• 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.

• 한국지하수토양환경학회지:지하수토양환경
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• 제22권2호
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• pp.17-25
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• 2017

The efficiency and mechanism of electrochemical phenol oxidation using persulfate (PS) and nanosized zero-valent iron (NZVI) were investigated. The pseudo-first-order rate constant for phenol removal by the electrochemical/PS/NZVI ($1mA^*cm^{-2}/12$ mM/6 mM) process was $0.81h^{-1}$, which was higher than those of the electrochemical/PS and PS/NZVI processes. The electrochemical/PS/NZVI system removed 1.5 mM phenol while consuming 6.6 mM PS, giving the highest stoichiometric efficiency (0.23) among the tested systems. The enhanced phenol removal rates and efficiencies observed for the electrochemical/PS/NZVI process were attributed to the interactions involving the three components, in which the electric current stimulated PS activation, NZVI depassivation, phenol oxidation, and PS regeneration by anodic or cathodic reactions. The electrochemical/PS/NZVI process effectively removed phenol oxidation products such as hydroquinone and 1,4-benzoquinone. Since the electric current enhances the reactivities of PS and NZVI, process performance can be optimized by effectively manipulating the current.

• 한국지하수토양환경학회지:지하수토양환경
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• 제22권1호
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• pp.41-48
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• 2017

Persulfate (PS) activated with nanosized zero-valent iron (NZVI) was tested as a reagent to remove phenol from groundwater. Batch degradation experiments indicated that NZVI/PS molar ratios between 1 : 2 and 1 : 5 were appropriate for complete removal of phenol, and that the time required for complete removal varied with different PS and NZVI dosages. Chloride ions up to 100 mM enhanced the phenol oxidation rate, and nitrate of any concentration up to 100 mM did not significantly affect the oxidation rate. NZVI showed greater performance than ferrous iron did as an activator for PS. A by-product was formed along with phenol degradation but subsequently was completely degraded, which showed the potential to attain mineralization with the NZVI/PS system. Tests with radical quenchers indicated that sulfate radicals were a predominant radical. The results of this study suggest that NZVI is a promising activator of PS for treating contaminated groundwater.

• 한국지하수토양환경학회지:지하수토양환경
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• 제17권6호
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• pp.43-51
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• 2012

Rreactivity of persulfate (PS) for oxidation of TCE under various conditions such as heat, $Fe^{2+}$, and UV was investigated. It was found that degradation rate of TCE increased with increasing temperature from 15 to $35^{\circ}C$. At pH 7.0, the rate constants (k) at 15, 25, 30, and $35^{\circ}C$ were 0.07, 0.30, 0.74, and $1.30h^{-1}$, respectively. For activation by $Fe^{2+}$, removal efficiency of TCE increased with increasing $Fe^{2+}$ concentration from 1.9 mM to 11 mM. The maximum removal efficiency of TCE was approximately 85% when pH of the solution dropped from 7.0 to 2.5. Degradation of TCE by UV-activated PS was the most effective, showing that the degradation rate of TCE increased with inreasing PS dosage; the rate constants (k) at 0.5, 2.5, and 10 mM were 34.2, 40.5, and $55.9h^{-1}$, respectively. Our results suggest that PS activation by UV/PS process could be the most effective in activation processes tested for TCE degradation. For oxidation process by PS, however, pH should be observed and adjusted to neutral conditions (i.e., 5.8-8.5) if necessary.

• 한국지하수토양환경학회지:지하수토양환경
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• 제28권1호
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• pp.15-24
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• 2023

A persulfate(PS)/sulfidated microscale zero-valent iron(S-mZVI) system was tested for treating a soil contaminated with phenol. Sulfidation of bare mZVI was conducted using a mechanochemical process utilizing a ball mill in order to improve persulfate activation capacity and stability of unmodified mZVI. The synthesized S-mZVI performed markedly better than the bare mZVI in activating PS. The optimum molar ratio of sulfur to mZVI was around 0.12. In the soil slurry experiments, a very rapid and complete removal of phenol was observed at the optimum molar ratios of PS to S-mZVI of 2:1 and PS to phenol of 16:1. The phenol removal efficiencies decreased as the water content of the slurries decreased. This was believed to be due to increased soil oxidant demand as the amount of soil was increased as relative to the water content. To evaluate the field applicability of the process, slurry experiments adopting high soil contents were carried out that simulated in-situ soil mixing conditions. These experiments resulted in substantially compromised degradation efficiencies of 54.3% and 43.8% within 4 hours. The current study generally shows that the PS/S-mZVI process has a potential to be developed into a remediation technology for soils contaminated with organics.

• Environmental Engineering Research
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• 제25권2호
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• pp.178-185
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• 2020

The aim of this study is to investigate the degradation of ciprofloxacin (CIP) from its aqueous solutions via different advanced oxidation processes (AOP). The effects of persulfate (PS) concentration, pH, zinc oxide nanoparticles (ZnO-NPs) dose, initial CIP concentration, and reaction time on the degradation of CIP were studied. It was found that the sonochemical (US) degradation is a less efficient process (with removal efficiency of 36%) compared to the sono-nano-chemical (US/ZnO) process which resulted in removal efficiency of 70%. Maximum removal of 99% was obtained using the sono-nano-chemical/PS (US/ZnO/PS) process at a frequency of 60 kHz, time of 10 min, pH of 7, initial CIP concentration of 25 mg/L, and PS concentration of 476.06 mg/L. The addition of PS and ZnO-NPs to the process enhanced the rate of US degradation of CIP. In addition, the kinetic parameters for the US/ZnO/PS process were obtained by fitting the kinetic data into the pseudo-first-order and pseudo-second-order kinetic models. The kinetic data was found to fit into the pseudo-first-order kinetic model than the pseudo-second-order model. The results showed that the AOP using US/ZnO/PS is a promising technique for the treatment of ciprofloxacin containing solutions.

• Journal of Industrial and Engineering Chemistry
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• 제67권
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• pp.301-311
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• 2018

In this study, the ion-gelation method was applied to fabricate novel Fe-carbon-bentonite-alginate beads ($Fe^0$/C-BABs). $Fe^0$/C-BABs could effectively control Fe release during persulfate (PS) activation in N-acetyl-p-aminophenol (APAP) oxidation. A novel two-stage approach that combined $Fe^0$/C-BABs and an oyster-shell-filled bed (OSFB) column was developed to address the low pH and high Fe concentration of the effluent of the traditional PS process. The application of the $Fe^0$/C-BABs and OSFB column regulated pH levels and Fe release during the advanced oxidation of APAP. The characteristics of $Fe^0$/C-BABs were also investigated through scanning electron microscopy, energy dispersive spectrometry, and Fourier transform infrared spectroscopy. The long-term operation performance of $Fe^0$/C-BABs in a continuous fixed-bed reactor under simultaneous PS and APAP feeding was also evaluated. The effects of initial PS concentration, pH, fixed-bed weight, in-flow rate, and dissolved oxygen (DO) were investigated. Under selected conditions, 86.3% efficiency was achieved during the first stage of APAP degradation (effluent pH of 3.05, Fe contents: $106.25mgL^{-1}$). Water quality improved after the effluent was passed through the OSFB column (effluent pH of 6.32, Fe contents: $21.43mgL^{-1}$). Moreover, this study analyzed the free radicals and intermediates produced during APAP degradation to identify the possible routes of APAP degradation.

• 유기물자원화
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• 제32권3호
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• pp.5-18
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• 2024

유기물 측정지표인 화학적산소요구량(COD)은 산화율이 낮아 난분해성 유기물까지 포함한 전체 유기물질의 총량관리에 한계를 가지고 있어 보다 정확한 측정이 가능한 총유기탄소(TOC)가 측정지표로 도입되어 사용되고 있다. 폐수 내 TOC 저감을 위해서는 여러 공정들이 적용가능하나 경기도 소재의 A사를 비롯한 여러 환경업체에서는 원폐수를 먼저 희석한 후 약품처리에 의한 응집침전과정을 거치고 후단에 활성탄을 사용하여 총유기탄소를 처리하고 있는 실정이다. 현장에서는 많은 물 사용과 약품사용으로 인한 슬러지가 과다하게 발생하는 문제가 있어 이를 대체할 수 있는 방안도출이 시급한 실정이다. 따라서 본 연구에서는 A사 실폐수의 TOC 저감효율 증진을 위해 두 가지 다른 방법을 적용하였다. 첫 번째 방법은 셀룰로오스 기반 유사-그래핀(CGLC)을 제조하여 현재 사용되고 있는 흡착제인 분말활성탄(PAC)의 대체가능성 평가에 관한 것이다. 첫 번째 연구를 통해서는 CGLC가 상업용 PAC보다 TOC 제거율에서 약 10% 정도의 높은 성능을 보여 수처리 현장에서 PAC의 대체 흡착제로 적용될 수 있는 가능성을 보여주었다. 두 번째 방법은 persulfate(PS) 활성화에 의해 생성되는 황산라디칼에 의한 TOC 제거에 관한 것이다. PS 활성화를 위해 CGLC와 PAC을 사용하는 것과 폐수의 높은 온도를 이용하는 두 가지 방법을 적용하였다. PAC과 CGLC를 PS 활성화물질로 사용한 결과, TOC 제거율은 실폐수내 존재하는 과량의 염소이온에 의해 CGLC와 PAC에 의한 TOC의 흡착제거량 보다 낮게 나타났다. 그렇지만 PS 활성화를 위해 현장 폐수의 높은 수온(55~60℃)을 이용한 결과 PAC 단독, CGLC 단독 그리고 PS 활성화에 탄소계 매질을 사용한 것보다 훨씬 큰 TOC 제거능을 보였으며, PS를 0.5% 이상 주입시 24 시간 이내에 95% 이상의 TOC 제거능을 보였다. 또한 PS를 0.3% 이상 주입시 A사의 폐수 배출기준인 75 ppm 이하로 TOC 농도를 낮출 수 있었다. 이러한 결과를 종합하면, 높은 온도의 원폐수에 PS만 첨가하는 간편한 공정으로도 TOC를 A사의 폐수 방류기준 이하로 처리하여 배출할 수 있는 것으로 나타났다.

• Korea-Australia Rheology Journal
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• 제21권3호
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• pp.185-191
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• 2009

Polystyrene/multi-walled carbon nanotube (PS/MWCNT) composites were prepared by the use of latex technology. The monodisperse PS latex was synthesized by an emulsifier-free emulsion polymerization from styrene/potassium persulfate/water system in the presence of ethanol. The MWCNTs were first treated with acid mixture to eliminate impurities, dispersed in deionized water driven by ultrasonicator, and then mixed with the PS latex. From these mixtures, PS/MWCNT composites were prepared by freeze-drying and subsequent compression molding. In the small-amplitude oscillatory shear experiments, both complex viscosity and storage modulus increased with increasing MWCNT content. A pronounced effect of MWCNT content was observed, resulting in larger storage modulus and stronger yield behavior at low frequencies when compared to unmodified PS. It showed a transition from viscous to elastic behavior with increasing MWCNT content. Over the MWCNT content of 3 wt%, the storage modulus was higher than the loss modulus across all frequencies.

• Bulletin of the Korean Chemical Society
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• 제33권9호
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• pp.2966-2970
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• 2012

Fullerene/polystyrene ($C_{60}$/PS) nano particle was prepared by using emulsion polymerization. Styrene and fullerene were emulsified in aqueous media in the presence of poly(N-vinyl pyridine) as an emulsion stabilizer, and polymerization was initiated by water soluble radical initiator, potassium persulfate. The obtained nano particles have an average diameter in the range of 400-500 nm. The fullerene contents in the nano particle can be controlled up to 15 wt % by varying the feed ratio, which was confirmed by themogravimetric analysis (TGA) and elemental analysis (EA). The structure and morphologies of the $C_{60}$/PS nano particles were examined by various analytical techniques such as dynamic light scattering (DLS), scanning electron microscope (SEM), transmission electron microscope (TEM), electron diffraction (ED) pattern, X-ray powder diffraction (XRD), and UV spectroscopy. Unlike conventional $C_{60}$/PS particles initiated by organic free radical initiators, in which the fullerene is copolymerized forming a covalent bond with styrene monomer, the prepared $C_{60}$/PS nano particles contain pristine fullerene as secondary particles homogeneously distributed in the polystyrene matrix.