Organic wastewater causes serious environmental pollution, and catalytic oxidation is promising technique for wastewater treatment. Developing green and effective catalysts is currently challenging. In this work, green synthesis of nano zerovalent iron loaded onto porous biochar derived from popcorn is conducted, and catalytic oxidation of Rhodamine B (RhB) is evaluated in the presence of H2O2. Effect of process factors is examined on catalytic performance for RhB removal. The mechanism of RhB removal is discussed by characterizations (Fourier transform infrared spectra and Raman) and UV–vis spectra. RhB removal is improved with high catalyst dosage, low initial RhB concentration, and high reaction temperature, while it is slightly influenced by carbonization temperature of biochar, H2O2 dosage and pH value. Under conditions of BC-250 1.0 g/L, H2O2 0.01 mol/L, pH 6.1, and temperature 30 °C, the removal rate of RhB is 92.27% at 50 min. Pseudo first-order kinetics is used to fitting experimental data, and the activation energy for RhB removal in BC-250/H2O2 system is 39 kJ/mol. RhB removal in BC-250/H2O2 system can be attributed to adsorption effect and catalytic oxidation with the dominant role of hydroxyl radical. This work gives insights into catalytic oxidation of organic wastewater using green catalyst.

In this study, we compared the MZVI (Microscale Zero-Valent Iron) and NZVI (Nanoscale Zero-Valent Iron) for reactivity and mobility in a column to reduce nitrate, which is a major pollutant in Korea, and investigated the effect of operational parameters on the NZVI filled column. For the comparison of MZVI and NZVI, samples were collected for 990 minutes using fractionator in the similar operation conditions (MZVI 10g, NZVI 2g). The nitrate reduction efficiency of NZVI was about 5 times higher than that of MZVI, which was about 7.45% and 38.75% when using MZVI and NZVI, respectively. In the mobility experiment, the MZVI descended due to gravity while NZVI moved up with water flow due to its small size. Furthermore, the optimum condition of NZVI filled column was determined by changing the flow rate and pH. The amount of Fe ions was increased as the pH of the nitrate solution was lowered, and the nitrate removal rate was similar due to the higher yield of hydroxyl groups. The removal rate of nitrate nitrogen was stable while flow rate was increased from 0.5 mL/min to 2.0 mL/min (empty bed contact time: 2.26 min to 0.57 min). NZVI has a high reduction rate of nitrate, but it also has a high mobility, so both of reactivity and mobility need to be considered when NZVI is applied for drinking water treatment.

This study investigated the decomposition of fenitrothion in Smithion, which is applied on the golf course for pesticide, by the integrated Zero-valent iron(ZVI) and Granular activated carbon(GAC) process. First, the removal efficiencies of the fenitrothion by ZVI and GAC, respectively, were investigated. Second, the removal efficiencies of the fenitrothion by the integrated ZVI and GAC were investigated. The removal efficiencies of fenitrothion by ZVI were higher than those of TOC. The removal efficiencies of fenitrothion and TOC by GAC were similar. As the dosages of ZVI and GAC were increased, the removal efficiencies of fenitrothion and TOC increased. However, as the dosages of ZVI for pretreatment were increased, the adsorptions of fenitrothion on GAC were hindered.

In this study, the reductive dechlorination of triclosan using zero-valent iron (ZVI, Fe0) and modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium-coated iron (Pd/Fe)) was experimentally investigated, and the reduction characteristics were evaluated by analyzing the reaction kinetics. Triclosan could be reductively decomposed using zero-valent iron. The degradation rates of triclosan were about 50% and 67% when Fe0 and Aw/Fe were used as reductants, respectively, after 8 h of reaction. For the Pd/Fe system, the degradation rate was about 57% after 1 h of reaction. Thus, Pd/Fe exhibited remarkable performance in the reductive degradation of triclosan. Several dechlorinated intermediates were predicted by GC-MS spectrum, and 2-phenoxyphenol was detected as the by-product of the decomposition reaction of triclosan, indicating that reductive dechlorination occurred continuously. As the reaction proceeded, the pH of the solution increased steadily; the pH increase for the Pd/Fe system was smaller than that for the Fe0 and Aw/Fe system. Further, zero-order, first-order, and second-order kinetic models were used to analyze the reaction kinetics. The first-order kinetic model was found to be the best with good correlation for the Fe0 and Aw/Fe system. However, for the Pd/Fe system, the experimental data were evaluated to be well fitted to the second-order kinetic model. The reaction rate constants (k) were in the order of Pd/Fe > Aw/Fe > Fe0, with the rate constant of Pd/Fe being much higher than that of the other two reductants.

In this study, the reductive decolorization of three acid and basic dyes using modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium coated iron (Pd/Fe)) at various pH conditions (pH 3 5) was experimentally investigated and the decolorization characteristics were evaluated by analyzing the absorbance spectra and reaction kinetics. In the case of acid dyes such as methyl orange and eriochrome black T, color removal efficiencies increased as initial pH of the dye solution decreased. However, the color removal of methylene blue, a basic dye, was not affected much by the initial pH and more than 70% of color was removed within 10 min. During the decolorization reaction, the absorbance of methyl orange (λmax = 464 nm) and eriochrome black T (λmax = 528 nm) decreased in the visible range but increased in the UV range. The absorbance of methylene blue (λmax = 664 nm) also decreased gradually in the visible range. Pseudo-zero order, pseudo-first order, and pseudo-second order kinetic models were used to analyze the reaction kinetics. The pseudo-second order kinetic model was found to be the best with good correlation. The decolorization reaction rate constants (k2) of methylene blue were relatively higher than those of methyl orange and eriochrome black T. The reaction rate constants of methyl orange and eriochrome black T increased with a decrease in the initial pH.

In order to treat groundwater containing high levels of nitrate, nitrate reduction by nano sized zero-valent iron (nZVI) was studied using batch experiments. Compared to nitrate removal efficiencies at different mass ratios of nitrate/Fe0, the removal efficiency at the mass ratio of 0.02% was the highest(54.59%). To enhance nitrate removal efficiency, surface modification of nZVI was performed using metallic catalysis such as Pd, Ni and Cu. Nitrate removal efficiency by Cu-nZVI (at catalyst/Fe0 mass ratio of 0.1%) was 66.34%. It showed that the removal efficiency of Cu-nZVI was greater than that of the other catalysts. The observed rate constant (kobs) of nitrate reduction by Cu-nZVI was estimated to 0.7501 min-1 at the Cu/Fe mass ratio of 0.1%. On the other hand, TEM images showed that the average particle sizes of synthetic nZVI and Cu-nZVI were 40~60 and 80~100 nm, respectively. The results imply that catalyst effects may be more important than particle size effects in the enhancement of nitrate reduction by nZVI.

광산배수가 지표에 노출되거나 주변 수계로 유입됨에 따라 나노크기의 철 교질물질이 형성되며, 이러한 철 교질물질은 심미적 오염을 발생시킬 뿐만 아니라 수생태계에도 악영향을 미친다. 이를 제어하기 위해 철 나노물질의 거동특성을 파악하는 것이 매우 중요한데, 아직까지 이에 대한 연구가 미흡하다. 본 연구는 영가철과 자철석을 이용하여 배경용액의 pH와 조성, 그리고 자연유기물에 따른 철 나노물질의 거동특성을 고찰하기 위해 수행되었다. 이를 위해 동적광산란분석기를 이용하여 철 나노물질의 입자크기와 표면 제타전위를 측정하였으며, DLVO (Derjaguin, Landau, Verwey, and Overbeek) 이론에 적용하여 응집 및 분산 등의 거동특성을 비교하였다. 철 나노물질은 영전하점 pH 근처에서는 입자간의 전기적 인력으로 인한 응집이 발생되며, 그보다 pH가 낮거나 높으면 전기적 반발력에 의해 분산이 잘되는 것을 확인하였다. 배경용액 내 양이온이 음이온보다 거동특성에 더 큰 영향을 끼치는 것을 확인하였으며, 특히 1가 양이온보다 2가 양이온이 입자표면간의 전기적인 인력 및 반발력에 더 큰 영향을 주는 것을 알 수 있었다. 수용상의 자연유기물은 철 나노물질을 코팅함으로써 표면을 음전하로 띠게 하여 분산이 잘 되게 하는 것을 확인하였다. 동일한 환경조건에서 자철석보다 영가철이 응집이 더 잘 되는 것으로 나타났는데, 이는 영가철의 낮은 안정성과 빠른 반응성으로 인해 철 산화물로 변질되기 때문인 것으로 판단된다.

This study examined the treatment characteristics of hard-to-degrade pollutants such as TCE which are found in organic solvent and cleaning wastewater by nZVI that have excellent oxidation and reduction characteristics. In addition, this study tried to find out the degradation characteristics of TCE by Fenton-like process, in which H2O2 is dosed additionally. In this study, different ratios of nZVI and H2O2, such as 1.0 mM : 0.5 mM, 1.0 mM : 1.0 mM, and 1.0 mM : 2.0 mM were used. When 1.0 mM of nZVI was dosed with 1.0 mM of H2O2, the removal efficiency of TOC was the highest and the first order rate constant was also the highest. When 1mM of nZVI was dosed with 0.5 mM of H2O2, the first order rate constant and removal efficiency were the lowest. The size of first order rate constant and removal efficiency was in the order of nZVI 1.0 mM : H2O2 1.0 mM ＞ nZVI 1.0 mM : H2O2 2.0 mM ＞ nZVI 1.0 mM : H2O2 0.5 mM ＞ H2O2 1.0 mM ＞ nZVI 1.0 mM. It is estimated that when 1.0 mM of nZVI is dosed with 1.0 mM of H2O2, Fe2+ ion generated by nZVI and H2O2 react in the stoichiometric molar ratio of 1:1, thus the first order rate constant and removal efficiency are the highest. And when 1.0 mM of nZVI is dosed with 2.0 mM of H2O2, excessive H2O2 work as a scavenger of OH radicals and excessive H2O2 reduce Fe3+ into Fe2+. As for the removal efficiency of TOC in TCE by simultaneous dose and sequential dose of nZVI and H2O2, sequential dose showed higher first order reaction rate and removal efficiency than simultaneous dose. It is estimated that when nZVI is dosed 30 minutes in advance, pre-treatment occurs and nanoscale Fe0 is oxidized to Fe2+ and TCE is pre-reduced and becomes easier to degrade. When H2O2 is dosed at this time, OH radicals are generated and degrade TCE actively.