Hydrometallurgy 101 (2010) 171–173

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / h y d r o m e t

Zinc recovery from steel-making wastes by acid pressure leaching and

hematite precipitation
Šárka Langová ⁎, Dalibor Matýsek
VŠB-Technical University of Ostrava, Czech Republic

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

Article history: The hydrometallurgical extraction of zinc from EAF dust and steel-making sludge was studied. These materials
Received 5 November 2009 were treated with sulphuric acid at elevated pressure using microwave heating. More than 92% of zinc can be
Received in revised form 6 January 2010 leached out using 0.3 M acid solution at 260 °C. Fe(II) remained in solution while most of the Fe(III) was
Accepted 6 January 2010
precipitated as hematite. The iron concentration in the leach liquor decreased markedly when hydrogen peroxide
Available online 15 January 2010
solution was added at the start of the experiment. In this case, zinc extraction reached almost 99%. The hydrolytic
precipitation of ferric sulphate was investigated at 200 °C for a low iron concentration. The reaction was found to
Keywords:
Zinc
be first-order with respect to Fe(III), and the apparent rate constant was 0.01 min− 1.
Sulphuric acid © 2010 Elsevier B.V. All rights reserved.
Steel-making wastes
Leaching
Hematite
Precipitation

1. Introduction at a temperature of 150 °C with a concentration of sulphuric acid of

Steel-making wastes are characterized as hazardous because of the
heavy metals (Zn, Pb, Cd, etc.) present. They also contain a high
concentration of iron oxide which could be recycled. Zinc is present as
easily leachable zincite (ZnO) and sparingly soluble zinc ferrite
(ZnFe2O4). Zinc and other metals can be recovered from the Electric
Arc Furnace (EAF) dust or steel-making sludge by pyrometallurgical
or hydrometallurgical treatment. In a Waelz kiln, after the carbother-
mic reduction of zinc oxide and zinc ferrite at temperatures higher
than 1500 K, zinc is evaporated, re-oxidized, and leached (Matsuno
et al., 1995).
A number of different aqueous solutions have been used for
hydrometallurgical treatment of EAF dusts. Sodium hydroxide and
ammonium chloride give high selectivity but do not leach zinc ferrite
(Dutra et al. 2006; Olper, 1993). There are several reports of sulphuric
acid processes at atmospheric pressure (Cruells et al. (1992), Jandová
et al. (2002), Jha and Duyvesteyn (1985)) although the results
depended greatly on the sample composition and leaching
conditions. Havlík et al. (2004, 2005) explored sulphuric acid leaching
both at atmospheric and elevated pressures and found that zinc
extraction decreased with increasing temperature. The maximum
value of selectivity was obtained by the minimal chosen acid/dust
ratio of 0.4. The maximum value for Zn-extraction of 84% was reached
⁎ Corresponding author.
E-mail addresses: sarka.langova@vsb.cz (Š. Langová), dalibor.matysek@vsb.cz
(D. Matýsek).
0.4 mol dm− 3. Hydrochloric acid has been found to be a very effective
lixiviant for the leaching of zinc ferrite (Baik and Fray, 2000) but zinc
cannot be extracted without also dissolving iron at the atmospheric
pressure. Oxidative leaching using acid ferric chloride has also been
reported as very effective (Leclerc et al., 2003, McElroy and Murray,
1996).
The dissolved iron must be removed before the electrolysis of zinc
sulphate. Various types of the precipitation and extraction processes
are described by Dutrizac (1976), Cheng et al. (2003) and Ismael and
Carvalho (2003). Hematite precipitation is the only commercial
precipitation process that does not yield a waste material. Lead and
cadmium can be removed from the zinc solution by cementation. A
previous paper (Langová et al., 2009) showed that >90% of zinc can be
recovered from ZnFe2O4 using 0.3 M HCl solution at 260 °C while only
∼2% iron remains dissolved.
The kinetics of hematite precipitation from the ferric sulphate
solution was studied by Cheng and Demopoulos (2004) who reported
that zinc sulphate enlarged the stability region of hematite. The
influence of reaction conditions on zinc and sulphur content and on
the precipitation properties was also investigated. In this study the
apparent kinetic constant of the ferric sulphate hydrolysis was
determined to be 0.01 min−1 and the reaction was found to be first-order
with respect to Fe(III) for 5.7–44.7 g Fe(III)/dm−3 (0.1–0.8 mol dm−3).
This study focusses on the selective leaching of zinc in sulphuric acid
at elevated pressure. The process developed for zinc ferrite leaching in
our previous work (Langová et al., 2009) was applied to both EAF dust
and dried sludge from the oxygen open hearth furnace (tandem furnace,

0304-386X/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2010.01.003
172 Š. Langová, D. Matýsek / Hydrometallurgy 101 (2010) 171–173

TF). Sulphuric acid was chosen because of the low cost and the potential
to use electrolysis to produce zinc cathode.

2. Experimental

Two types of steel-making wastes were investigated — the EAF

dust and dried sludge from the oxygen open hearth furnace (tandem
furnace). Both samples were 100% <180 μm, the major elemental
composition is shown in Table 1. The Fe(II) content was determined
using dichromate titration.
The phase composition in Table 2 was determined using XRD (Seifert
ID 3003, CoKα, 0.05° 2Θ steps with count time of 3 s) and Rietveld
analysis. These results are only semi-quantitative because the franklin- Fig. 1. Variation of metal extraction after 100 min with temperature from EAF dust in
0.3M H2SO4 solution. ♦ - Zn, ■ - Fe, ▲ - Pb, × - Cd.
ite/magnetite ratio is very difficult to determine due to the very
significant overlap of peaks. The evaluation of the metal extraction was
made regarding the chemical analysis. Both materials also contained
also some oxides and salts of lead, calcite, and fluorosilicates.
Pressure leaching was performed in a water cooled 600 W
microwave reactor (Ertec Magnum II). The volume of the Teflon
crucible was 108 cm3. The reaction vessel was covered with the specially
shaped PTFE cap and metal rupture disk. 1 g of solid sample was mixed
with 50 ml of sulphuric acid solution and heated. The influence of the
temperature, acid concentration, and time was studied. After filtration
and washing, the leach liquors and solid residues were analysed by AAS,
selected residues were subjected to XRD.
Precipitation of hematite was carried out in the same reactor using
synthetic solutions. The solution pH was measured before and after
each experiment. The precipitates and solutions were analysed. Fig. 2. Effect of initial sulphuric acid concentration on metal extraction from EAF dust
and TF sludge at 260 °C after 100 min. ♦ - Zn (EAF), ■ - Fe (EAF), ▲ - Zn (TF), × - Fe (TF).

3. Results and discussion

3.1. Leaching
The time, initial acid concentration, and liquid/solid ratio were chosen
on the basis of the preliminary experiments and with respect to the results
with hydrochloric acid (Langová et al., 2009). The effect of temperature on
zinc leaching in 0.3 M H2SO4 solution after 100 minutes is shown in Fig. 1.
It can be seen that a temperature above 250 °C is necessary for leaching
more than 90% of zinc. At temperatures up to approximately 150 °C, zinc
ferrite is being dissolved stoichiometrically. At higher temperatures
hematite starts to precipitate (Langová et al., 2009) and the iron extraction
decreases. Sulphuric acid produced by the hydrolysis of ferric sulphate
allows further dissolution of zinc ferrite and magnetite.
Fig. 2 shows that the optimal initial acid concentration is
0.3 mol dm− 3 for which over 90% of zinc was extracted from both
EAF dust and TF sludge. At higher acid concentrations the iron
dissolution increases and the zinc/iron ratio in solution becomes less
favourable, the iron being predominantly Fe(II). It can be seen from
Fig. 3 that the zinc extraction reaches a maximum value after 100 min
at 260 °C in 0.3 mol dm− 3 H2SO4. Extended time leads to reduction of
the iron content in solution due to hematite precipitation. The Fe
concentration in the leach liquor decreased markedly when hydro-
gen peroxide was added to the starting solution. Only 3% of the iron
remained in solution while 11% remained without peroxide. The zinc
extraction in the presence of peroxide was almost 99%. But H2O2
probably decomposes too quickly and cannot be fully exploited.
Increasing the molar ratio of H2O2 to iron did not reduce the Fe(II)
concentration. It would be better to blow oxygen into the reactor
during the process. In the autoclave used in the present study, the
elevated pressure was only due to the vapour pressure of the acid
solution. The concentrations of total iron and Fe(II) in the leach
liquors without the oxidizing agent and with hydrogen peroxide are
shown in Table 3.
The mineralogical and chemical compositions of the solid residues
after leaching EAF dust and TF sludge for 100 min in 0.3 M H2SO4 at
260 °C are shown in Tables 4 and 5. In addition to hematite, lead
sulphate and calcium sulphate were present. Graphite was probably
contained in both samples but it can settle on the wall of the crucible
and it was not found by the XRD analysis because of inhomogeneity
and low content. For the purpose of recycling the iron oxide back to
the ironmaking process, lead and zinc can be removed and recovered
by washing with dilute acetic or hydrochloric acid.

Table 1
Chemical composition of studied samples (wt.%).

Sample Zn Fe Pb Cd Ca Fe(II)

EAF dust 8 45 2.1 0.04 3.7 6.4

TF sludge 14 52 1.8 0.02 0.7 8.8

Table 2
Mineralogical composition of the dust and sludge (wt.%).

Sample Zincite Franklinite Magnetite Wüstite Hematite Graphite

EAF dust 4 37 40 5 3 3
TF sludge 6 35 36 5 3 4 Fig. 3. Time dependence of metal extraction from EAF dust in 0.3 M H2SO4 solution at
260 °C. ♦ - Zn, ■ - Fe.
 Š. Langová, D. Matýsek / Hydrometallurgy 101 (2010) 171–173 173

Table 3 zinc can be leached in 100 min using 0.3 M H2SO4 solution at 260 °C.
Iron content in the leach liquor after the EAF dust treatment in the absence/presence of Fe(II) originated from wüstite and magnetite remained in solution
H2O2 solution (mg dm− 3).
while most of Fe(III) was hydrolytically precipitated as hematite. In
Without H2O2 With H2O2 the presence of hydrogen peroxide, a great proportion of the iron
Fe(II) 584 140 precipitated and the zinc extraction increased to ∼99%. The zinc/iron
Fe(total) 836 280 ratio in solution was excellent for subsequent processing. The solid
residues from EAF dust and TF sludge contained about 90% hematite,
0.2–0.3% zinc and a few percent each of PbSO4, CaSO4, and graphite.
Table 4 Compared with atmospheric leaching (Langová et al., 2007), the leach
Mineralogical composition of the solid residue from EAF dust and TF sludge (wt.%). liquors contained a low concentration of iron thereby removing any
Sample Fe2O3 PbSO4 CaSO4 Graphite Amorph. requirement to add an alkali to the leach solution to precipitate iron.
EAF dust 92 3 5 0 0
On the other hand, the zinc concentration is lower and spending on
TF sludge 89 2 0 3 6 thickening would be higher. The kinetics of the hematite precipitation
of the ferric sulphate solution was studied. The reaction was
ascertained to be first-order with respect to Fe(III). The apparent
Table 5 kinetic constant was determined to be 0.01 min− 1.
Chemical composition of the solid residue from EAF dust and TF sludge (wt.%).

Sample Zn Fe Pb

EAF dust 0.20 64 3.7

Acknowledgements
TF sludge 0.30 62 2.0
The present study was supported by the Grant Agency (GA 104/06/
1606) and by the Ministry of Education of the Czech Republic (MSM
6198910016).

Fig. 4. Effect of time on the Fe(III) concentration and acidity at 200 °C. ♦ — c(Fe), ■ — pH.
3.2. Precipitation
When the method of the pressure leaching with diluted sulphuric
acid was used subsequently the iron concentration in the leach liquors
originated from EAF dust and TF sludge varied from 1 up to 3 g dm− 3.
Hence the reaction kinetics of the hematite precipitation was
investigated for the initial Fe(III) concentration of 2.5 g dm− 3. Zn
concentration of 20 g dm− 3 was chosen regarding the electrolysis
requirements. The results are shown in Fig. 4. The acidity increases
with time because sulphuric acid is being formed. The linear time
dependence of ln c(Fe), where c is the molar concentration, indicates
that the reaction is first-order with respect to Fe(III). The apparent
kinetic constant was determined to be 0.01 min− 1. This is in good
agreement with the value determined for higher iron concentrations
by Cheng and Demopoulos (2004).
4. Conclusions
Selective leaching of zinc from EAF dust and TF sludge with
sulphuric acid at elevated temperature was studied. More than 92% of
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