대한환경공학회지 (Journal of Korean Society of Environmental Engineers)

  • 제38권11호
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  • Pages.603-610
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  • 2016
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  • 1225-5025(pISSN)
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  • 2383-7810(eISSN)
대한환경공학회 (Korean Society of Environmental Engineers)
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폐 알칼리망간전지의 산 침출액으로부터 버네사이트(δ-MnO2)의 제조 및 1-naphthol 제거

Preparation of Birnessite (δ-MnO2) from Acid Leaching Solution of Spent Alkaline Manganese Batteries and Removals of 1-naphthol

  • 엄원숙 (서울과학기술대학교 환경공학과) ;
  • 이한샘 (서울과학기술대학교 환경공학과) ;
  • 이동석 (강원대학교 환경공학과) ;
  • 신현상 (서울과학기술대학교 환경공학과)
  • Eom, Won-Suk (Department of Environmental Engineering, Seoul National University of Sience and Technology) ;
  • Lee, Han-Saem (Department of Environmental Engineering, Seoul National University of Sience and Technology) ;
  • Rhee, Dong-Seok (Department of Environmental Engineering, Kangwon National University) ;
  • Shin, Hyun-Sang (Department of Environmental Engineering, Seoul National University of Sience and Technology)
  • 투고 : 2016.10.12
  • 심사 : 2016.11.18
  • 발행 : 2016.11.30
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초록

본 연구에서는 폐 알칼리망간전지 분말(spent alkaline manganese battery powder, SABP <8 mesh)의 산 침출액으로부터 분리한 망간이온을 이용하여 산화-중합반응 촉매인 버네사이트를 제조하였고, 1-naphthol (1-NP)을 대상으로 페놀계 화합물의 제거 반응성을 조사하였다. 망간산화물의 결정상과 반응성은 순수 망간시약($MnSO_4$, $MnCl_2$)을 사용하여 합성한 망간산화물(manganese oxide, MOs) 및 기존의 McKenzie 합성방법에 의한 Acid birnessite (A-Bir)의 결과와도 비교 평가하였다. SABP에 존재하는 망간과 아연이온은 과산화수소 존재 하에서의 황산 침출($1.0M\;H_2SO_4+10.5%\;H_2O_2$, solid/liquid (S/L)비=1/10 g/mL, $60^{\circ}C$)을 통해 각각 약 96%와 98% 회수하였다. 산 침출액으로부터 망간이온은 수산화물(NaOH) 침전을 통해 pH 8과 pH>13 조건에서 각각 69.0%와 94.3% 분리하였다. 1-NP 제거능을 토대로 SABP 산 침출액으로부터 알칼리(NaOH) 수열합성법에 의한 망간산화물의 제조를 위한 적정 OH/Mn 혼합비(M/M)는 6.0이었고, XRD 분석을 통해 버네사이트(${\delta}-MnO_2$) 결정상을 가짐을 확인하였다. pH 8 (${Mn^{2+}}_{(aq)}$)과 pH>13 ($Mn(OH)_{2(s)}$)에서 회수한 망간을 사용하여 얻은 망간산화물의 1-NP 제거 반응속도(k, at pH 6)는 각각 0.112, $0106min^{-1}$으로서 $MnSO_4$ 시약을 사용하여 얻은 망간산화물의 결과($0.117min^{-1}$)와 유사하였다. 이상의 연구를 통해 폐 알칼리망간전지 분말로부터 얻은 버네사이트는 미량 유해물질 제거를 위한 산화-중합 반응 촉매로 활용 가능함을 알 수 있었으며, 버네사이트 제조를 위한 폐 알칼리망간전지의 재활용 흐름도를 제시하였다.

This work studies the synthesis of birnessite (${\delta}-MnO_2$), a catalyst of oxidative-coupling reactions, from the powder of spent alkaline manganese batteries (SABP, <8 mesh) and evaluate its reactivity for 1-naphthol (1-NP) removals. Manganese oxides using commercial reagents ($MnSO_4$, $MnCl_2$) and the acid birnessite (A-Bir) by McKenzie method were also synthesized, and their crystallinity and reactivity for 1-NP were compared with one another. 96% Mn and 98% Zn were extracted from SABP by acid leaching at the condition of solid/liquid (S/L) ratio 1:10 in $1.0M\;H_2SO_4+10.5%\;H_2O_2$ at $60^{\circ}C$. From the acid leaching solution, 69% (at pH 8) and 94.3% (pH>13) of Mn were separated by hydroxide precipitation. Optimal OH/Mn mixing ratio (mol/mol) for the manganese oxide (MO) synthesis by alkaline (NaOH) hydrothermal techniques was 6.0. Under this condition, the best 1-NP removal efficiency was observed and XRD analysis confirmed that the MOs are corresponding to birnessite. Kinetic constants (k, at pH 6) for the 1-NP removals of the birnessites obtained from Mn recovered at pH 8 (${Mn^{2+}}_{(aq)}$) and pH>13 ($Mn(OH)_{2(s)}$) are 0.112 and $0.106min^{-1}$, respectively, which are similar to that from $MnSO_4$ reagent ($0.117min^{-1}$). The results indicated that the birnessite prepared from the SABP as a raw material could be used as an oxidative-coupling catalyst for removals of trace phenolic compounds in soil and water, and propose the recycle scheme of SAB for the birnessite synthesis.

키워드

참고문헌

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