• Journal of Korean Society of Environmental Engineers
• /
• v.31 no.2
• /
• pp.125-131
• /
• 2009

Reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs) and its toxicity change were predicted by the linear free energy relationship (LFER) model to assess the zero-valent iron (ZVI) and anaerobic dechlorinating bacteria (ADB) as electron donors in PCDDs dechlorination. Reductive dechlorination of PCDDs involves 256 reactions linking 76 congeners with highly variable toxicities, so is challenging to assess the overall effect of this process on the environmental impact of PCDD contamination. The Gibbs free energies of PCDDs in aqueous solution were updated to density functional theory (DFT) calculation level from thermodynamic results of literatures. All of dechlorination kinetics of PCDDs was evaluated from the linear correlation between the experimental dechlorination kinetics of PCDDs and the calculated thermodynamics of PCDDs. As a result, it was predicted that over 100 years would be taken for the complete dechlorination of octachlorinated dibenzo-p-dioxin (OCDD) to non-chlorinated compound (dibenzo-p-dioxin, DD), and the toxic equivalent quantity (TEQ) of PCDDs could increase to 10 times larger from initial TEQ with the dechlorination process. The results imply that the single reductive dechlorination using ZVI or ADB is not suitable for the treatment strategy of PCDDs contaminated soil, sediment and fly ash. This LFER approach is applicable for the prediction of dechlorination process for organohalogen compounds and for the assessment of electron donating system for treatment strategies.

• Clean Technology
• /
• v.18 no.1
• /
• pp.76-82
• /
• 2012

The paper includes utlization of zeolite as potential adsorbent to remove a hazardous malachite green from waste water. The adsorption studies were carried out at 298, 308 and 318 K and effects of temperature, contact time, initial concentration on the adsorption were measured. On the basis of adsorption data Langmuir and Freundlich adsorption isotherm model were also confirmed. The equilibrium process was described well by Freundlich isotherm model, showing a selective adsorption by irregular energy of zeolite surface. From determined isotherm constants, zeolite could be employed as effective treatment for removal of malachite green. From kinetic experiments, the adsorption process followed the pseudo second order model, and the adsorption rate constant ($k_2$) decreased with increasing initial concentration of malachite green. Thermodynamic parameters like activation energy, change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption. The activation energy calculated from Arrhenius equation indicated that the adsorption of malachite green on the zeolite was physical process. The negative free energy change (${\Delta}G^{\circ}$ =-6.47~-9.07 kJ/mol) and the positive enthalpy change (${\Delta}H^{\circ}$ = +32.414 kJ/mol) indicated the spontaneous and endothermic nature of the adsorption in the temperature range 298~318 K.

• Journal of Advanced Marine Engineering and Technology
• /
• v.8 no.1
• /
• pp.17-36
• /
• 1984

Since 1973, the competition on the development of fuel saving type internal combustion engines has become severe by the two times oil shock, and new type engines are reported every several months. Whenever these new type engines are developed, new designs are required and they will be offered in the market after performing the endurance test for a long time. But the engine market is faced with a heavy burden of finance, as the developing of a new engine requires tremendous expenses. For this reason, the computer simulation method has been lately developed to cope with it. The computer simulation method can be available to perform the reasonable research works by the theoretical analysis before carrying out practical experiments. With these processes, the developing expenses are cut down and the period of development is curtailed. The object of this study is the development of simulation computer program for the small naturally aspirated four-stroke diesel engine which is intended to product by the original design of our country. The process of simulation is firstly investigated for the ideal engine cycle, and secondly for the real engine cycle. In the ideal engine cycle, each step of the cycle is simulated by the energy balance according to the first law of thermodynamics, and then the engine performance is calculated. In the real cycle imulation program, the injection rate, the preparation rate and the combustion rate of fuel and the heat transfer through the wall of combustion chamber are considered. In this case, the injection rate is supposed as constant through the crank angle interval of injection and the combustion rate is calculated by the Whitehouse-Way equation and the heat transfer is calculated by the Annand's equation. The simulated values are compared with measured values of the YANMAR NS90(C) engine and Mitsubishi 4D30 engine, and the following conclusions are drawn. 1. The heat loss by the exhaust gas is well agree with each other in the lower load, but the measured value is greater than the calculated value in the higher load. The maximum error rate is about 15% in the full load. 2. The calculated quantity of heat transfer to the cooling water is greater than the measured value. The maximum error rate is about 11.8%. 3. The mean effective pressure, the fuel consumption, the power and the torque are well agree with each other. The maximum error is occurred in the fuel consumption, and its error rate is about 7%. From the above remarks, it may be concluded that the prediction of the engine performance is possibly by using the developed program, although the program needs to reform by adding the simulation of intake and exhaust process and assumping more reliable mechanical efficiency, volumetric efficiency, preparation rate and combustion rate.

• Korean Chemical Engineering Research
• /
• v.58 no.2
• /
• pp.235-247
• /
• 2020

Simulation study and validation on 50 L/hr pilot-scale Bunsen process was carried out in order to investigate thermodynamics parameters, suitable reactor type, separator configuration, and the optimal conditions of reactors and separation. Sulfur-Iodine is thermochemical process using iodine and sulfur compounds for producing hydrogen from decomposition of water as net reaction. Understanding in phase separation and reaction of Bunsen Process is crucial since Bunsen Process acts as an intermediate process among three reactions. Electrolyte Non-Random Two-Liquid model is implemented in simulation as thermodynamic model. The simulation results are validated with the thermodynamic parameters and the 50 L/hr pilot-scale experimental data. The SO₂ conversions of PFR and CSTR were compared as varying the temperature and reactor volume in order to investigate suitable type of reactor. Impurities in H₂SO₄ phase and HI_X phase were investigated for 3-phase separator (vapor-liquid-liquid) and two 2-phase separators (vapor-liquid & liquid-liquid) in order to select separation configuration with better performance. The process optimization on reactor and phase separator is carried out to find the operating conditions and feed conditions that can reach the maximum SO₂ conversion and the minimum H₂SO₄ impurities in HI_X phase. For reactor optimization, the maximum 98% SO₂ conversion was obtained with fixed iodine and water inlet flow rate when the diameter and length of PFR reactor are 0.20 m and 7.6m. Inlet water and iodine flow rate is reduced by 17% and 22% to reach the maximum 10% SO₂ conversion with fixed temperature and PFR size (diameter: 3/8", length:3 m). When temperature (121℃) and PFR size (diameter: 0.2, length:7.6 m) are applied to the feed composition optimization, inlet water and iodine flow rate is reduced by 17% and 22% to reach the maximum 10% SO₂ conversion.

• Transactions of the Korean Society of Mechanical Engineers B
• /
• v.37 no.8
• /
• pp.733-741
• /
• 2013

This is the first paper on the combustion characteristics of landfill gas in a constant volume combustion chamber for a large displacement volume commercial engine, and it discusses the fundamental characteristics of fuel from the viewpoint of thermochemistry and thermodynamics and compares these results with experimental ones. The results show that the final pressures obtained from theoretical analysis vary under the same heating value owing to the change in the constant volume specific heat owing to the difference in the burned gas composition according to the fuel gas compositions; furthermore, the stoichiometric ratios and trends of analytical and experimental pressures coincide very well, although some minor differences are observed between the two. The root cause of the difference is the heat transfer, which changes the specific heat and lowers the temperature considerably, in the real combustion process. In addition, the large chamber volume and ignition position promote the heat transfer to the wall. Finally, the fuel conversion efficiency increases as the methane mol fraction decreases, and it is maximum when the stoichiometric ratio ranges from 0.8 to 0.9. These increases due to the composition and stoichiometric ratio could sufficiently compensate the decrease due to the specific heat ratio drop, LFG might be more advantageous than pure methane in a real engine.

• Clean Technology
• /
• v.11 no.3
• /
• pp.117-122
• /
• 2005

N-vinyl caprolactam (NVCL), a kind of N-vinyl amide monomer, must be dissolved in continuous phase ($scCO_2$) for dispersion polymerization in supercritical carbon dioxide. Phase behavior of $CO_2$+NVCL is very important and necessary for determining initial polymerization condition and for monomer extraction from final polymer. There is the limitation of experimental method for obtaining pure properties of the monomer because of the possibility of polymerization. And N-methyl caprolactam (NMCL) is the useful solvent for the gas treating process. In the viewpoint of molecular thermodynamics, NVCL and NMCL have same functional group i.e. ${\varepsilon}$-caprolactam. In the case of NVCL, hydrogen of amide group is substituted with vinyl group and for NMCL, hydrogen of amide group is substituted with methyl group. We suggested modified group contribution method for this ${\varepsilon}$-caprolactam derivatives. This new group contribution parameter was applied to correlate $CO_2$ + N-vinyl caprolactam or N-methyl caprolactam system.

• Clean Technology
• /
• v.27 no.2
• /
• pp.182-189
• /
• 2021

The adsorption of disperse yellow 3 (DY 3) on granular activated carbon (GAC) was investigated for isothermal adsorption and kinetic and thermodynamic parameters by experimenting with initial concentration, contact time, temperature, and pH of the dye as adsorption parameters. In the pH change experiment, the adsorption percent of DY 3 on activated carbon was highest in the acidic region, pH 3 due to electrostatic attraction between the surface of the activated carbon with positive charge and the anion (OH^-) of DY 3. The adsorption equilibrium data of DY 3 fit the Langmuir isothermal adsorption equation best, and it was found that activated carbon can effectively remove DY 3 from the calculated separation factor (R_L). The heat of adsorption-related constant (B) from the Temkin equation did not exceed 20 J mol^-1, indicating that it is a physical adsorption process. The pseudo second order kinetic model fits well within 10.72% of the error percent in the kinetic experiments. The plots for Weber and Morris intraparticle diffusion model were divided into two straight lines. The intraparticle diffusion rate was slow because the slope of the stage 2 (intraparticle diffusion) was smaller than that of stage 1 (boundary layer diffusion). Therefore, it was confirmed that the intraparticle diffusion was rate controlling step. The free energy change of the DY 3 adsorption by activated carbon showed negative values at 298 ~ 318 K. As the temperature increased, the spontaneity increased. The enthalpy change of the adsorption reaction of DY 3 by activated carbon was 0.65 kJ mol^-1, which was an endothermic reaction, and the entropy change was 2.14 J mol^-1 K^-1.