Journal of Hazardous Materials 278 (2014) 4954

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Anglesite and silver recovery from jarosite residues through roasting

and suldization-otation in zinc hydrometallurgy
Haisheng Han, Wei Sun , Yuehua Hu, Baoliang Jia, Honghu Tang
School of Mineral Processing and Bioengineering, Central South University, Changsha 410083, China

h i g h l i g h t s

Jarosite precipitate hindered the recovery of valuable minerals.

Under 600700 C, jarosite decomposed and released the encapsulated valuable minerals.
The bared valuable minerals were easily collected by otation process.
The new process was promising for dealing with jarosite residues.

a r t i c l e i n f o a b s t r a c t

Article history: Hazardous jarosite residues contain abundant valuable minerals that are difcult to be recovered by tradi-
Received 20 February 2014 tional otation process. This study presents a new route, roasting combined with suldization-otation,
Received in revised form 1 May 2014 for the recovery of anglesite and silver from jarosite residues of zinc hydrometallurgy. Surface appearance
Accepted 29 May 2014
and elemental distribution of jarosite residues was examined by scanning electron microscopy and energy
Available online 5 June 2014
dispersive X-ray spectrometry analysis, respectively. Decomposition and transformation mechanisms of
jarosite residues were illustrated by differential thermal analysis. Results showed that after roasting com-
Keywords:
bined with otation, the grade and recovery of lead were 43.89% and 66.86%, respectively, and those of
Jarosite residues
Metal recovery
silver were 1.3 kg/t and 81.60%, respectively. At 600700 C, jarosite was decomposed to release encap-
Roasting sulated valuable minerals such as anglesite (PbSO4 ) and silver mineral; silver jarosite decomposed into
Suldization-otation silver sulfate (Ag2 SO4 ); and zinc ferrite (ZnOFe2 O3 ) decomposed into zinc sulfate (ZnSO4 ) and hematite
Zinc hydrometallurgy (Fe2 O3 ). Bared anglesite and silver minerals were modied by sodium sulde and easily collected by
otation collectors. This study demonstrates that the combination of roasting and suldization-otation
provides a promising process for the recovery of zinc, lead, and silver from jarosite residues of zinc
hydrometallurgy.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Jarosite process is of great importance for iron (Fe) removal from zinc (Zn)
leaching solution [1,2]. In China, substantial jarosite residues are produced from
traditional zinc hydrometallurgical process [3,4]. Most of the jarosite residues have
to be stored due to the presence of contaminating heavy metals such as zinc (Zn),
lead (Pb), indium (In), germanium (Ge), cobalt (Co), and silver (Ag) [5]. Accumula-
tion of these residues not only takes up massive land but also aggravates a series of
environmental problems in terrestrial ecosystems. Additionally, some toxic ingre-
dients of jarosite residues, such as arsenic (As) and cadmium (Cd), can be dissolved
in rain water [6,7], threatening the health of aquatic systems.
In jarosite process iron is precipitated from the hot acid (pH 0.52.0) leach-
ing solution at elevated temperatures (9597 C) in the presence of sodium or
ammonium ions [8]. Jarosite is a basic iron sulfate complex whose formation
is represented by the following equilibrium [8]: 3Fe2 (SO4 )3 + M2 SO4 + 12H2 O
Corresponding author. Tel.: +86 731 88830482.
E-mail address: hanhaishengjingji@126.com (W. Sun).
2MFe3 (SO4 )(OH)6 + 6H2 SO4 , where M is any of the ions Na+ , NH4 + , H3 O+ , Li+ , K+ , Ag+ ,
Pb2+ ; and some metal impurities, such as Zn, Cd, nickel (Ni), and Co, can replace
Fe in the crystal lattice of jarosite, as demonstrated [8,9]. The reaction of precip-
itation liberates acid, which must be neutralized by some agents. During jarosite
process, Zn calcine usually serves as a neutralizer and is partially dissolved, with
the rest staying with jarosite precipitate. Consequently, jarosite residues produced
during zinc hydrometallurgy mainly present in three phases: jarosite, Zn ferrite, and
anglesite. And considerable amounts of Zn and valuable metals such as Pb, Ag, In,
Ga, Ge are lost in addition to having contaminated residues, leading to potential
environmental problems [1,5].
Great research effort has been made to develop clean processes to treat such
jarosite residues. Ju et al. [3] have proposed a clean hydrometallurgical route to
recover Zn, Ag, Pb, Cu, Ca and Fe from hazardous jarosite residues, in which jarosite
residues are initially activated and decomposed by sintering at 650 C, then leached
with aqueous NH4 Cl; the leaching extraction of Zn, Pb, Cu, Cd, and Ag is more than
95%. In China, factories adopt rotary kilns to fume Zn, In, and Pb, whereas in India and
Italy, factories chose to produce construction and ceramic materials with jarosites
[1012]. Additionally, Rashchi et al. [13] have adopted otation process to recover
anglesite from zinc leach residues which provided a novel idea for valuable min-
erals from jarosite residues. However single process seems not to be efcient to

http://dx.doi.org/10.1016/j.jhazmat.2014.05.091
0304-3894/ 2014 Elsevier B.V. All rights reserved.
50 H. Han et al. / Journal of Hazardous Materials 278 (2014) 4954
recover the valuable minerals from jarosite residues and roasting combined with
hydrometallurgy process have some shortcomings such as high xed investment
and high operation cost.
Flotation process is recognized as one of the most efcient and cost-effective
processes. However few otation researches with regard to recovering valuable
minerals from jarosite residues were studied. This study presents a new route,
roasting combined with suldization-otation, for the recovery of Zn, anglesite,
and Ag from jarosite residues in zinc hydrometallurgy. Jarosite was decomposed
to hematite, sulfur (S) dioxide, and some sulfates by roasting; valuable metals
were released from jarosite lattice or jarosite inclusions and then collected by
suldization-otation. Surface appearance and element distribution of jarosite
residuals were examined by scanning electron microscopy (SEM) and energy
dispersive X-ray spectrometry (EDS) analysis, respectively. Decomposition and
transformation mechanisms of jarosite residues were illustrated by differential
thermal analysis (DTA). The results were discussed to improve fundamental under-
standing of the mechanism of the new process.
2. Experimental
2.1. Jarosite residues
Jarosite residues were obtained from Zijin Smelting Plant
(Neimenggu, China), one of the largest smelters of Zn in China.
The iron precipitation is carried out in a modied jarosite process,
and the modication consists a pre-neutralization of the hot acid
solution with zinc calcine. The calcine which is not solubilized is
recycled to the hot acid leaching step and the leach solution at
pH 1.51.7 is sent to the jarosite precipitation stage. Such pre-
neutralization reduces the necessity of adding zinc calcine in the
precipitation stage. Jarosite precipitation is carried out at 9095 C
and pH 0.51.8. The jarosite residues were oven-dried for 1 h at
Fig. 1. A otation owsheet for the closed-circuit process of jarosite residue treatment.
8090 C and then subjected to multi-elemental and X-ray diffrac-
tion (XRD) analysis.
2.2. Experimental approach
A series of roasting experiments were conducted to nd out the
optimal roasting conditions. Each 20 g of dried jarosite residue sam-
ples were blended with 4 g of metallurgical coke and the mixture
was transferred into a ceramic crucible. The samples were loaded
into a mufe furnace that was set to a certain temperature vary-
ing from 450 C to 750 C, with an intervening step of every 50 C.
XRD patterns of each sintered sample were obtained to identify the
decomposition effect.
Washing was carried out in an agitator bath at the solid-to-
liquid ratio of 1:5. Roasted jarosite residues were soaked in washing
water for 15 min and then ltered, dried, and weighted. Pb and Ag
analysis was performed by X-ray uorescence (XRF) spectrome-
try.
After washing, the otation procedure was carried out in a Den-
ver D-12 otation machine (cell volume, 1.5 L). Five-hundred gram
of washed jarosite residues served as the otation material. Sodium
sulde (Na2 S) were added to the pulp and conditioned for 30 min
for suldization. The pulp was adjusted to pH 5.06.0 using either
sodium carbonate or sulfuric acid. Ammonium dibutyl dithio-
phosphate, diethyl dithiocarbamate, and 2-mercaptobenzothiazole
served as the otation collectors and the slurry was conditioned
for 3 min after each collector agent. After otation, the tailings and
the concentrates were ltered, dried, and weighted as described
above. Pb and Ag analysis was performed by XRF spectrometry. A
 H. Han et al. / Journal of Hazardous Materials 278 (2014) 4954 51

Table 1
Multi-elemental composition of jarosite residues after drying at 8090 C for 1 h.

Elements Unit Pb Zn Ag Fe Cu Cd Ba S Si Others

Before roasting % 8.48 5.94 0.022 28.81 0.2 3.64 0.18 10.79 1.17 40.77
After roasting % 9.32 6.37 0.024 32.03 0.23 4.40 0.21 5.28 1.32 40.72
After washing % 10.32 1.28 0.025 33.85 0.25 4.48 0.22 3.01 1.22 45.34
Liquor after washing g/L 0.08 11.36 0.007 0.02 5.63

Note: Roasting at 600 C for 1 h; not detected.

otation owsheet for the closed-circuit process of jarosite residue

treatment is shown in Fig. 1.

2.3. Analytical methods

The residue samples were subjected to quantitative analysis

with XRF and phase analysis with XRD. The leaching liquor was
diluted for elemental composition analysis. Surface appearance of
jarosite residues was examined by SEM analysis. Element distribu-
tion of jarosite residues before and after roasting was illustrated
by EDS analysis. Decomposition and transformation mechanisms
of jarosite residues at different temperatures were explored by
DTA.

3. Results and discussion

3.1. Chemical composition of jarosite residues

Fig. 3. The effect of roasting temperature to lead recovery.

Line 2 of Table 1 shows the elemental composition of jarosite
residues before roasting and demonstrates that jarosite samples
contained many valuable metals such as Pb, Zn, Cu, and Ag. Fig. 2 is
the XRD patterns of the jarosite sample and indicate that the main
phases of the residues were jarosite (KFe3 (SO4 )2 (OH)6 ), anglesite
(PbSO4 ), and Zn ferrite (ZnFe2 O4 ).
3.2. The effects of roasting and suldization-otation
Figs. 3 and 4 show the effect of roasting temperature to ota-
tion process and indicate that the recovery of Pb and Ag went
through three stages with the temperature rising from 25 C to
900 C. Low roasting temperature seemed not to be effective to
otation process. when temperature increased from 400 C to
500 C the recoveries of Pb and Ag were stable. The recovery of Pb
was between 40% and 45% and that of Ag was between 50% and
55%. However the recovery increased sharply with the roasting
temperature rising from 500 C to 600 C and became stable
between 600 C and 900 C. Thus 600700 C was the optimum
roasting temperature for otation process.
Line 5 of Table 1 is the elemental composition of washing water
and demonstrates that most Zn in jarosite residues was trans-
formed into the washing water after roasting and thus the jarosite
residue can be processed in smelting system. Table 2 shows the
results of the closed-circuit experiment of jarosite residue treat-
ment at 600 C. After otation, the grade and recovery of Pb were
43.89% and 66.86%, respectively, and those of Ag were 1.3 kg/t and
81.60%, respectively. These results prove that the combination of
roasting and suldization-otation signicantly contributed to the
recovery of Zn, Pb, and Ag from jarosite residues in zinc hydro-
metallurgy.

Fig. 2. XRD patterns of jarosite residues after drying at 8090 C for 1 h. Fig. 4. The effect of roasting temperature to silver recovery.
52 H. Han et al. / Journal of Hazardous Materials 278 (2014) 4954

Table 2
Results of the closed-circuit experiment of jarosite residue treatment.

Products Yield (%) Pb (%) Ag (%) Pb recovery (%) Ag recovery (%)

Concentrate 15.72 43.89 0.13 66.86 81.60

Tailings 84.28 4.27 0.005 33.14 13.06
Feed 100.0 10.32 0.025 100 100.0

3.3. The transformation of valuable metals during roasting
Fig. 5 shows the SEM-EDS analysis of jarosite residue slice. SEM
image indicates that most of the valuable particles were encap-
sulated by jarosite before roasting (Fig. 5a). Combined with EDS
patterns, particles Nos. 1 and 3 were identied as Zn ferrite and
particle No. 2 was anglesite (Fig. 5b and c). This situation would
seriously hamper selective otation because of similar surface
properties of the valuable particles and jarosite.
Roasting helped to break the capsule structure and expose the
valuable minerals, as shown in Fig. 6. After roasting, the particles
became bare and independent (Fig. 6a); particles Nos. 1 and 3 were
both iron oxide and particle No. 2 was anglesite (Fig. 6b and c).
3.4. Thermal decomposition of jarosite residues
Fig. 7 is the XRD patterns of jarosite residues after roasting at
different temperatures for 1 h. At 450 C, Jarosite was decomposed
to mikasaite (Fe2 [SO4 ]3 ), potassium sulfate (K2 SO4 ), hematite, and
trace of magnetite, and the recovery of Pb and Ag were both below
30% by otation. At 600 C and 750 C, jarosite was decomposed to
K sulfate, hematite, and magnetite; the recovery of Pb and Ag was
satisfying (Figs. 3 and 4).
According to the XRD patterns, the decomposition reactions of
jarosite residues at 600700 C can be summarized as follows:
2KFe3 (SO4 )2 (OH)6 3Fe2 O3 + K2 SO4 + 3SO3 +6H2 O (1)
2AgFe3 (SO4 )2 (OH)6 3Fe2 O3 + Ag2 SO4 + 3SO3 6H2 O (2)
ZnO Fe2 O3 + SO3 ZnSO4 + Fe2 O3 (3)
2Ag2 S + O2 2Ag2 O + 2SO2 (4)
Ag2 SO4 + 2CO 2Ag + SO2 +2CO2 (5)
3Fe2 O3 + CO 2Fe3 O4 + CO2 (6)
At 600700 C, jarosite was decomposed to release encapsulated
valuable minerals, such as anglesite and Ag minerals; Ag-jarosite
decomposed to silver sulfate (Ag2 SO4 ); and zinc ferrite (ZnOFe2 O3 )
decomposed to zinc sulfate (ZnSO4 ) and hematite (Fe2 O3 ).
Fig. 8 is the differential thermal patterns of jarosite residues
during temperature-rise from 30 C to 700 C and demonstrates
that the jarosite residues went through four stages. In the rst
stage, jarosite residues lost weight due to evaporation of water
(e.g., free and absorbed water). The second stage (250350 C)
might be a crystallization water removing process of Zn vitriol. In
the third stage (350490 C), an exothermic decomposition peak

Fig. 5. SEM image (a, crosses indicate particle Nos. 13) and EDS patterns of jarosite residue before roasting ((b) particle No. 1, O: 19.25%; S: 1.52%; Fe: 53.12%; and Zn:
26.11%; (c) particle No. 2, O: 15.42; Sr: 6.43; S: 14.7%; Pb: 36.08%; Ca: 1.31%; Ba: 23.45%; and Fe: 2.6%; and (d) particle No. 3, O; 17.58%; Fe: 56.38%; and Zn: 26.03%).
 H. Han et al. / Journal of Hazardous Materials 278 (2014) 4954 53

Fig. 6. SEM image (a, crosses indicate particle Nos. 13) and EDS patterns of jarosite residues after roasting ((b) particle No. 1, O: 18.46%; Fe: 56.28%; and Zn: 25.26%; (c)
particle No. 2, O: 15.85%; Sr: 6.53%; S: 13.11%; Pb: 51.15%; and Ba: 3.37%; and (d) particle No. 2, O: 11.67%; S: 2.26%; Pb: 4.38%; Fe: 78.33%; and Zn: 3.36%).

was outstanding, and jarosite started to decompose into mikasaite

(Fe2 [SO4 ]3 ), K sulfate (K2 SO4 ), and hematite (Fe2 O3 ). In the last
stage (490700 C), mikasaite (Fe2 [SO4 ]3 ) was decomposed into
hematite and sulfur trioxide (SO3 ) was released.
The differential thermal patterns were generally consistent with
the XRD patterns (Fig. 7). Together, the above results indicate that
roasting at a high temperature destroys jarosite crystal lattice,
which helps to liberate valuable minerals, such as Ag and Fe min-
erals, from the lattice and transform into the corresponding oxide

Fig. 8. Differential thermal patterns of jarosite residues (TG: thermogravimetric

curve; DSC: differential scanning calorimetry; DTG: derivative thermogravimetry).

or sulfate. Such transformation (thermal decomposition) creates

favorable conditions for the recovery of valuable minerals by ota-
tion process.

4. Conclusions

In jarosite residues, zinc ferrite, anglesite, and silver miner-

als were encapsulated or wrapped by jarosite precipitates. This
situation seriously hampers selective otation because of simi-
Fig. 7. XRD patterns of jarosite residues after roasting at different temperatures for lar surface properties of the minerals. Roasting helps to break the
1 h. jarosite capsule and expose the valuable minerals. At 600700 C,
54 H. Han et al. / Journal of Hazardous Materials 278 (2014) 4954
jarosite is decomposed to release valuable minerals encapsulated.
Bared anglesite and silver sulfate were modied by sodium sul-
de and easily collected by collectors. This study proves that the
combination of roasting and suldization-otation provides a
promising process for the recovery of zinc, lead, and silver from
jarosite residues of zinc hydrometallurgy. Compared with the pre-
vious ndings with regards to roasting of jarosite to recover silver
and lead, otation process is not only of high efcient but also
cost-effective and environmental friendly.
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