Preparation of Birnessite (δ-MnO<sub>2</sub>) from Acid Leaching Solution of Spent Alkaline Manganese Batteries and Removals of 1-naphthol

Eom, Won-Suk; Lee, Han-Saem; Rhee, Dong-Seok; Shin, Hyun-Sang; Eom, Won-Suk; Lee, Han-Saem; Rhee, Dong-Seok; Shin, Hyun-Sang

doi:2016.38.11.603

The Korean text of this paper can be translated into multiple languages on the website of http://jksee.or.kr through Google Translator.

J Korean Soc Environ Eng > Volume 38(11); 2016 > Article

Original Paper

J Korean Soc Environ Eng 2016;38(11): 603-610. doi: https://doi.org/10.4491/KSEE.2016.38.11.603

폐 알칼리망간전지의 산 침출액으로부터 버네사이트(δ-MnO₂)의 제조 및 1-naphthol 제거

엄원숙¹, 이한샘¹, 이동석², 신현상¹

¹서울과학기술대학교 환경공학과
²강원대학교 환경공학과

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

Won-Suk Eom¹, Han-Saem Lee¹, Dong-Seok Rhee², Hyun-Sang Shin¹

¹Department of Environmental Engineering, Seoul National University of Sience and Technology
²Department of Environmental Engineering, Kangwon National University

Corresponding author

Hyun-Sang Shin ,Tel: 02-970-6625, Fax: 02-971-5776, Email: hyuns@seoultech.ac.kr

Received: October 12, 2016; Revised: November 10, 2016; Accepted: November 18, 2016. Published online: November 30, 2016.

ABSTRACT

This work studies the synthesis of birnessite (δ-MnO₂), 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 (MnSO₄, MnCl₂) 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 1.0 M H2SO₄ + 10.5% H₂O₂ at 60℃. 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 (Mn²⁺(aq)) and pH>13 (Mn(OH)_2(s)) are 0.112 and 0.106 min^-1, respectively, which are similar to that from MnSO₄ reagent (0.117 min^-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.

Key Words: Spent Alkaline Battery, Acid Leaching, Mn Separation, Birnessite, Oxidative-Transformation