Hyperfine Interactions (2005) 161:33–42

DOI 10.1007/s10751-005-9189-x * Springer 2005

Hydrometallurgical Extraction of Zinc and

Copper – A 57Fe-Mössbauer and XRD Approach

A. F. MULABA-BAFUBIANDI1,*,j and F. B. WAANDERS2

1
Extraction Metallurgy Department, Faculty of Engineering, Technikon Witwatersrand, P.O. Box
526, Wits 2050, South Africa; e-mail: antoinemulaba@hotmail.com
2
School of Chemical and Minerals Engineering, North-West University (Potchefstroom campus),
Potchefstroom, 2531, South Africa; e-mail: chifbw@puk.ac.za

Abstract. The most commonly used route in the hydrometallurgical extraction of zinc and copper
from a sulphide ore is the concentrate–roast–leach–electro winning process. In the present in-
vestigation a zinc–copper ore from the Maranda mine, located in the Murchison Greenstone Belt,
South Africa, containing sphalerite (ZnS) and chalcopyrite (CuFeS2), was studied. The 57Fe-
Mössbauer spectrum of the concentrate yielded pyrite, chalcopyrite and clinochlore, consistent
with XRD data. Optimal roasting conditions were found to be 900-C for 3 h and the calcine
produced contained according to X-ray diffractometry equal amounts of franklinite (ZnFe2O4) and
zinc oxide (ZnO) and half the amount of willemite (Zn2SiO4). The Mössbauer spectrum showed
predominantly franklinite (59%), hematite (6%) and other Zn- or Cu-depleted ferrites (35%). The
latter could not be detected by XRD analyses as peak overlapping with other species occurred.
Leaching was done with HCl, H2SO4 and HNO3, to determine which process would result in
maximum recovery of Zn and Cu. More than 80% of both were recovered by using either one of
the three techniques. From the residue of the leaching, the Fe-compounds were precipitated and
<1% of the Zn and Cu was not recovered.
57
Key Words: Fe-Mössbauer spectroscopy, leaching, roasting, sulphide ore, XRD-analyses.

1. Introduction
Zinc in nature occurs mainly in sulphide ores as sphalerite (ZnS), but mostly
other minerals such as pyrite (FeS2), magnetite (Fe3O4), chalcopyrite (CuFeS2),
pyrrhotite (Fe1jxS) and gangue materials accompany the ore [1]. The iron pres-
ent in the ore makes recovery of the valuable zinc more difficult as zinc ferrites
are being co-produced during high temperature roasting and their insolubility in
relative dilute sulphuric acid results in a significant amount of zinc remaining in
the residue and thus a source of metal loss. However the most commonly used

* Author for correspondence.

j
From January 2005 the Technikon Witwatersrand (TWR) will complete the merger with the
Rand Afrikaanse Universiteit (RAU) to form the University of Johannesburg (UJ).
34 A. F. MULABA-BAFUBIANDI AND F. B. WAANDERS

route in the hydrometallurgical extraction of zinc and copper from such sul-
phide ores is the concentrate–roast–leach–electro winning process. Firstly the
ore is concentrated by means of flotation to eliminate all the gangue materials.
The concentrate is then roasted to produce a calcine that will be leachable to
extract the zinc and copper and finally electro winning is used to obtain the pure
metal.
The first step in the process of beneficiation of the run-of-mine (ROM) ore is
flotation, which is a technique that permits the recovery of the valuable ore
minerals in the concentrate, from solution through the introduction of surface-
active agents such as xanthate [2]. After flotation, roasting follows and various
authors [3–7] have studied the roasting process of sulphide ores where the Fe is
liberated and then precipitated to ensure maximum zinc and copper recovery.
The calcine which is formed during roasting typically contains zinc and copper
in the form of oxides (ZnO, CuO), sulphates (ZnSO4, CuSO4) and ferrites (Zn,
Cu1jxMx)OFe2O3 or (Zn, Cu)Fe2O4 and thus the roasting process ensures that
compounds suitable for further leaching are produced. Leaching, the final step to
produce a solution containing the valuable metals to be extracted by electro
winning, is described as a heterogeneous (solid/liquid) reaction and is normally
conducted by means of adding an acid to the roast product, which can be a
complex process [8] involving various chemical reactions to occur in parallel or
in series. In the present investigation a zinc–copper ore from the Maranda mine,
located in the Murchison Greenstone Belt in South Africa was studied. The main
ore minerals, as determined by X-ray diffractometry conducted at the mine, were
sphalerite (ZnS, 40%), pyrite (FeS2, 26%), magnetite (Fe3O4, 8%), chalcopyrite
(CuFeS2, 8%) and pyrrhotite (Fe1jxS, 4%), with the gangue material (14%) being
clinochlore (Mg, Fe)6(Si, Al)4O10(OH)8.

2. Experimental
The as-received ore from the mine was ground to a particle size of 80 mm. The
composition of the ore was confirmed from both mineralogical and chemical
analyses. For the flotation of the ground ore, xanthate SNPX was used as a
collector and dowfroth 400 was used as a frother. After bulk flotation of the
ore most of the gangue material was removed and the concentrate was sub-
jected to X-ray diffractometry and 57Fe-Mössbauer spectroscopy. Consequently,
roasting of the concentrate was done on 25-g batch samples, which were put in a
ceramic crucible lined with silica and then put into a laboratory furnace. The
roasting temperatures varied from 700 to 1000-C and the duration of the roasting
varied between 2 and 4 h until optimum roasting conditions were found to
produce a calcine suitable for leaching. After completion of each batch roasting
process the samples were again subjected to XRD and Mössbauer spectroscopy.
Neutral agitation leaching of the calcine, mixed with HCl, HNO3 or H2SO4
was conducted in a 1-L laboratory beaker to determine the optimum leaching