Journal of Korean Society of Environmental Engineers (대한환경공학회지)

Korean Society of Environmental Engineers (대한환경공학회)
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A Comparative Study on the Removals of 1-Naphthol by Natural Manganese Oxides and Birnessite

천연망간산화물과 버네사이트에 의한 1-Naphthol의 제거 특성 비교

  • Lee, Doo-Hee (Department of Environmental Engineering, Seoul National University of Technology) ;
  • Harn, Yoon-I (Department of Environmental Engineering, Seoul National University of Technology) ;
  • Kang, Ki-Hoon (Dealim Industrial Inc.) ;
  • Shin, Hyun-Sang (Department of Environmental Engineering, Seoul National University of Technology)
  • Received : 2009.04.10
  • Accepted : 2009.04.28
  • Published : 2009.04.30
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Abstract

In this study, four natural Mn oxides ($NMO_1-NMO_4$) was characterized using x-ray diffraction, scanning electron microscopy, and their removal efficiency for 1-naphthol (1-NP) in aqueous phase, using batch reactor, was investigated. The results were compared with one another and a synthetic manganese oxide, birnessite. The NMOs have a various Mn minerals including pyrolusite (${\beta}-MnO_2$), cryptomeltane (${\alpha}-MnO_2$) as well as birnessite (${\delta}-MnO_2$) depending on their sources, which results in different removal efficiencies (removals, kinetics) and reaction types (sorption or oxidative-transformation). The comparative study showed that $NMO_1$ (electrolytic Mn oxide) have a higher removal efficiency for 1-NP via oxidative-transformation compared to birnessite. The 1-NP removals by NMOs were followed by pseudo-first order reaction, and the surface area-normalized specific rate constants ($K_{surf},\;L/m^2$ min) determined were in order of $NMO_1(3.31{\times}10^{-3})$>${\delta}-MnO_2(1.48{\times}10^{-3}){\fallingdotseq}NMO_3(1.46{\times}10^{-3})$>$NMO_2(0.83{\times}10^{-3})$>$NMO_4(0.67{\times}10^{-3})$. From the solvent extraction experiments with the Mn oxide precipitates after reaction, it was observed that the oxidative-transformation rates of 1-NP were in order of $NMO_1{\fallingdotseq}{\delta}-MnO_2$>$NMO_3$>$NMO_4{\gg}NMO_2$ and the analysis of HPLC chromatogram and UV-Vis. absorption ratios ($A_{2/4}$, $A_{2/6}$) on the supernatant confirmed that the reaction products were oligomers formed by oxidative-coupling reaction. Results from this study proved that natural Mn oxide (except $NMO_2$) used in this experiment can be effectively applied for the removal of naphthols in aqueous phase, and the removal efficiencies are depending on the surface characters of the Mn oxides.

본 연구에서는 망간원석을 포함한 4종의 천연망간산화물($NMO_1\;NMO_4$)을 대상으로 물질특성(결정상, 표면형태)과 1-naphthol (1-NP)에 대한 제거반응 특성을 회분식 실험을 통하여 수행하였고, 그 결과를 버네사이트에서의 결과와 비교 분석하였다. 천연망간산화물은 출처에 따라 버네사이트(${\delta}-MnO_2$)외에도 크립토멜란(${\alpha}-MnO_2$), 연망간석(${\beta}-MnO_2$) 등의 다양한 표면 특성을 동시에 가지고 있었으며, 이러한 표면 특성으로 인해 제거효율(제거율, 반응속도) 및 제거반응(흡착 또는 산화-변환제거)에서 차이를 보였다. 특히, $NMO_1$(전해망간산화물)은 버네사이트에 비교해서도 우수한 1-NP의 산화-변환 제거효율을 보임을 알 수 있었다. 망간산화물에 의한 1-NP의 제거는 모두 유사-일차속도 식을 따랐으며, 각 망간산화물의 비표면적으로 표준화하여 얻은 속도상수($k_{surf},\;L/m^2$ min) 값은 $NMO_1(3.31{\times}10^{-3})$>${\delta}-MnO_2(1.48{\times}10^{-3}){\fallingdotseq}NMO_3(1.46{\times}10^{-3})$>$NMO_2(0.83{\times}10^{-3})$>$NMO_4(0.67{\times}10^{-3})$의 순이었다. 또한, 반응후 침전층에 대한 용매추출실험을 통해 평가한 1-NP의 산화-변환 반응효율은 $NMO_1{\fallingdotseq}{\delta}-MnO_2$>$NMO_3$>$NMO_4{\gg}NMO_2$의 순이었으며, 반응산물은 반응여액(상등액)에 대한 HPLC 크로마토그램, UV-vis. 흡광도비($A_{2/4}$, $A_{2/6}$) 분석을 통해 버네사이트에서와 같이 1-napthol의 산화-결합 반응에 의한 것임을 확인하였다. 이상의 결과로부터 본 실험에 사용한 천연망간산화물($NMO_2$ 제외)은 1-NP의 제거에 효과적으로 적용될 수 있으며, 반응효율은 망간산화물의 출처에 따른 표면특성에 따라 차이가 있음을 확인하였다.

Keywords

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