Economic and Environmental Geology (자원환경지질)

The Korean Society of Economic and Environmental Geology (대한자원환경지질학회)
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Evaluation of Manganese Removal from Acid Mine Drainage by Oxidation and Neutralization Method

산화법과 중화법을 이용한 산성광산배수 내 망간 제거 평가

  • Kim, Bum-Jun (Department of Integrated Energy and Infra System, Graduate School, Kangwon National University) ;
  • Ji, Won-Hyun (Institute of Mine Reclamation Technology, Mine Reclamation Corporation (MIRECO)) ;
  • Ko, Myoung-Soo (Department of Integrated Energy and Infra System, Graduate School, Kangwon National University)
  • 김범준 (강원대학교 에너지.인프라 시스템 융합학과) ;
  • 지원현 (한국광해관리공단 기술연구소) ;
  • 고명수 (강원대학교 에너지.인프라 시스템 융합학과)
  • Received : 2020.07.31
  • Accepted : 2020.12.02
  • Published : 2020.12.28
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Abstract

Two oxidizing agents (KMnO4, H2O2), and one neutralizing agent (NaOH) were applied to evaluate Mn removal in mine drainage. A Mn2+ solution and artificial mine drainage were prepared to identify the Fe2+ influence on Mn2+ removal. The initial concentrations of Mn2+ and Fe2+ were 0.1 mM and 1.0 mM, respectively. The injection amount of oxidizing and neutralizing agents were set to ratios of 0.1, 0.67, 1.0, and 2.0 with respect to the Mn2+ mole concentration. KMnO4 exhibited a higher removal efficiency of Mn2+ than did H2O2 and NaOH, where approximately 90% of Mn2+ was removed by KMnO4. A black MnO2 was precipitated that indicated the oxidation of Mn2+ to Mn4+ after an oxidizing agent was added. In addition, MnO2 (pyrolusite) is a stable precipitate under pH-Eh conditions in the solution. However, relatively low removal ratios (6%) of Mn2+ were observed in the artificial mine drainage that included 1.0 mM of Fe2+. The rapid oxidation tendency of Fe2+ as compared to that of Mn2+ was determined to be the main reason for the low removal ratios of Mn2+. The oxidation of Fe2+ showed a decrease of Fe concentration in solution after injection of the oxidizing and neutralizing agents. In addition, Mn7+ of KMnO4 was reduced to Mn2+ by Fe2+ oxidation. Thus, the concentrations of Mn increased in artificial mine drainage. These results revealed that the oxidation method is more effective than the neutralization method for Mn removal in solution. It should also be mentioned that to achieve the Mn removal in mine drainage, Fe2+ removal must be conducted prior to Mn2+ oxidation.

이 연구에서는 KMnO4, H2O2, NaOH와 같은 산화제와 중화제를 사용하여 광산배수 내 Mn 제거효율을 확인하고 광산배수에 다량으로 존재하는 Fe2+의 영향을 파악하고자 하였다. 용액 내 Fe2+의 유무에 따라 Mn의 제거여부를 확인하기 위하여 초기농도 0.1 mM의 Mn2+ 용액을 준비하였다. 이때, 광산배수모사 용액의 Fe2+ 농도는 1 mM이 되도록 조성하였다. 산화제와 중화제의 주입량은 용액 내 Mn2+를 기준으로 각각의 몰비가 0.1, 0.67, 1.0, 2.0이 되도록 주입하였으며, Mn2+의 제거효율은 산화제인 KMnO4를 주입한 경우 최대 90%로 가장 높은 결과를 보였다. 산화제 주입 후 검은색의 MnO2 침전물이 형성되어 Mn2+의 산화제거를 확인하였고, 반응용액의 pH-Eh 조건에서 Mn 산화물인 Pyrolusite (MnO2)가 안정함을 확인하였다. 그러나 용액 내 Fe2+가 존재하는 광산배수 모사용액에서는 용액 내 Mn2+의 제거율이 6%로 매우 낮은 결과를 보였다. 이러한 결과는 Mn2+의 산화보다 Fe2+의 산화가 더욱 빠르게 진행되면서 Mn 산화물 형성을 저해하기 때문으로 판단된다. 산화제 및 중화제 주입 후 용액 내 Fe의 농도가 급격히 감소하는 결과는 Fe2+의 산화에 기인한 것으로 판단된다. 또한, Fe2+의 산화 과정에서 KMnO4의 Mn7+가 Mn2+로 환원되어 광산배수 모사 용액의 용존 Mn의 농도가 오히려 증가하는 결과를 보이기도 하였다. 이상의 결과로 보아, 용액에 존재하는 Mn을 제거하기 위해서는 산화법이 중화법보다 더 효과적이며, 광산배수에 존재하는 다량의 Fe2+를 먼저 제거한 후 용존 Mn의 제거를 진행하는 것이 효과적인 것으로 판단된다.

Keywords

References

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