• 한국군사과학기술학회지
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• 제10권1호
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• pp.123-129
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• 2007

A 2-step process for the safe destruction of chemical wafare agents(agent hydrolysis followed by supercritical water oxidation) was studied to obtain kinetic data for the pilot plant design. This process is simple to operate by using commercial equipments and could be applied as an alternative technology to incineration. Sarin(GB) and sulfur mustard(HD) were hydrolysed in sodium hydroxide and water respectively and their hydrolysates and OPA, which is binary agent for GB were oxidized in a continuous flow supercritical water oxidation system. Destruction efficiencies of the materials were above 99.99% in supercritical water.

• 한국환경과학회지
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• 제14권10호
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• pp.919-928
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• 2005

This study introduces the development of new supercritical water oxidation(SCW)(multiple step oxidation) to destruct recalcitrant organic substances totally and safely by using sodium nitrate as an oxidant. This method has solved the problems of conventional SCW, such as precipitation of salt due to lowered permittivity, pressure increase following rapid rise of reaction temperature, and corrosion of reactor due to the generation of strong acid. Destruction condition and rate in the supercritical water were examined using Polyvinyl Chloride(PVC) and ion exchange resins as organic substances. The experiment was carried out at $450^{\circ}C$ for 30min, which is relatively lower than the temperature for supercritical water oxidation $(600-650^{\circ}C)$. The decomposition rates of various incombustible organic substances were very high [PVC$(87.5\%)$, Anion exchange resin$(98.6\%)$, Cationexchange resin$(98.0\%)$]. It was observed that hetero atoms existed in organic compounds and chlorine was neutralized by sodium (salt formation). However, relatively large amount of sodium nitrate (4 equivalent) was required to raise the decomposition ratio. For complete oxidation of PCB was intended, the amount of oxidizer was an important parameter.

• 한국환경과학회지
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• 제14권5호
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• pp.513-520
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• 2005

For the destruction of toxic chlorinated organic compounds, this study proposes improved supercritical water oxidation method (multistep oxidation) using sodium nitrate as an oxidizer. This method solves the problems involved in the existing supercritical water oxidation method. Multistep oxidation means that $NaNO_3$ is oxidized to $N_2\;via\;NaNO_2$ and NO. Toxic and hard to destroy organic substances like para-dichlorobenzen(4-DCBz), polychlorinate biphenyl(PCB) ware oxidized to non toxic substances in a condition, in which rapid pressure and temperature rise is restrained as much as possible. 4-dichlorobenzene(4-DCBz) and Polychlorinate biphenyl(PCB) in condition$(450^{\circ}C,\;p_w=0.25g/cm^3,\;30min)$ Was discomposed perfectly.

• 한국환경과학회:학술대회논문집
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• 한국환경과학회 2005년도 봄 학술발표회지 제14권(제1호)
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• pp.267-271
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• 2005

This experiment was carried out at 450"C, which is relatively lower than the temperature for supercritical water oxidation (600-650$^{\circ}C$). In this experiment, the decomposition rates of various incombustible organic substances were very high. In addition, it was confirmed that hetero atoms existed in organic compounds and chlorine was neutralized by sodium(salt formation).However, to raise the decomposition rate, relatively large amount of sodium nitrate(3-4 times the equivalent weight) was required. When complete oxidation is intended as in the case with PCB, the amount of oxidizer and decomposition cost is important. But when vaporization reduction is required as in the case with nuclear wastes, the amount of radioactive wastes increases instead. But as can be seen in the result of XRD measurement, unreacted sodium nitrate remained unchanged. If oxidation reaction of organic substance simply depends on collision frequency, unreacted sodium nitrate can be recovered and reused, then oxidation equivalent weight would be sufficient. In the gas generated, toxic gas was not found. As the supercritical water medium has high reactivity, it is difficult to generate relatively low energy level SO$_{X}$, and NO$_{X}$.

• 한국환경보건학회지
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• 제30권2호
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• pp.133-139
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• 2004

The objective of this study was to investigate the destruction efficiency and to determine the fundamental parameters of oxidation kinetics under the supercritical water(SCW) condition. Target material was cephradine, toxic and antibiotic material, in the pharmaceutical wastewater. For this purpose, the effect of reaction temperature and oxidant were investigated on the destruction efficiency of cephradine. And the oxidation kinetics of cephradine was derived by using a empirical power-law model. The experiment was carried out in a cylindrical batch reactor made of Hastelloy C-276 which was endurable high temperature and pressure. The destruction efficiency of cephradine increased with increment of the temperature and reaction time. Also the type of oxidants was effected and oxidants(Air and $H_2O$$_2$) were enhanced the destruction efficiency. The global oxidation kinetics for cephradine has led to two rate expressions according to type of oxidant. - In the presence of air oxidant: Rate=k. $e^{-Ea}$RT/(Ceph.)$^{1.0}$ ( $O_2$)$^{0.51}$$\pm$0.05(k=3.27${\times}$$10^{5}$ sec. Ea=63.25 kJ/mole) - In the presence of $H_2O$$_2$ oxidant : Rate=kㆍ $e^{-Ea}$RT/(Ceph.)$^{1.0}$ ($H_2O$$_2$)$^{0.62}$$\pm$0.02(k=2.76${\times}$$10^4$/sec. Ea=47.65 kJ/mole)ole))

• Korean Chemical Engineering Research
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• 제59권1호
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• pp.85-93
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• 2021

For accurate and reliable process design for phenol oxidation in a plug flow reactor with supercritical water, modeling can be very insightful. Here, the velocity and density distribution along the reactor have been predicted by a numerical model and variations of temperature and phenol mass fraction are calculated under various flow conditions. The numerical model shows that as we proceed along the length of the reactor the temperature falls from above 430 ℃ to approximately 380 ℃. This is because the generated heat from the exothermic reaction is less that the amount lost through the walls of the reactor. Also, along the length, the linear velocity falls to less than one-third of the initial value while the density more than doubles. This is due to the fall in temperature which results in higher density which in turn demands a lower velocity to satisfy the continuity equation. Having a higher oxygen concentration at the reactor inlet leads to much faster phenol destruction; this leads to lower capital costs (shorter reactor will be required); however, the operational expenditures will increase for supplying the needed oxygen. The phenol destruction depends heavily on the kinetic parameters and can be as high as 99.9%. Using different kinetic parameters is shown to significantly influence the predicted distributions inside the reactor and final phenol conversion. These results demonstrate the importance of selecting kinetic parameters carefully particularly when these predictions are used for reactor design.

• 대한화학회지
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• 제58권1호
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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%.

• Korean Chemical Engineering Research
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• 제45권1호
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• pp.46-51
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• 2007

본 연구에서는 전력 산업에서 발생하는 폐기물 중의 하나인 Poly Chlorinated Biphenyls(PCBs)를 함유한 절연유를 초임계수 내에서 완전산화반응을 통해서 제거하는 전산모사를 수행하였다. 절연유의 주성분을 노말 데칸으로 선정하였으며, 초임계수 내의 절연유의 함량은 3.0 wt％로 가정하였다. 초임계수 내에서의 물성 추산을 위해서 Peng-Robinson 상태방정식을 사용하였으며, 전산모사를 통해서 초임계수 내에서 3.0 wt％의 절연유 및 과잉 산소가 모두 용해되는 현상을 잘 설명할 수 있었다.

• 플랜트 저널
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• 제4권2호
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• pp.60-65
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• 2008

As the operating conditions in a supercritical oxidation reactor are set in high temperature with high pressure causing a reactor suffering from the harsh circumstances. It means the reactor adopts itself with Fe-Cr alloy in acidic atmosphere with low pH value and Ni alloy in basic atmosphere with high pH value due to its superior corrosion resistance. The study, whose target waster water is pertinent to the latter part, has selected Ni alloy such as ostenite type stainless steel 304 and 316, superstainless steel AL6XN, Inconel 625, MAT 21, and titanium Gr. 5 in order to measure corrosion resistance against those samples under the same conditions of temperature and pressure applied for a supercritical oxidation reactor. The result shows the identifiable difference in corrosion resistance by observing the surface states through a scanning probe microscope as well as measuring the weight loss through making the samples above deposited in wastewater for two-week and four-week stay. The purpose of this corrosion experiment is to identify the most corrosion-resistant material among sample species pre-selected according to pH concentration of wastewater in pursue of applying for a reactor exposed to the extreme corrosion environment. It is because such a reactor made of a verified material enables to safeguard a stable operation under the supercritical wastewater processing facility.

• Environmental Engineering Research
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• 제11권6호
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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.