• Korean Chemical Engineering Research
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• v.44 no.6
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• pp.659-668
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• 2006

The optimization of supercritical water oxidation (SCWO) process for decomposing nitromethane was studied by means of a design of experiments. The optimum operating region for the SCWO process to minimize COD and T-N of treated water was obtained in a lab scale unit. The authors had compared the results from a SCWO pilot plant with those from a lab scale system to explore the problems of scale-up of SCWO process. The COD and T-N in treated waters were selected as key process output variables (KPOV) for optimization, and the reaction temperature (Temp) and the mole ratio of nitromethane to ammonium hydroxide (NAR) were selected as key process input variables (KPIV) through the preliminary tests. The central composite design as a statistical design of experiments was applied to the optimization, and the experimental results were analyzed by means of the response surface method. From the main effects analysis, it was declared that COD of treated water steeply decreased with increasing Temp but slightly decreased with an increase in NAR, and T-N decreased with increasing both Temp and NAR. At lower Temp as $420{\sim}430^{\circ}C$, the T-N steeply decreased with an increase in NAR, however its variation was negligible at higher Temp above $450^{\circ}C$. The regression equations for COD and T-N were obtained as quadratic models with coded Temp and NAR, and they were confirmed with coefficient of determination ($r^2$) and normality of standardized residuals. The optimum operating region was defined as Temp $450-460^{\circ}C$ and NAR 1.03-1.08 by the intersection area of COD < 2 mg/L and T-N < 40 mg/L with regression equations and considering corrosion prevention. To confirm the optimization results and investigate the scale-up problems of SCWO process, the nitromethane was decomposed in a pilot plant. The experimental results from a SCWO pilot plant were compared with regression equations of COD and T-N, respectively. The results of COD and T-N from a pilot plant could be predicted well with regression equations which were derived in a lab scale SCWO system, although the errors of pilot plant data were larger than lab ones. The predictabilities were confirmed by the parity plots and the normality analyses of standardized residuals.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.7 no.3
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• pp.175-182
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• 2009

The spent cationic exchange resins and anionic exchange resins were separated from mixed spent exchange resins by a fluidized bed gravimetric separator. The separated resins were identified by an elemental analysis and thermogravimetric analysis. The each test sample was prepared by diluting the slurry made by wet ball milling the cationic exchange resins and the anionic exchange resins separated as a spherical granular form for 24 hours. The resulting test samples showed a slurry form of less than $75{\mu}m$ of particle size and 25,000ppm of $COD_{cr}$. The decomposition conditions of each test samples from a thermal power plant were obtained with a lab-scale(reactor volume : 220mL) supercritical water oxidation(SCWO) facility. Then pilot plant(reactor volume : 24 L) tests were performed with the test samples from a thermal power plant and a nuclear power plant successively. Based on the optimal decomposition conditions and the operation experiences by lab-scale facility and the pilot plant, a commercial plant(capacity : 150kg/h) can be installed in a nuclear power plant was designed.

• 기계와재료
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• v.10 no.3 s.37
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• pp.63-70
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• 1998

• Journal of the Korean Chemical Society
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• v.58 no.1
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• pp.76-79
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• 2014

Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is $440^{\circ}C$, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2003.11a
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• pp.78-82
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• 2003

For the decomposition of laundry wastewater containing Fe-EDTA produced from the steam generators in nuclear power plants, Supercritical Water Oxidation (SCWO) Process, Photocatalytic Oxidation (PO) Process, and Dielectric Barrier Discharge (DBD) Atmospheric Pressure Plasma Process were evaluated. Even though EDTA was converted over 99.98 % by the SCWO process, it was estimated that the countermeasure against corrosion of the equipment should be reinforced for the process stability. It was considered that the PO process is not appropriate for the decomposition of high concentrated laundry wastewater since the conversion ratio of EDTA was around 10 %. Finally, High efficiency of the decomposition of organic matter (methylene blue) was obtained using DBD process even low energy was supplied. However there is still room for the evaluation of EDTA decomposition in order that the DBD process should be applied for the field samples.

• Korean Chemical Engineering Research
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• v.44 no.6
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• pp.650-658
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• 2006

The recycling of TDA from solid waste of TDI plant(TDI-R) by near-critical hydrolysis reaction had been studied by means of a statistical design of experiment. The main and interaction effects of process variables had been defined from the experiments in a batch reactor and the correlation equation with process variables for TDA yield had been obtained from the experiments in a continuous pilot plant. It was confirmed that the effects of reaction temperature, catalyst type and concentration, and the weight ratio of water to TDI-R(WR) on TDA yield were significant. TDA yield decreased with increases in reaction temperature and catalyst concentration, and increased with an increase in WR. As a catalyst, NaOH was more effective than $Na_2CO_3$ for TDA yield. The interaction effects between catalyst concentration and temperature, WR and temperature, catalyst type and reaction time on TDA yield had been defined as significant. Although the effect of catalyst concentration on TDA yield at $300^{\circ}C$ as subcritical water was insignificant, the TDA yield decreased with increasing catalyst concentration at $400^{\circ}C$ as supercritical water. On the other hand, the yield increased with an increase in WR at $300^{\circ}C$ but showed negligible effect with WR at $400^{\circ}C$. The optimization of process variables for TDA yield has been explored with a pilot plant for scale-up. The catalyst concentration and WR were selected as process variables with respect to economic feasibility and efficiency. The effects of process variables on TDA yield had been explored by means of central composite design. The TDA yield increased with an increase in catalyst concentration. It showed maximum value at below 2.5 of WR and then decreased with an increase in WR. However, the ratio at which the TDA yield showed a maximum value increased with increasing catalyst concentration. The correlation equation of a quadratic model with catalyst concentration and WR had been obtained by the regression analysis of experimental results in a pilot plant.

• Environmental engineer
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• s.177
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• pp.62-68
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• 2001

한화석유화학(주) 중앙연구소는 1994년부터 고농도 난분해성 및 독성폐수 처리에 99.9$\%$ 이상의 탁월한 COD 처리효과를 나타내는 초임계수 산화 기술을 순수 국내 기술로 개발하는 연구를 추진하여 왔다. 한화종합화학(주) 중앙연구소에서는 서강대학교와 한국화학연구소가 보유한 실험실 단계의 초임계 유체 기술과 SCWO 기술을 공동 연구를 통하여 5년 동안 자체적으로 기술 개발을 진행하였고, 제0585호 국산신기술인증(KT)을 받았으

• Korean Chemical Engineering Research
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• v.43 no.2
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• pp.318-323
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• 2005

Supercritical water oxidation (SCWO, P>221 bar, T>$374^{\circ}C$) is a promising method for the decomposition of refractory organic compounds. In this study, the SCWO of Ethylenediaminetetraacetic acid (EDTA) was carried out in a tubular-type continusous reactor system with an $H_2O_2$ oxidant at $387-500^{\circ}C$, 250 bar and residence time (RT) of 15.9-88.9 s. The decomposition efficiencies increased with increasing temperature and oxidant amount, while it was inversely proportional to feed flow rate. The decomposition efficiency of 99.6% was obtained at $500^{\circ}C$, 250 bar, oxidant amount of 400% and residence time of 40.1 s. The effect of temperature on the decomposition efficiency was more significant than that of oxidant amount. In the case of the decomposition efficiency of 5,000 mg/L of EDTA (3,063 mg/L as $COD_{Cr}$), the decompostion of 99% or higher was obtained at the condition of over 40.1 s (RT) and 200 stoichiometric % of $H_2O_2$ in the supercritical water of $500^{\circ}C$ and 250 bar.

• Environmental Engineering Research
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• v.11 no.6
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• pp.311-317
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• 2006

Feasibility of destroying synthetic and actual leachate containing humic acids and ammonia compounds by supercritical water oxidation (SCWO) was evaluated. In this study, destruction efficiencies of humic acids and ammonia respectively were investigated at various reaction temperatures and residence times under pressure a supercritical pressure (280 atm). To lower reaction temperature, chemical oxidants were used. The experiment was carried out in a cylindrical batch reactor made of Hastelloy C-276 that can withstand high temperature and pressure. Concentrations of humic acids and ammonia were measured using a $COD_{Cr}$ method and an ammonia selective electrode, respectively. The optimal destructive condition of humic acids in the presence of stoichiometric oxygen(air) was 3 min at $380^{\circ}C$, but the temperature could be lowered to subcritical region ($360^{\circ}C$) along with $H_2O_2$ as an oxidant. For ammonia, the optimal destructive condition with air was 5 min at $660^{\circ}C$, but it was possible to operate the process for 3 minutes at $550^{\circ}C$ or 2 min at $600^{\circ}C$ along with $H_2O_2$ as an oxidant. At 2 min and $550^{\circ}C$ along with $H_2O_2$ as an oxidant, humic and ammonia compounds in the actual leachate were easily destructed and the effluent quality met the Korea Standard Leachate Quality.

• Korean Chemical Engineering Research
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• v.44 no.6
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• pp.636-643
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• 2006

Supercritical water oxidation of DMMP using continuous flow reactor was studied at temperature ranging from 440 to $540^{\circ}C$ and a fixed pressure of 242 bar. The range of residence times in the reactor was from 10 to 26 s, and oxygen excess value varied from -40 to 200%. Destruction efficiencies (DE) of DMMP were greater than 99.7% at $540^{\circ}C$, and increased as the DMMP concentrations were increased. DE of DMMP were significantly affected by oxygen concentration under stoichiometric amount, but showed little difference over stoichiometric amount. On the basis of 30 data with conversions greater than 85%, kinetic correlations for the DE of DMMP were developed. The pre-exponential factor was $(1.10{\pm}0.76){\times}10^6$, and the activation energy was $90.66{\pm}3.87kJ/mol$, and the reaction orders for DMMP and oxygen were $1.02{\pm}0.03$, $0.32{\pm}0.03$, respectively. The model predictions agreed well with the experimental data.