Minerals Engineering 35 (2012) 5760

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Technical Note

Recovery of iron from zinc calcines by reduction roasting and magnetic separation
Ning Peng a, Bing Peng a,b,, Li-Yuan Chai a,b, Mi Li a, Ji-Ming Wang a, Huan Yan a, Yuan Yuan a
a
b

Institute of Environmental Science and Engineering, School of Metallurgical Science and Engineering, Central South University, 410083 Changsha, Hunan, China
Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, 410083 Changsha, Hunan, China

a r t i c l e

i n f o

Article history:
Received 22 February 2012
Accepted 15 May 2012
Available online 16 June 2012
Keywords:
Reduction roasting
Magnetic separation
Zinc calcine
Zinc ferrite

a b s t r a c t
A new method to recover iron from high iron-bearing zinc calcine was developed. Zinc ferrite (ZnFe2O4)
in zinc calcine was decomposed to zinc oxide and magnetite after roasting under a reducing atmosphere
at temperatures over 700 C. A mineral dressing by magnetic separation was used to recover magnetite
from the roasted products. The effects of the roasting temperature and magnetic induction intensity on
the grade and recovery of iron were investigated. Ultrasonic treatment and mechanical milling played an
important part in breaking the encapsulated magnetic phases before magnetic separation. The results
show that iron recovery increases with roasting temperature and magnetic induction intensity, and ultrasonic treatment and mechanical milling promote the recovery of iron by 20% compared to the roasted
zinc calcine subjected to magnetic separation at the same magnitude.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Zinc ferrite is generated during the desulphurising roasting process of sphalerite, It is hardly soluble at mild acid conditions and
could form hazardous residues (Erdem and zverdi, 2011; Swarnkar et al., 1996). The concerns are not only environmental but economic, as well. Because of the depletion of zinc ores and the rapid
rise of metal prices.
Various hydrometallurgical and pyrometallurgical processes for
zinc recovery from wastes containing zinc ferrite are currently
used. High zinc recovery is achieved in hydrometallurgical processes. However, the sophisticated purication process and high
environmental risk make these leaching processes unsuitable for
mass production (Dutra et al., 2006; Jha et al., 2001; Leclerc
et al., 2003; Soylak et al., 2007; Vahidi et al., 2009). In pyrometallurgical methods, zinc ferrite is converted into soluble zinc and
iron compounds under high temperature. However, there exist
large difculties for the further treatment of roasting residues. Also
they are necessary to employ the same long purication processes
following the extraction, as in hydrometallurgical processes (Holloway and Etsell, 2008; Jiang et al., 2006; Turan et al., 2004).
This paper focuses on the separation of iron from zinc calcine by
a reduction roasting-magnetic separation process. In this process, a
mixture of carbon monoxide (CO) and nitrogen (N2) is applied as a
reducing agent. The reactions during roasting process are as
follows.
Corresponding author at: Institute of Environmental Science and Engineering,
School of Metallurgical Science and Engineering, Central South University, 410083
Changsha, Hunan, China. Tel.: +86 731 88830875; fax: +86 731 88710171.
E-mail address: pb1956@yahoo.cn (B. Peng).
0892-6875/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2012.05.014

3ZnFe2 O4 CO 3ZnO 2Fe3 O4 CO2

ZnFe2 O4 CO ZnO 2FeO CO2

The magnetite in the roasting product is recovered by magnetic

separation, and the zinc oxide enters the tailing of magnetic separation and returns to the traditional zinc process as a raw material.
This process has the advantages of a lower roasting temperature
than the traditional process and a simple processing ow. In this
study, the effect of the roasting temperature and the magnetic
induction intensity on the separation of iron was investigated.
Meanwhile, the effects of pre-treatment including sonication and
milling prior to magnetic separation on the iron grade of concentrate were analysed.
2. Materials and methods
2.1. Materials
The high-iron zinc calcine sample with approximately 54.8%
zinc and 12.68% iron, which was used in this study, was obtained
from a zinc hydrometallurgical plant located in Inner Mongolia,
China. The sample was sieved to obtain a required fraction of
below 200 meshes (75 lm) and was dried at 70 C for 24 h.
2.2. Reduction roasting
In roasting process, the samples were heated under a nitrogenrich atmosphere to a desired reduction temperature and carbon
monoxide gas was later introduced for reduction. After 2 h, the
reducing gas mixture was replaced by nitrogen, and the roasting
product was cooled to room temperature in nitrogen. Roasting

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N. Peng et al. / Minerals Engineering 35 (2012) 5760

Fig. 1. Mssbauer spectrum of (A) original material and (B) product roasted at 850 C and the effect of (C) roasting temperature, (D) magnetic intensity, (E) ultrasonic
pretreatment and (F) mechanical milling on the recovery and grade of iron in concentrate.

temperatures ranging from 700 C to 900 C at 50 C increments

were examined, while duration time and volume fraction of CO
were held constant at 2 h and 10%, respectively.

(potassium dichromate titration for Fe and EDTA titration for Zn)

and SEM.

2.4. Pre-treatment
2.3. Magnetic separations
Magnetic separation (MS) was performed on a slurry of reduced
samples (10% in solid) using a Davis tube tester. A MS scheme under constant slurry ow rate and a targeted magnetic induction
intensity ranging from 700 to 1700 G was used for MS. The eld
was then switched off and the magnetic fraction was washed
through using 12 L water. The magnetic fractions were ltered,
dried, weighed and subjected to such assays as chemical analysis

A specied sonic processor (Shanghais, FS-300, 20 kHz, and

300 W) was employed for sonication of the mixture of ethanol
(100 ml) and roasting products (5 g). The reaction time was maintained between 0 and 40 min in 10 min increments. The treated
products were used directly for MS.
The wet milling operation was conducted in a planetary ball
with a hardened chrome steel via in a mixture with a roasting
product-to-water ratio of 1:20 at room temperature and a rotation

N. Peng et al. / Minerals Engineering 35 (2012) 5760

59

Fig. 2. SEM spectrum of (A) concentrate of direct MS, (B) concentrate which pretreated by ultrasonic, (C) concentrate which pretreated by milling obtained in 950 G magnetic
and (D) Particle size distribution of (AC).

speed 300 r/min. The time of milling varies from 0 to 40 min, and
the treatment of the processing product was the same as that of
ultrasonic pre-treatment.
2.5. Characterisations of samples
The morphology of the samples was observed by a scanning
electron microscope (JEOL.LTD, JSM-6360LV). The Mssbauer spectrum (Wissel uniform accelerated Mssbauer spectrograph system) was used to characterise the iron phases change in the
roasting process. Analysis of the particle size distribution (Hydro
2000MU-A) was carried out to determine the size reduction caused
by sonication and milling.
3. Results and discussion
3.1. Result of magnetic roasting-magnetic dressing
The Mssbauer spectra were determined at room temperature
using 57Co (Pd) as a radio source (Fig. 1). As observed in Fig. 1A,
the presence of only doublets suggests that the paramagnetic
mineral phase consisted mainly of zinc ferrite. In Fig. 1B, the
doublet is also related to zinc ferrite and two of the superimposed

sextets that are determined to be the magnetite A-site sextet and

magnetite B-site sextet, respectively. The left sextet is related to
a type of magnetic FeZn solid solution (Chen and Xin, 1992;
Morrish and Clark, 1975). Conrmed by the results of Mssbauer
spectra analysis, the zinc ferrite in zinc calcine was well decomposed into zinc oxide and magnetite.
Fig. 1C shows that the recovery of iron increases signicantly
with the increase in roasting temperature in 950 G. But when the
temperature reached 900 C, although the recovery is much higher
than the recovery achieved under 850 C, the grade of iron decreases sharply and becomes similar to that observed in zinc calcine due to the tight self-sintering of samples. Fig. 1D shows that
the recovery increases sharply and reaches its peak of 64.2% when
the magnetic induction intensity is maintained at 1160 G, after
which a constant recovery is observed when the magnetic induction intensity is increased to 1640 G. While the grade uctuate between 18% and 20% Sonication (20 kHz, 300 W) was applied to
disperse the particle encapsulation prior to the MS at 950 G (see
Fig. 1E) Obviously, the recovery of iron is strongly dependent on
the time of the ultrasonic process and reaches its maximum value
of 58.34% at 20 min, which is nearly 20% higher than the result of
direct MS. However, a slight downward trend is observed with a
further increase of sonication time. For the milling, it is shown in
Fig. 1F that both the recovery and grade achieve their maximum

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N. Peng et al. / Minerals Engineering 35 (2012) 5760

at a grinding duration of 20 min. The reduction of both recovery

and grade are considerably more pronounced than that of sonication after 20 min.
3.2. Result of micro-analysis
The SEM spectrums and particle size analysis of the samples
after magnetic operation were carried out. Fig. 2AC shows the
SEM spectrum of concentrate of MS at a magnetic eld of 950 G
for a product roasted at 850 C. Comparison of Fig. 2A and B reveals
that the physically combined particles disappeared after sonication. This result means that sonication could destroy the physical
enfoldment of particles and cause the rise of iron recovery. It can
be seen from Fig. 2C that the self-sintering structure has been destructed at some extent. Consequently, superne particles could be
found in these gures. From Fig. 2 D, it is evident that the particle
size of sonication samples is smaller than that of unsonicated samples, while the milling samples achieve the biggest particle size
reduction among the three tested samples; therefore, the increase
of iron grade in milling-MS concentration appears to be the result
of the reduction in particle size.

4. Conclusions
The results of this study show that zinc ferrite was decomposed
to form zinc oxide and magnetite in the presence of a reducing gas
mixture. As observed from the results of direct MS, the recovery of
iron increases with the increase of roasting temperature and magnetic induction intensity, while the grade of iron in concentrate is
quite difcult to increase. The sonication pre-treatment can crush
the physical inclusion of particles and promote the recovery of
iron, but it can do little to increase the iron grade. The milling
pre-treatment can break the self-sintering aggregation to a certain
extent and promote the recovery and grade of iron in concentrate.

Acknowledgements
The authors would also like to thank the National High
Technology Research and Development Programme of China
(2011AA061001), the National Scientic Research Project of Welfare (Environmental) Industry (2011467062), the National Science
Found for Distinguished Young Scholars of China (50925417) and
the National Natural Science Foundation of China (50830301) for
their support of this study.
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