Simultaneous recovery of zinc and manganese dioxide from household alkaline batteries through hydrometallurgical processing

doi:10.1016/j.jpowsour.2004.05.019

Journal of Power Sources

Volume 136, Issue 1, 10 September 2004, Pages 191-196

https://doi.org/10.1016/j.jpowsour.2004.05.019 Get rights and content

Abstract

This paper describes the leaching experiments and the electrowinning tests to recover Zn and Mn from spent household alkaline batteries. After the dismantling of the batteries, the black powder was analyzed and found to contain 21 wt.% Zn and 45%wt. Mn. Therefore, it was considered that recovery of these metals would be interesting due to their relatively large amounts in this kind of waste. Batch laboratory experiments were carried out to develop an acid leaching procedure and to determine appropriate leaching conditions to maximize zinc extraction and to study the leaching behavior of Mn. An experimental study was undertaken to evaluate the feasibility of simultaneous recovery of zinc and particulate manganese dioxide using a laboratory cell. The results from these electrowinning experiments are also presented in this paper.

Introduction

Nowadays, large amounts of materials are been discarded as waste, but some of them could be recovered instead. Recycling rates for metals are growing in many developed countries. In the 1980s, the lead, zinc and tin industries were in a crisis caused by stagnation of the market, and secondary raw materials from lead batteries, zinc plant leach operations and steel plant dusts were accumulated as observed by Engh [1], who predicted an increasing in metal recovery from scrap and wastes. Used household batteries could be one of the secondary sources of metals, and the recycling of these wastes would offer economic benefits through the recovery of the valuable materials, as well as the preservation of raw materials in the interest of the sustainable development.

During the last decade, the producers of batteries were engaged trying to find substitutes for toxic substances still used in batteries, to match environmental requirements; although, the basic systems of the batteries and its composition (steel, plastic, zinc, manganese dioxide, steel casings, paper, carbon, and brass) still remains the same.

Most of these materials can be technically recovered by means of mechanical and chemical treatment. The materials recovered show some advantages as they could be returned to the batteries production as raw material or can be used for other purposes. The steel scrap can be sold to steel mills; manganese could be sold to the steel industry, and zinc can be used in metallurgical industries.

Several processes for the recycling of batteries [2], [3], [4], [5], [6], [7], [8], [9] have been proposed, mainly in Europe, and the pyrometallurgical processes are the most used.

Hydrometallurgical processes have also been proposed to recycle batteries. According to Bartolozzi [10] the recovery of Zn and MnO₂ was obtained after the acid leaching of batteries followed by electrolysis. The Batenus process that recycles mixed batteries uses sulfuric acid leaching and solvent extraction, electrolysis, ion exchange, precipitation and reverse osmosis to recover valuable products [11]. Rabah [12] studied the treatment of batteries by acid leaching and Zn precipitation by oxalic acid and Mn precipitation by Na₂CO₃.

Section snippets

Alkaline batteries

Most portable devices require AA, C or D batteries, which corresponds to the largest percentage of batteries used for general household purposes. Alkaline batteries are included in this group as non-rechargeable batteries (primary cells), which are designed to be fully discharged, and present the advantage of a life time longer than the zinc–carbon cells. The alkaline cell uses an electrochemical system where zinc and manganese dioxide are the anode and the cathode, respectively. Powdered zinc

Experimental procedures

A consignment of used alkaline batteries was dismantled using a hammer mill, and the residual fine portion obtained (0.208 mm) containing the metals to be recovered was treated hydrometallurgically. After chemical analysis to determine the total composition of the samples, a leaching procedure was performed aiming to recovery the metals from the aqueous solution using electrowinning of both metals, Zn and Mn.

All chemical analysis in this study were performed using an atomic absorption

Characterization of dry powder

The X-ray diffraction spectrum is shown in Fig. 1 and the results of chemical analysis are listed in Table 1.

The results of chemical analysis show expressive amount of Zn and Mn, which represents 66% of the total mass of the sample. According to the X-ray spectrum, ZnO is the main zinc compound found in the dry powder. Mn of different valences was found in the X-ray spectrum, not only Mn₂O₃ as suggested by the literature. In fact, it can not be predicted that all batteries were submitted to the

Conclusions

1.
The presence of 45% Mn and 21% Zn in pulverized alkaline battery powder makes this an attractive source for a simultaneous recovery.
2.
Leaching at low acid concentration an dissolve all Zn and 40% of Mn contained in dry powder.
3.
Zinc and manganese can be recovered by simultaneous electrowinning of its aqueous solutions with lead anode and aluminum.

Acknowledgements

The authors would like to thank to Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP), project 98/10882-9 and 98/01227-7, for the financial support for this project.

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Citation Excerpt :
From the proposed pre-treatment, the anode is fully separated from the remaining components. From the conducted bibliographic research regarding the recycling of alkaline batteries, most of the developed work aimed at recovering zinc (Barrett et al., 2011; Deep et al., 2011, 2016; Ebin et al., 2016, 2017; Kunický et al., 2012; López et al., 2017; Lorero et al., 2020; Maryam Sadeghi et al., 2017; Souza et al., 2001; Vellingiri et al., 2018) or recovering zinc along with manganese (Abid Charef et al., 2017; Andak et al., 2019; Belardi et al., 2012, 2014; de Souza and Tenório, 2004; Ebin et al., 2016; Ippolito et al., 2016; Lannoo et al., 2019; Leite et al., 2019; Salgado et al., 2003; Tran et al., 2020; Veloso et al., 2005; Xará et al., 2015). Under a different approach, a recent study, conducted by Wei et al. (2021), showed the potential of employing the leaching solutions to develop an electrolytic rechargeable battery.
In the present study, a leaner process for recovering zinc from spent alkaline batteries is studied at a laboratory scale. Such process is part of a diagram, under development, that aims at maximizing the value of all the battery components while reducing the costs of treatment and the environmental footprint involved in recycling this waste. It starts by a physical and selective pre-treatment stage that separates the anode from the remaining components followed by neutral leaching (three washing cycles at room temperature, S/L ratio of 1/5 (w/v), magnetic stirring for 15 min and settling during 45 min), acid leaching of the washed solid (4 mol/L of sulphuric acid, S/L ratio of 1/3 (w/v), 120 min at room temperature under magnetic stirring) and, finally, electrowinning of zinc from the pregnant leach solution (100 mA/cm², 120 min under slow magnetic stirring). By leaching the anode alone, it is possible to obtain a solution rich in zinc (86 g/L), with very low concentration of other metals (<0.08 g/L). Such solution was adequate for zinc electrowinning, allowing an average recovery rate of 58%, without applying any purification stages, at the same time regenerating sulphuric acid for its recirculation. In conclusion, the results demonstrate that a more specific physical pre-treatment stage is highly desirable to recycle spent alkaline batteries in order to reduce the number of stages involved and the overall complexity, thus, reducing the costs involved and the potential environmental impacts, while maintaining high recovery rates of zinc.

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Short communicationSimultaneous recovery of zinc and manganese dioxide from household alkaline batteries through hydrometallurgical processing

Abstract

Introduction

Section snippets

Alkaline batteries

Experimental procedures

Characterization of dry powder

Conclusions

Acknowledgements

J. Power Sources

Resour. Conserv. Recycl.

Recycling of used Ni-MH Rechargeable Batteries, in: Proceedings of the Third International Symposium on Recycling of Metals and Engineered Materials

The Minerals, Metals & Materials Society, vol. 1

Short communication
Simultaneous recovery of zinc and manganese dioxide from household alkaline batteries through hydrometallurgical processing