• 대한환경공학회지
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• 제33권10호
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• pp.723-730
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• 2011

본 연구는 토양이나 지하수 원위치 화학적 산화법(In-Situ Chemical Oxidation, ISCO)에서 사용할 수 있는 산화제 Persulfate를 상온에서 활용할 수 있도록 RDX를 처리대상물질로 연구하였다. Persulfate로 RDX를 처리한 결과, 반응은 유사1차반응으로 나타났으며 온도가 증가함에 따라 분해속도도 증가하였고, 이 때 활성화에너지(Activation energy)는 $1.14{\times}10^2kJ/mol$으로 산정되었다. Persulfate에 의한 RDX의 분해반응속도는 pH에 비례하여 증가하였으며, pH값이 4, 6, 8일 때 반응속도의 변화가 크지 않았다. 그러나 pH 10에서는 13배 이상 증가하였는데, persulfate에 의한 산화가 아니라 alkaline hydrolysis로 나타났다. Persulfate에 의한 RDX의 분해반응속도는 persulfate/RDX의 몰 비율에 따라 선형적으로 증가하였으며, $70^{\circ}C$에서 측정한 비례상수는 $4{\times}10^{-4}$ ($min^{-1}$/몰 비율)이었다. 용액 내 천연유기물(NOM) 농도가 증가함에 따라 persulfate에 의한 RDX 분해속도 선형 감소하였으며 $70^{\circ}C$, persulfate/RDX 몰비 10/1에서 측정한 비례상수는 $1.21{\times}10^{-4}$ ($min^{-1}{\cdot}L/mg-NOM$)이었다. 반응속도의 감소는 NOM 첨가량에 선형적으로 비례하였다. NOM 20 mg/L을 첨가한 반응의 Ea값은, 무첨가 반응에서 산정된 Ea값과 3.3% 오차에 불과하였는데, 이는 NOM의 첨가가 본래의 산화반응을 변화시키지는 않음을 의미한다.

• 한국지하수토양환경학회지:지하수토양환경
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• 제25권4호
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• pp.77-86
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• 2020

Persulfate-based advanced oxidation processes (AOPs) can oxidize various organic pollutants. In this study, persulfate/Fe(II) system was utilized in phenol removal, and the effect of various organic and inorganic chelators on Fe(II)-medicated persulfate activation was investigated. The feasibility of persulfate/Fe(II)/chelator in cleanup of phenol-contaminated sediment was confirmed through toxicity assessment. In persulfate/Fe(II) conditions, the rate and extent of phenol removal increased in proportion to persulfate concentration. In chelator injection condition, the rate of phenol removal was inversely proportional to chelator concentration when it was injected above optimum ratio. Thiosulfate showed greater chelation tendency with persulfate than citrate and interfered with persulfate access to Fe(II), making the latter a more suitable chelator for enhancing persulfate activation. In contaminated clay sediment condition, 100% phenol removal was obtained within an hour without chelator, with the removal rate increased up to four times as compared to the rate with chelator addition. A clay sediment toxicity assessment at persulfate:Fe(II):phenol 20:10:1 ratio indicated 71.3% toxicity reduction with 100% phenol removal efficiency. Therefore, persulfate/Fe(II) system demonstrated its potential utility in toxicity reduction and cleanup of organic contaminants in sediments.

• 한국환경과학회지
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• 제32권1호
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• pp.57-65
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• 2023

The advanced oxidation treatment using persulfate and zero-valent iron (ZVI) has been evaluated as a very effective technology for remediation of soil and groundwater contamination. However, the high rate of the initial reaction of persulfate with ZVI causes over-consumption of an injected persulfate, and the excessively generated active species show a low transfer rate to the target pollutant. In this study, ZVI was modified using selenium with very low reactivity in the water environment with the aim of controlling the persulfate activation rate by controlling the reactivity of ZVI. Selenium-modified ZVI (Se/ZVI) was confirmed to have a selenium coating on the surface through SEM/EDS analysis, and low reductive reactivity to trichlroethylene (TCE) was observed. As a result of inducing the persulfate activation using the synthesized Se/ZVI, the persulfated consumption rate was greatly reduced, and the decomposition rate of the model contaminant, anisole, was also reduced in proportion. However, the final decomposition efficiency was rather increased, which seems to be the result of preventing persulfate over-consumption. This is because the transfer efficiency of the active species (SO4-∙) of persulfate to the target contaminant has been improved. Selenium on the surface of Se/ZVI was not significantly dissolved even under oxidation conditions by persulfate, and most of it was present in the form of Se/ZVI. It was confirmed that the persulfate activation rate could be controlled by controlling the reactivity of ZVI, which could greatly contribute to the improvement of the persulfate oxidation efficiency.

• 대한환경공학회지
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• 제31권7호
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• pp.549-556
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• 2009

Trichloroethylene (TCE)와 tetrachloroethylene (PCE)은 주로 드라이클리닝 및 산업 세척액으로 쓰이는 염소계 화합물이며, 발암성 물질로 알려져 있다. In situ chemical oxidation (ISCO)는 토양 및 지하수를 처리하는 기술로, 지표 아래에 존재하는 오염된 지역까지 산화제를 전달하여 오염물질을 처리하는 기술이다. ISCO에 사용되는 산화제 중 persulfate는 강력한 산화제인 sulfate 라디칼 (${SO_4}^{-{\cdot}}$)을 발생시켜 처리하는 기법으로, 본 연구에서는 TCE와 PCE의 분해에 persulfate 산화공정을 적용하여 초기 pH (3, 6, 9, 12), persulfate의 농도 (0.01, 0.05, 0.1, 0.3, 0.5 M), 초기오염물질농도 (10, 30, 50, 70, 100 mg/L)에 대한 영향을 알아보았다. 초기 pH가 3 일 때, TCE와 PCE는 각각 93.2%와 89.3%로 가장 높은 처리효율을 나타낸 반면, 초기 pH가 12 일 때, TCE 55.0%와 PCE 31.2%로 가장 낮은 효율을 보여 pH가 높아질수록 처리효율이 감소하는 것을 확인할 수 있었다. 또한 persulfate의 농도가 증가할수록 TCE/PCE의 처리효율이 증가하였으며, 가장 높은 persulfate의 농도 (0.5 M)에서의 처리효율은 96.5% (TCE), 95.7% (PCE) 였다. 반면 초기오염농도가 높아질수록 처리효율은 낮아지는 경향이 나타났다. 본 연구에서 얻어진 가장 빠른 분해속도를 나타내는 조건은 pH 3, persulfate 농도 0.5 M, 그리고 오염물질 (TCE/PCE) 농도 10 mg/L이었고, 이때 구해진 1차 분해속도 상수 ($k_{obs}$)는 1.04 (TCE)와 1.31 (PCE) $h^{-1}$ 였다.

• 한국환경과학회지
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• 제26권11호
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• pp.1201-1208
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• 2017

Oxidative degradation of chlorinated ethenes was carried out using heat-activated persulfate. The activation rate of persulfate was dependent on the temperature and the activation reaction rate could be explained based on the Arrhenius equation. The activation energy of persulfate was 19.3 kcal/mol under the assumption that the reaction between the sulfate radical and tricholoroethene (TCE) is very fast. Activation could be achieved at a moderate temperature, so that the adverse effects due to high temperature in the soil environment were mitigated. The reaction rate of TCE was directly proportional to the concentration of persulfate, indicating that the remediation rate can be controlled by the concentration of the injected persulfate. The solution was acidized after the oxidation, and this was dependent on the oxidation temperature. The consumption rate of persulfate was high in the presence of the target organic, but the self-decomposition rate became very low as the target was completely removed.

• Journal of Applied Biological Chemistry
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• 제61권4호
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• pp.383-389
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• 2018

Degradation of the insecticide O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate (chlorpyrifos) in aqueous solution was investigated using iron salts and potassium persulfate during ZVI treatment through a series of batch experiments. The degradation rate of chlorpyrifos increased with increases in the concentrations of iron salts and potassium persulfate in the aqueous system. Ferric chloride was found to be the most effective iron salt for the ZVI-mediated degradation of chlorpyrifos in aqueous solution. Further, the iron salts tested could be arranged in the following order in terms of their effectiveness: $FeCl_3$> $Fe_2(SO_4)_3$> $Fe(NO_3)_3$. The persulfate-ZVI system could significantly degrade chlorpyrifos present in the aqueous medium. This revealed that chlorpyrifos degradation by treatment with $Fe^0$ was promoted on adding ferric chloride and potassium persulfate. The kinetics of the degradation of chlorpyrifos by persulfate-amended $Fe^0$ was higher than that for iron-salt-amended $Fe^0$. This suggests that using a sequential $Fe^0$ reduction-ferric chloride or $Fe^0$ reduction-persulfate process may be an effective strategy to enhance the removal of chlorpyrifos in contaminated water.

• 한국지하수토양환경학회지:지하수토양환경
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• 제26권1호
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• pp.45-53
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• 2021

The removal of 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution by coupled electro-oxidation and Fe(II) activated persulfate oxidation process was investigated. The electrochemical oxidation was performed using carbon sheet electrode and persulfate using Fe(II) ion as an activator. The oxidation efficiency was investigated by varying current density (2 - 10 mA/㎠), electrolyte (Na2SO4) concentration (10 - 100 mM), persulfate concentration (5 - 20 mM), and Fe(II) concentration (10 - 20 mM). The 2,4-D removal efficiency was in the order of Fe(II) activated persulfate-assisted electrochemical oxidation (Fe(II)/PS/ECO, 91%) > persulfate-electrochemical oxidation (PS/ECO, 51%) > electro-oxidation (EO, 36%). The persulfate can be activated by electron transfer in PS/ECO system, however, the addition of Fe(II) as an activator enhanced 2,4-D degradation in the Fe(II)/PS/ECO system. The 2,4-D removal efficiency was not affected by the initial pHs (3 - 9). The presence of anions (Cl- and HCO3-) inhibited the 2,4-D removal in Fe(II)/PS/ECO system due to scavenging of sulfate radical. Scavenger experiment using tert-butyl alcohol (TBA) and methanol (MeOH) confirmed that although both sulfate (SO4•-) and hydroxyl (•OH) radicals existed in Fe(II)/PS/ECO system, hydroxyl radical (SO4•-) was the predominant radical.

• Journal of Electrochemical Science and Technology
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• 제10권2호
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• pp.115-122
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• 2019

In order to improve the current efficiency and reduce the energy consumption in the electrosynthesis of ammonium persulfate, electrolytic properties of a perfluorosulfonic cation exchange membrane named PGN membrane and the $Al_2O_3$ ceramic membrane in the electrosynthesis of ammonium persulfate were studied and compared in a pilot electrolytic cell using a welded platinum titanium as the anode and a Pb-Sb alloy as the cathode. The effect of cell voltage, electrolyte flow rate and electrolysis time of the electrolytes on the current efficiency and the energy consumption were studied. The results indicated that the PGN membrane could improve current efficiency to 95.12% and reduce energy consumption to $1110kWh\;t^{-1}$ (energy consumption per ton of the ammonium persulfate generated) under the optimal operating conditions and the highest current efficiency of the $Al_2O_3$ ceramic membrane was 72.61% with its lowest energy consumption of $1779kWh\;t^{-1}$. Among 5 times of the electrolysis of the electrolytes, the lowest current efficiency of the PGN membrane was 85.25% with the highest energy consumption of $1244kWh\;t^{-1}$ while the lowest current efficiency of the $Al_2O_3$ ceramic membrane was 67.44% with the highest energy consumption of $1915kWh\;t^{-1}$, which suggested the PGN membrane could be used in the 5-stage electrolytic cell for the industrially continuous electrosynthesis of ammonium persulfate. Therefore the PGN membrane can be efficient to improve the current efficiency and reduce the energy consumption and can be applied in the industrial electrosynthesis of ammonium persulfate.

• 한국지하수토양환경학회지:지하수토양환경
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• 제17권2호
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• pp.7-14
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• 2012

Batch tests were carried out to evaluate the thermal treatment of low volatile organic compounds in low-permeability soil. The chemical oxidation by sodium persulfate catalyzed by heat and Fe (II) was evaluated. Enhanced persulfate oxidation of n-decane (C-10), n-dodecane (C-12), n-tetradecane (C-14), n-hexadecane (C-16), and phenanthrene was observed with thermal catalyst, indicating increased sulfate radical production. Slight enhancement of the pollutants oxidation was observed when initial sodium persulfate concentration increased from 5 to 50 g/L. However, the removal efficiency greatly decreased as soil/water ratio increased. It indicates that mass transfer of the pollutants as well as the contact between the pollutants and sulfate radical were inhibited in the presence of solids. In addition, more pollutants can be adsorbed on soil particles and soil oxidant demand increased when soil/water ratio becomes higher. The oxidation of the pollutants was significantly improved when catalyzed by Fe(II). The sodium persulfate consumption increased at the same time because the residual Fe(II) acts as the sulfate radical scavenger.

• 한국물환경학회지
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• 제25권1호
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• pp.151-158
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• 2009

The objective of this study was to determine on optimum ratio of oxidant and catalyst and to evaluate affecting factors such as anions and cations on persulfate oxidation of organic pollutant. Fe(II) activated the persulfate anion to produce a sulfate free radicals and thus effectively used to degrade the target organic pollutant in aqueous system. The chloride ions reacted with sulfate radical produced the $Cl^{\cdot}$ atom and had positive effects on the oxidation of organic pollutant at the initial stage. However, it was observed that chloride ions had the scavenging effects on the rate of oxidation of organic pollutant. Cations and some heavy metals were partly able to activate the persulfate anion to generate a sulfate free radical. However, high levels of cations inhibited the oxidation of organic pollutant.