each of four electrolytes(NaCl, KCl, $NaNO_3$ and $KNO_3$) were measured at 298.15 K. The measurements of activity coefficients were carried out in the electrochemical cell coupled with two ion-selective electrodes(cation and anion), and the solubilities were measured by the gravimetric analysis of saturated solutions in equilibrium with the solid phase of L-alanine. To model the activity coefficients and solubilities of amino acid in the amino acid/electrolyte aqueous solutions, thermodynamic relations of the residual Helmholtz free energy in the amino acid/electrolyte aqueous solutions were developed based on the perturbed-chain statistical associating fluid theory(PC-SAFT) combined with the primitive mean spherical approximation(primitive-MSA). In the present model, it is assumed that the zwitterions of L-alanine are associated with each other and cross-associated with water molecules, and also cross-associated with the cation and anion dissociated from an electrolyte(inorganic salt). The activity coefficients and solubilities of L-Alanine calculated from the theoretical model proposed in this work are found to be well agreeable with experimental data.

• Clean Technology
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• v.22 no.1
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• pp.35-44
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• 2016

In this study, a computational chemistry methodology called as molecular modeling was been applied to explain several experiment results mechanistically. The reaction chosen for this study was to remove carbon dioxide, known as a primary greenhouse gas, by an epoxide via the carbon dioxide fixation to produce carbonates. This reaction inherently needs the use of catalysts because it has a significantly high activation barrier (55~59 kcal/mol). Among various types of catalysts, we studied in zeolitic imidazolate framework 90 (ZIF-90)/ionic liquid immobilized ZIF-90 (IL-ZIF-90), polystyrene-supported quaternized ammonium salt, KI/KI-glycine, and dimethylethanolamine (DMEA). First, probable reaction pathways were proposed based on calculated energetics by computational chemistry. The energetics was then used for the thermodynamic interpretation on the activity of catalysts. In the case of ZIF-90/IL-ZIF-90 and KI/KI-glycine, IL-ZIF-90 and KI-glycine showed better yields compared to their counterparts. The calculation proposed interesting results that it is not from the lowering of activation energy but from the unstable intermediates of ZIF-90 and KI-glycine. For DMEA, the calculated activation energy was ~42 kcal/mol, much lower than that of the non-catalytic reaction. A possible reaction pathway was located to confirm the interaction between −NH group from ammonium and oxygen from epoxide for polystyrene-supported quaternized ammonium salt.

• Tunnel and Underground Space
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• v.21 no.5
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• pp.394-405
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• 2011

In this paper, we applied coupled non-isothermal, multiphase fluid flow and geomechanical numerical modeling using TOUGH-FLAC coupled analysis to study the complex thermodynamic and geomechanical performance of underground lined rock caverns (LRC) for compressed air energy storage (CAES). Mechanical stress in concrete linings as well as pressure and temperature within a storage cavern were examined during initial and long-term operation of the storage cavern for CAES. Our geomechanical analysis showed that effective stresses could decrease due to air penetration pressure, and tangential tensile stress could develop in the linings as a result of the air pressure exerted on the inner surface of the lining, which would result in tensile fracturing. According to the simulation in which the tensile tangential stresses resulted in radial cracks, increment of linings' permeability and air leakage though the linings, tensile fracturing occurred at the top and at the side wall of the cavern, and the permeability could increase to $5.0{\times}10^{-13}m^2$ from initially prescribed $10{\times}10^{-20}m^2$. However, this air leakage was minor (about 0.02% of the daily air injection rate) and did not significantly impact the overall storage pressure that was kept constant thanks to sufficiently air tight surrounding rocks, which supports the validity of the concrete-lined underground caverns for CAES.

• Ocean and Polar Research
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• v.44 no.4
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• pp.269-285
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• 2022

The interaction between ocean and ice shelf is a critical physical process in relation to water mass transformations and ice shelf melting/freezing at the ocean-ice interface. However, it remains challenging to thoroughly understand the process due to a lack of observational data with respect to ice shelf cavities. This is the first study to simulate the variability and circulation of water mass both overlying the continental shelf and underneath an ice shelf and an ice tongue in the Terra Nova Bay (TNB), East Antarctica. To explore the properties of water mass and circulation patterns in the TNB and the corresponding effects on sub ice shelf basal melting, we explicitly incorporate the dynamic-thermodynamic processes acting on the ice shelf in the Regional Ocean Modeling System. The simulated water mass formation and circulation in the TNB region agree well with previous studies. The model results show that the TNB circulation is dominated by the geostrophic currents driven by lateral density gradients induced by the releasing of brine or freshwater at the polynya of the TNB. Meanwhile, the circulation dynamics in the cavity under the Nansen Ice shelf (NIS) are different from those in the TNB. The gravity-driven bottom current induced by High Salinity Shelf Water (HSSW) formed at the TNB polynya flows towards the grounding line, and the buoyance-driven flow associated with glacial meltwater generated by the HSSW emerges from the cavity along the ice base. Both current systems compose the thermohaline overturning circulation in the NIS cavity. This study estimates the NIS basal melting rate to be 0.98 m/a, which is comparable to the previously observed melt rate. However, the melting rate shows a significant variation in space and time.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.18 no.10
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• pp.136-152
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• 2017

The thermodynamic models, PC-SAFT (Perturbed-Chain Statistical Associated Fluid Theory) state equation and the Two-model approach liquid activity coefficient model NRTL (Non Random Two Liquid) + Henry + Peng-Robinson, for modeling the Rectisol process using methanol aqueous solution as the $CO_2$ removal solvent were compared. In addition, to determine the new binary interaction parameters of the PC-SAFT state equations and the Henry's constant of the two-model approach, absorption equilibrium experiments between carbon dioxide and methanol at 273.25K and 262.35K were carried out and regression analysis was performed. The accuracy of the newly determined parameters was verified through the regression results of the experimental data. These model equations and validated parameters were used to model the carbon dioxide removal process. In the case of using the two-model approach, the methanol solvent flow rate required to remove 99.00% of $CO_2$ was estimated to be approximately 43.72% higher, the cooling water consumption in the distillation tower was 39.22% higher, and the steam consumption was 43.09% higher than that using PC-SAFT EOS. In conclusion, the Rectisol process operating under high pressure was designed to be larger than that using the PC-SAFT state equation when modeled using the liquid activity coefficient model equation with Henry's relation. For this reason, if the quantity of low-solubility gas components dissolved in a liquid at a constant temperature is proportional to the partial pressure of the gas phase, the carbon dioxide with high solubility in methanol does not predict the absorption characteristics between methanol and carbon dioxide.