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PII: S0304-3894(14)00446-4
DOI: http://dx.doi.org/doi:10.1016/j.jhazmat.2014.05.091
Reference: HAZMAT 15998
Please cite this article as: H. Han, W. Sun, Y. Hu, B. Jia, H. Tang, Anglesite
and silver recovery from jarosite residues through roasting and sulfidization-
flotation in zinc hydrometallurgy, Journal of Hazardous Materials (2014),
http://dx.doi.org/10.1016/j.jhazmat.2014.05.091
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Highlights
Jarosite precipitate hindered the recovery of valuable minerals.
Under 600‐700℃, jarosite decomposed and released the encapsulated valuable
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minerals.
The bared valuable minerals were easily collected by flotation process.
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The new process was promising for dealing with jarosite residues.
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Anglesite and silver recovery from jarosite residues through roasting and
Haisheng Han, Wei Sun, Yuehua Hu, Baoliang Jia, Honghu Tang
School of Mineral Processing and Bioengineering, Central South University, Changsha 410083, China
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Corresponding author: Wei Sun (School of Mineral Processing and Bioengineering, Central South
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University, Changsha 410083, China) Tel: 0086-731-88830482; E-mail: hanhaishengjingji@126.com
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Abstract
Hazardous jarosite residues contain abundant valuable minerals that are difficult to be
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recovered by traditional flotation process. This study presents a new route, roasting combined
with sulfidization-flotation, for the recovery of anglesite and silver from jarosite residues of
zinc hydrometallurgy. Surface appearance and elemental distribution of jarosite residues was
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examined by scanning electron microscopy and energy dispersive X-ray spectrometry
analysis, respectively. Decomposition and transformation mechanisms of jarosite residues
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were illustrated by differential thermal analysis. Results showed that after roasting combined
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with flotation, the grade and recovery of lead were 43.89% and 66.86%, respectively, and
those of silver were 1.3 kg/t and 81.60%, respectively. At 600-700°C, jarosite was
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decomposed to release encapsulated valuable minerals such as anglesite (PbSO4) and silver
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mineral; silver jarosite decomposed into silver sulfate (Ag2SO4); and zinc ferrite (ZnO·Fe2O3)
decomposed into zinc sulfate (ZnSO4) and hematite (Fe2O3). Bared anglesite and silver
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minerals were modified by sodium sulfide and easily collected by flotation collectors. This
study demonstrates that the combination of roasting and sulfidization-flotation provides a
promising process for the recovery of zinc, lead, and silver from jarosite residues of zinc
hydrometallurgy.
Key words: Jarosite residues; metal recovery; roasting; sulfidization-flotation; zinc
hydrometallurgy
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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
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(Ge), cobalt (Co), and silver (Ag) [5]. Accumulation of these residues not only takes up
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massive land but also aggravates a series of environmental problems in terrestrial ecosystems.
Additionally, some toxic ingredients of jarosite residues, such as arsenic (As) and cadmium
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(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 0.5-2.0) leaching solution
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at elevated temperatures (95–97℃) in the presence of sodium or ammonium ions [8]. Jarosite
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is a basic iron sulfate complex whose formation is represented by the following equilibrium
[8]: 3Fe2 ( SO4 ) 3 + M 2 SO4 + 12 H 2 O ↔ 2 MFe3 ( SO4 ) 2 (OH ) 6 + 6 H 2 SO4 , where M is any of the
ions Na+, NH4+, H3O+, Li+, K+, Ag+, 1/2 Pb2+; and some metal impurities, such as Zn, Cd,
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nickel (Ni), and Co, can replace Fe in the crystal lattice of jarosite, as demonstrated [8, 9].
The reaction of precipitation liberates acid, which must be neutralized by some agents. During
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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
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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
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addition to having contaminated residues, leading to potential environmental problems [1, 5].
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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,
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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 NH4Cl; 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 [10-12]. Additionally, Rashchi et al. [13]
have adopted flotation process to recover anglesite from zinc leach residues which provided a
novel idea for valuable minerals from jarosite residues. However single process seems not to
be efficient to recover the valuable minerals from jarosite residues and roasting combined
with hydrometallurgy process have some shortcomings such as high fixed investment and
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high operation cost.
Flotation process is recognized as one of the most efficient and cost-effective processes.
However few flotation researches with regard to recovering valuable minerals from jarosite
residues were studied. This study presents a new route, roasting combined with
sulfidization-flotation, for the recovery of Zn, anglesite, and Ag from jarosite residues in zinc
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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
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collected by sulfidization-flotation. Surface appearance and element distribution of jarosite
residuals were examined by scanning electron microscopy (SEM) and energy dispersive
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X-ray spectrometry (EDS) analysis, respectively. Decomposition and transformation
mechanisms of jarosite residues were illustrated by differential thermal analysis (DTA). The
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results were discussed to improve fundamental understanding of the mechanism of the new
process.
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2 Experimental
2.1 Jarosite residues
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Jarosite residues were obtained from Zijin Smelting Plant (Neimenggu , China), one of
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the largest smelters of Zn in China. The iron precipitation is carried out in a modified jarosite
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process, and the modification 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
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leach solution at pH 1.5–1.7 is sent to the jarosite precipitation stage. Such pre-neutralization
reduces the necessity of adding zinc calcine in the precipitation stage. Jarosite precipitation is
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carried out at 90-95°C and pH 0.5-1.8. The jarosite residues were oven-dried for 1 h at 80–
90°C and then subjected to multi-elemental and X-ray diffraction (XRD) analysis.
2.2 Experimental approach
A series of roasting experiments were conducted to find out the optimal roasting
conditions. Each 20 g of dried jarosite residue samples were blended with 4 g of metallurgical
coke and the mixture was transferred into a ceramic crucible. The samples were loaded into a
muffle furnace that was set to a certain temperature varying from 450°C to 750°C, with an
intervening step of every 50°C. XRD patterns of each sintered sample were obtained to
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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 filtered, dried, and
weighted. Pb and Ag analysis was performed by X-Ray fluorescence (XRF) spectrometry.
After washing, the flotation procedure was carried out in a Denver D-12 flotation
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machine (cell volume, 1.5 L). Five-hundred gram of washed jarosite residues served as the
flotation material. Sodium sulfide (Na2S) were added to the pulp and conditioned for 30 min
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for sulfidization. The pulp was adjusted to pH 5.0–6.0 using either sodium carbonate or
sulfuric acid. Ammonium dibutyl dithiophosphate, diethyl dithiocarbamate, and
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2-mercaptobenzothiazole served as the flotation collectors and the slurry was conditioned for
3 min after each collector agent. After flotation, the tailings and the concentrates were filtered,
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dried, and weighted as described above. Pb and Ag analysis was performed by XRF
spectrometry. A flotation flowsheet for the closed-circuit process of jarosite residue treatment
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is shown in Fig. 1.
2.3 Analytical methods
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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
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jarosite residues before and after roasting was illustrated by EDS analysis. Decomposition and
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that the recovery of Pb and Ag went through three stages with the temperature rising from
25℃ to 900℃. Low roasting temperature seemed not to be effective to flotation process.
when temperature increased from 400℃ to 500℃ the recoveries of Pb and Ag were stable.
The recovery of Pb was between 40- 45% and that of Ag was between 50-55%. However the
recovery increased sharply with the roasting temperature rising from 500℃ to 600℃ and
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became stable between 600℃ and 900℃. Thus 600-700℃ was the the optimum roasting
temperature for flotation process.
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Line 5 of Table 1 is the elemental composition of washing water and demonstrates that
most Zn in jarosite residues was transformed into the washing water after roasting and thus
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the jarosite residue can be processed in smelting system. Table 2 shows the results of the
closed-circuit experiment of jarosite residue treatment at 600℃. After flotation, the grade and
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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
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sulfidization-flotation significantly contributed to the recovery of Zn, Pb, and Ag from jarosite
residues in zinc hydrometallurgy.
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3.2 The transformation of valuable metals during roasting
Figs. 5 show the SEM-EDS analysis of jarosite residue slice. SEM image indicates that
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most of the valuable particles were encapsulated by jarosite before roasting (Fig. 5a).
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Combined with EDS patterns, particles No. 1 and 3 were identified as Zn ferrite and particle
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No. 2 was anglesite (Fig. 5b–c). This situation would seriously hamper selective flotation
because of similar surface properties of the valuable particles and jarosite.
Roasting helped to break the capsule structure and expose the valuable minerals, as
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shown in Figs. 6. After roasting, the particles became bare and independent (Fig. 6a); particles
No. 1 and 3 were both iron oxide and particle No. 2 was anglesite (Fig. 6b-c).
3.3 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 (K2SO4),
hematite, and trace of magnetite, and the recovery of Pb and Ag were both below 30% by
flotation. At 600°C and 750°C, jarosite was decomposed to K sulfate, hematite, and magnetite;
the recovery of Pb and Ag was satisfying (Fig. 3 and Fig.4).
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According to the XRD patterns, the decomposition reactions of jarosite residues at
600–700°C can be summarized as follows:
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ZnO·Fe2 O3 + SO3 → ZnSO 4 + Fe2 O3
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(3)
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Ag 2 SO4 + 2CO → 2 Ag + SO2 ↑ +2CO2 ↑ (5)
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3Fe 2O 3 + CO → 2Fe3O 4 + CO 2 ↑ (6)
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as anglesite and Ag minerals; Ag-jarosite decomposed to silver sulfate (Ag2SO4); and zinc
ferrite (ZnO·Fe2O3) decomposed to zinc sulfate (ZnSO4) and hematite (Fe2O3).
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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
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first stage, jarosite residues lost weight due to evaporation of water (e.g., free and absorbed
water). The second stage (250–350°C) might be a crystallization water removing process of
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Zn vitriol. In the third stage (350 – 490°C), an exothermic decomposition peak was
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outstanding, and jarosite started to decompose into mikasaite (Fe2[SO4]3), K sulfate (K2SO4),
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and hematite (Fe2O3). In the last stage (490–700°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).
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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 minerals, from the
lattice and transform into the corresponding oxide or sulfate. Such transformation (thermal
decomposition) creates favorable conditions for the recovery of valuable minerals by flotation
process.
4 Conclusions
In jarosite residues, zinc ferrite, anglesite, and silver minerals were encapsulated or
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wrapped by jarosite precipitates. This situation seriously hampers selective flotation because
of similar surface properties of the minerals. Roasting helps to break the jarosite capsule and
expose the valuable minerals. At 600-700°C, jarosite is decomposed to release valuable
minerals encapsulated. Bared anglesite and silver sulfate were modified by sodium sulfide
and easily collected by collectors. This study proves that the combination of roasting and
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sulfidization-flotation provides a promising process for the recovery of zinc, lead, and silver
from jarosite residues of zinc hydrometallurgy. Compared with the previous findings with
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regards to roasting of jarosite to recover silver and lead, flotation process is not only of high
efficient but also cost-effective and environmental friendly.
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Reference
[1] J. Dutrizac, T. Chen, A mineralogical study of the jarosite phase formed during the autoclave leaching of zinc
concentrate, Canadian metallurgical quarterly, 23 (1984) 147‐157.
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[2] S. Acharya, S. Anand, R. Das, Iron rejection through jarosite precipitation during acid pressure leaching of
zinc leach residue, Hydrometallurgy, 31 (1992) 101‐110.
[3] S. Ju, Y. Zhang, Y. Zhang, P. Xue, Y. Wang, Clean hydrometallurgical route to recover zinc, silver, lead,
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copper, cadmium and iron from hazardous jarosite residues produced during zinc hydrometallurgy, Journal of
hazardous materials, 192 (2011) 554‐558.
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[4] S.‐m. Ning, Z.‐f. Chen, Recovery of zinc and indium from jarosite residues, Chinese Journal of Nonferrous
Metals(China), 7 (1997) 56‐58.
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[5] J. Dutrizac, O. Dinardo, The co‐precipitation of copper and zinc with lead jarosite, Hydrometallurgy, 11
(1983) 61‐78.
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[6] A. Özverdİ, M. Erdem, Environmental risk assessment and stabilization/solidification of zinc extraction
residue: I. Environmental risk assessment, Hydrometallurgy, 100 (2010) 103‐109.
[7] M. Erdem, A. Özverdi, Environmental risk assessment and stabilization/solidification of zinc extraction
residue: II. Stabilization/solidification, Hydrometallurgy, 105 (2011) 270‐276.
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[8] J. Dutrizac, The behavior of impurities during jarosite precipitation, Hydrometallurgical process
fundamentals, (1982) 125‐169.
[9] J. Dutrizac, Jarosite‐type compounds and their application in the metallurgical industry, J. Metals, 35 (1982)
A70‐A70.
[10] P. Asokan, M. Saxena, S.R. Asolekar, Hazardous jarosite use in developing non‐hazardous product for
engineering application, Journal of hazardous materials, 137 (2006) 1589‐1599.
[11] A. Pappu, S. Mohini, R.A. Shyam, Hazardous Jarosite use in advance non‐hazardous product for
engineering application, Journal of Hazardous Materials, 137 (2006) 1589‐1599.
[12] P. Asokan, M. Saxena, S. Asolekar, Recycling hazardous jarosite waste using coal combustion residues,
Materials Characterization, 61 (2010) 1342‐1355.
[13] F. Rashchi, A. Dashti, M. Arabpour‐Yazdi, H. Abdizadeh, Anglesite flotation: a study for lead recovery from
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zinc leach residue, Minerals Engineering, 18 (2005) 205‐212.
Figure captions
Fig. 1 A flotation flowsheet for the closed-circuit process of jarosite residue treatment.
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Fig. 3 The effect of roasting temperature to lead recovery.
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Fig. 4 The effect of roasting temperature to silver recovery.
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Fig. 5 SEM image (a, crosses indicate particles No. 1–3) 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;
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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%;
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Fig. 6 SEM image (a, crosses indicate particles No. 1-3) 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:
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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%;
Fig. 7 XRD patterns of jarosite residues after roasting at different temperatures for 1 h.
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Fig. 8 Differential thermal patterns of jarosite residues (TG: Thermogravimetric curve; DSC: Differential
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Table captions
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Table 1 Multi-elemental composition of jarosite residues after drying at 80–90°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
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% 10.32 1.28 0.025 33.85 0.25 4.48 0.22 3.01 1.22 45.34
Liquor after
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g/L 0.08 11.36 - 0.007 0.02 - - 5.63 - -
washing
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Table 2 Results of the closed-circuit experiment of jarosite residue treatment.
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Jarosite residues
Roasting
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Adjusting pH
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Collector for 9 min
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Adjusting pH
Collector for 9 min
Foaming agent for 2 min
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Adjusting pH
Collector for 9 min
Na2 S for 30 min
Scavenging Ⅱ
Concentration
Concentrate of Pb and Ag
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Fig. 1 A flotation flowsheet for the closed-circuit process of jarosite residue treatment.
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1000
900
800
▲ ▲
▲ ▲-Jarosite
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700 △ -PbSO4
Inrensity(counts)
◆-ZnFe2O4
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600
500
400
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300
△
▲ ▲
▲ △
200 ▲
▲
▲
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△
100 △▲ ▲▲ △
△
◆ ◆ ▲▲ △
◆ ▲ ▲
◆ ▲
0
10 20 30 40 50 60 70 80
Two-Theta(deg)
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Fig. 2 XRD patterns of jarosite residues after drying at 80–90°C for 1 h.
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50
70
Grade of Pb
40 Recovery of Pb
60
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Recovery /%
Grade /%
50
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30
40
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20
30
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10 20
0 100 200 300 400 500 600 700 800 900 1000
Temperature /℃
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Fig.3 The effect of roasting temperature to lead recovery
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1400 100
1200 90
Grade of Ag
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Recovery of Ag
80
1000
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Grade /(g/t)
Recovery /%
70
800
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60
600
50
400
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40
200
30
0 100 200 300 400 500 600 700 800 900 1000
Temperature /℃
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Fig.4 The effect of roasting temperature to silver recovery
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1
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2 3
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a
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c (NO.2) d (NO.3)
Fig. 5 SEM image (a, crosses indicate particles No. 1–3) and EDS patterns of jarosite residue before
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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%;
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3
2
1
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a b (NO.1)
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c (NO.2) d (NO.3)
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Fig. 6 SEM image (a, crosses indicate particles No. 1-3) and EDS patterns of jarosite residues after roasting
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(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%;
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◇
▲-Jarosite
◆ △-Mikasaite
◆-Hematite
◇-Magnetite
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●-Hydroxide sulfate
★-Iron sulfate
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◇
◆
◇
◇
◆ T 750℃
★ ◇ ◆ ◆
◇ ◆ ◇ ◆ ★ ◇ ★
◆ ◆ ◆★
◇
◆
cr
◆
◇ T 600℃
◆ ◆ ◆ ◆ ◆
◇ ◆
◇ ◇ ◇ ◆ ◆
◇
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△
◆
△ △ ●● △
△
△
◇ T 450℃
◇ △ ◇ ◆◆ △ ◆ ◆ ◆ ◆ ◆ ◆ ◆
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▲
▲
▲
T 25℃
▲ ▲
▲ ▲ ▲ ▲
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▲ ▲ ▲ ▲ ▲▲
▲ ▲ ▲
10 20 30 40 50 60 70 80
Two-Theta(deg)
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Fig. 7 XRD patterns of jarosite residues after roasting at different temperatures for 1 h.
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DSC/(mW/mg) DTG/(%/min)
t
DSC 1.6
0.00
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DTG
90 1.4
-0.05
1.2
cr
284.09℃
1.0 -0.10
80
TG/%
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Stage Ⅱ Stage Ⅳ 0.6
70 Stage Ⅲ -0.20
0.4
663.77℃
-0.25
412.14℃ 0.2
60
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0.0 -0.30
54.09℃
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