Original Article

Waste Management & Research

29(2) 165–171

Recovery of zinc from leach residues ! The Author(s) 2011

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with minimum iron dissolution using DOI: 10.1177/0734242X10372661
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oxidative leaching

Reza Alizadeh1, Fereshteh Rashchi1 and Ehsan Vahidi1,2

Abstract
Leaching was performed to recover zinc from a zinc leach residue which contained 9.87% Zn and 4.93% Fe. During sulfuric
acid leaching, Fe was dissolved as well as Zn which can reduce the Zn extraction efficiency. Leaching the residue in the
presence of an oxidizing reagent such as hydrogen peroxide or manganese dioxide significantly reduced the iron content of the
leach liquor. Effect of pH, temperature, solid/liquid ratio, reaction time and hydrogen peroxide or manganese dioxide con-
centration on the recovery of zinc and iron in non-oxidative and oxidative leaching conditions were investigated. By using the
optimum oxidative leaching conditions, iron recovery reduced from 70% in non-oxidative leaching to 0.4 and 5% in the pres-
ence of MnO2 and H2O2, respectively, with acceptable Zn recovery. This reduction in the iron content was due to the different
iron compounds formed at different conditions.

Keywords
Zinc, iron, leach residue, recovery, oxidative leaching
Date received: 10 January 2010; accepted: 11 April 2010

Introduction iron dissolves as well as the desired metal. Therefore, iron

Extraction of valuable metals or minerals from ores by pyromet-
allurgical and /or hydrometallurgical processes usually results in
a huge amount of wastes and tailings. Some of these by-products
of the primary extraction may contain residual metals or min-
erals of commercial value which may be reprocessed. The huge
quantities of these tailings results in wasting base metal values,
and causes environmental pollution. Therefore, there is a great
interest to recover the valuable metal species as well as hazard-
ous compounds from the wastes, selectively. Hydrometallurgy,
as a widely used technology in today’s production of base and
precious metals, is more environmentally suitable and economic
to treat materials containing low valuable metals and has
received extensive attention by researchers interested in recover-
ing base metals from wastes (Veglio et al., 2003; Espiari et al.,
2006; Kul and Topkaya, 2008; Li et al., 2008; Vahidi et al., 2009).
Today a part of zinc is recovered from different secondary
resources such as zinc ash, zinc dross, flue dusts, etc.; which
contain different levels of zinc and impurities depending on
their sources. However, zinc is dissolved following the disso-
lution of many other metals such as Fe, Ca, Mg, etc. As a
result, the acid consumption is high, and complex purifica-
tion processes are required (Wen-qing et al., 2007).
Iron is present as an undesirable component of zinc ores,
concentrates and calcine oxides. During the leaching process,
constitutes a severe impurity in zinc solutions and must be
removed before electrolysis (Ismael and Carvalho, 2003).
Iron causes some difficulties in the case of purification pro-
cesses as well, especially where solvent extraction is used. In
this case, co-extraction of zinc together with the iron species
present in the solution occurs, reducing the extraction effi-
ciency (Banza et al., 2002).
To overcome this problem, iron has to be separated from
zinc. This can be done by several methods such as precipita-
tion of iron as goethite (Dutrizac and Monhemius, 1986;
Torfs and Vliegen, 1996), hematite (Ropenack, 1982) or
even jarosite (Scott et al., 1986, Buban et al., 1999).
Recently, oxidative leaching has also been used to remove
iron from the solution (Banza et al., 2002).
1
School of Metallurgy and Materials Engineering, College of
Engineering, University of Tehran, Tehran, Iran.
2
Iranian Standard and Quality Inspection Co., PO Box 14395-617,
Tehran, Iran.
Corresponding author:
Fereshteh Rashchi, School of Metallurgy and Materials Engineering,
College of Engineering, University of Tehran, Tehran, Iran
Email: Rashchi@ut.ac.ir
166
Otherwise, if iron is not removed from the solution,
besides its effect on the reduction of extraction efficiency,
exposure of residues containing iron and contaminated
with heavy metals, such as Zn, Se, In, Ge and sulfur to atmo-
spheric conditions will cause environmental problems (Berg
and Borve, 1996; Welham et al., 2000).
Hofirek and Kerfoot, (1992) reported a process for recov-
ering Zn, Pb, Cu and precious metals from a zinc plant res-
idue by leaching with spent electrolyte. The leach residue was
obtained during the leaching of the concentrate in dilute sul-
furic acid (Bhat and Natrajan, 1987; Ghosh et al., 1989).
Zinc concentrate/oxide ore undergoes leaching according to
reaction (1)
ZnO þ H2 SO4 ! ZnSO4 þ H2 O ð1Þ
The objective of this research was to study extraction of
zinc from a zinc leach residue produced in a plant using zinc
oxide/carbonate ores as the feed, with minimum iron disso-
lution. For this purpose, both non-oxidative and oxidative
leaching conditions were applied. The parameters investi-
gated were pH, temperature, solid/liquid (S/L) ratio, reaction
time and concentration of hydrogen peroxide (H2O2) and
manganese dioxide (MnO2).
Materials and methods
Zinc leach residue sample was ground and sieved. An atomic
absorption spectrophotometer (AAS), Perkin-Elmer model
AA300 and an X-ray diffraction analyser (XRD), Philips
model PW 1730 were used to determine element content
and mineral phases of the samples, respectively. The XRD
results were analysed by PCPDFWIN software.
In the leaching experiments, sulfuric acid from Merck
with a purity of 95–98% and a density of 1.82 g mL–1 was
used. Leaching tests were carried out in a 2-L beaker. The
reaction mixture was agitated by mechanical stirrer and
heated on a thermostatic bath. The target temperature was
controlled within  5  C. A Buchner funnel was used for the
filtration step. Leaching tests were carried out at non-oxida-
tive (N.O) and oxidative conditions by using either H2O2
(O.H) or MnO2 (O.M). It should be noted that non-oxidative
is referred to the leaching condition in the absence of chem-
ical oxidizing reagents where some oxidation by air (oxygen)
can be expected. However, adding oxidizing reagents intro-
duces a higher oxidative medium and increases the electrical
potential to higher levels. It is worth mentioning that at the
end of leaching tests and at the filtration step two solid
phases were separated. One phase with the finer particles
(about half of the total weight of solid phase) remained on
the filter paper (named A) by simply decanting the top part
of the suspension, and coarser particles remained settled
down in the beaker (named B). These two solid residues
were analysed by XRD separately to determine their
Waste Management & Research 29(2)
iron compounds. Either hydrogen peroxide or manganese
dioxide was continuously added to the pulp during the leach-
ing step. The leach liquor and the residue were analysed for
zinc and iron contents by AAS.
Results and discussion
AAS analysis was performed to determine the zinc and iron
content of the received zinc leach residue. From the AAS
results (Table 1), the sample contained approximately 10%
zinc and approximately 5% iron. The result of XRD analysis
is shown in Figure 1. Based on the peaks detected and their
respective intensities, it can be concluded that the filter cake
used as the sample, consisted of the major phases of PbSO4,
ZnSO4.H2O, CaSO4.2H2O, SiO2 and Fe2O3.
Non-oxidative leaching
Effect of pH: Several batch leach tests were conducted to
determine the optimum conditions for extraction of zinc.
Figure 2 shows the correlation between zinc and iron extrac-
tion and pH, after leaching for 120 min at 75  C and S/L ¼
1/7. Zinc recovery increased up to 95% with pH down to 1.5
and remained almost constant at higher acid concentrations,
namely lower pHs. Increasing the acid concentration did also
increase the extraction of undesirable constituents such as
iron and silica as well as the reagent consumption
(Habashi, 1993). It should be mentioned that extraction of
zinc depends on the iron content of the ore (Bodas, 1996).
The higher the iron content, the lower was the zinc extraction
recovery in weakly acidic solutions (Frenay, 1985).
Effect of leaching time: Figure 3 illustrates the time
dependence of metal extraction at pH ¼ 1.5 and S/L ratio of
1/7 at 75  C. As can be seen, the extraction rate of zinc was
higher than for iron. Furthermore, if the leaching period was
long enough, almost all the zinc could be extracted at the
applied conditions. Nearly, 97.5% Zn was extracted in
150 min at 75  C and pH ¼ 1.5, but the problem was that at
this condition extraction of iron was also high (about 65%).
Effect of solid : liquid ratio: As can be seen in
Figure 4, the recovery of zinc increased by decreasing the
solid : liquid ratio and hence the excess of acid consumption.
The optimum S/L ratio was determined to be 1/7 (i.e. 0.14).
Effect of temperature: The influence of temperature
on metal extraction is shown in Figure 5. Leaching time was
Table 1. AAS analysis of the sample from the zinc leach
residue
Element Zn Fe
Amount (wt.%) 9.87 4.93
Alizadeh et al. 167

500

A : SiO2

A+C+D
450 B : Fe2O3
C : PbSO4

D+E+ F+G
400 D : CaSO42H2O
E : ZnSO4H2O
F : KAI2(Si3AI)O10(OH)2
350
G : CaAI2Si3O10(OH)2

300
LIn (Counts)

A+C+E+F
250

200 C

150

B+C+D
C

B+E+G

A+B
C+F
F+G

100
E G

B+C
A
C

G
D

G
G
D

F
B

A
B
F

F
50

0
20 30 40 50 60 70 80 90 100
2-theta-Scale

Figure 1. X-ray diffraction pattern of the filter cake (zinc leach residue).

100 100
Zn
90
80
Metal extraction (%)

Zinc extraction (%)

80
60 Fe
70
40
60

20 50

0 40
0 0.5 1 1.5 2 2.5 3 0.05 0.1 0.15 0.2 0.25 0.3
pH S/L ratio

Figure 2. Effect of pH on metal extraction: T ¼ 75  C, S/L ¼ 1/7, Figure 4. Effect of S/L ratio on Zn extraction: pH ¼ 2.5,
t ¼ 120 min. t ¼ 120 min, T ¼ 75  C.

100 100

Zn Zn
80 80
Metal extraction (%)

Metal extraction (%)

Fe
60 Fe 60

40 40

20 20

0 0
0 30 60 90 120 150 0 20 40 60 80 100
Time (min) Temperature (°C)

Figure 3. Effect of leaching time on metal extraction: Figure 5. Effect of leaching temperature on metal extraction:
T ¼ 75  C, S/L ¼ 1/7, pH ¼ 1.5. S/L ¼ 1/7 ratio, pH ¼ 1.5, t ¼ 120 min.
168 Waste Management & Research 29(2)

120 min, pH ¼ 1.5 and the solid : liquid ratio was kept con-
stant at 1 : 7. Clearly, the reaction temperature had a signif-
icant impact on the leaching efficiency. Increasing the
leaching temperature from 25 to 90  C increased the recovery
of both zinc and iron. The temperature of 75  C was sufficient
for the extraction of zinc and for leaching over 72% of iron.
Similar results were observed by previous researchers. Espiari
et al. (2006) also showed that zinc recovery increased with
temperature. Abdel-Aal, (2002) studied leaching of a zinc
silicate ore-containing willemite and hemi-morphite and
observed that as temperature was increased from 40 to
70  C, zinc extraction was enhanced from 70 to 95%.
The optimum conditions obtained here for the recovery of
zinc from the zinc leach residue via the acidic leaching tech-
nique, can be summarized as follows: pH ¼ 1.5, S/L ¼ 1/7,
temperature ¼ 75  C and 2 h leaching time which recovered
approximately 95% Zn and 72% Fe. The most important
factor limiting higher zinc recoveries was the co-existence
of iron with zinc along the leaching process. In order to elim-
inate the interference by iron, namely to reduce the iron
recovery, oxidative leaching tests were performed in the pres-
ence of two oxidants. The effects of either hydrogen peroxide
or manganese dioxide on zinc and iron extraction were inves-
tigated in the following tests.
about 62.5 L t–1 of H2O2, the iron dissolution decreased from
over 90% to less than 5%.
Figure 7 shows the effect of pH and time on metal extrac-
tion in the presence of 130 L t–1 of H2O2 at different pH
values of 1, 1.5, 2 and 2.5. As can be seen, although zinc
extraction was a function of both pH and time, specifically,
iron extraction was not so affected either by pH or time at
over 120 min. The amount of zinc extracted increased at
180 min. It seems that the optimum time and favored pH,
where the iron concentration in solution was the lowest and
the amount of zinc leached was acceptable, could be approx-
imately 180 min leaching time and a pH value around 1.
Effect of MnO2 on metal extraction: Figure 8
shows Zn and Fe extraction as a function of MnO2 concen-
tration. It can be seen that within the investigated range zinc
and iron extraction were practically unaffected by the
amount of MnO2. The presence of only 5 g kg–1 of MnO2
100
pH = 1
80
Metal extraction (%)

pH = 1.5
pH = 2
60
Oxidative leaching pH = 2.5
Zn
Effect of H2O2 on metal extraction: Figure 6 40
shows the effect of H2O2 concentration on the metal extrac-
20
tion. As can be seen, by increasing the oxidant concentration,
the zinc recovery remained almost constant; however, the Fe
0
iron recovery decreased significantly from approximately 0 30 60 90 120 150 180 210 240
82% to less than approximately 5%. About 100 mL of Time (min)
H2O2 per kg of sample was required to decrease iron recov-
ery to less than 5%. These results were consistent with the Figure 7. Effect of time of leaching on metal extraction at
findings of Banza et al. (2002). They showed that by adding different pH values: T ¼ 75  C, S/L ¼ 1/7, [H2O2] ¼ 100 L t–1.

100
100
80 Zn
Metal extraction (%)

Metal extraction (%)

80
Zn
60
60

40
40

20 20
Fe Fe
0 0
0 25 50 75 100 150 200 0 10 20 30 40 50
H2O2 consumption (L t–1) MnO2 consumption (g kg–1)

Figure 6. Effect of H2O2 consumption on metal extraction: Figure 8. Effect of MnO2 concentration on Zn and Fe
T ¼ 70  C, S/L ¼ 1/7, pH ¼ 1, t ¼ 180 min. extraction: T ¼ 75  C, S/L ¼ 1/7, pH ¼ 2, t ¼ 180 min.
Alizadeh et al. 169

already reduced the Fe extraction significantly. Under this

100 20
condition, the amount of iron extracted was reduced to
Zn
80 16 approximately 0.4%, which was much lower than the 5%
Zn extraction (%)

Fe extraction (%)
in the presence of H2O2; however, Zn extraction at this con-
60 12 dition was approximately 80% which was lower than that
when using H2O2 (90%; Figure 6).
40 8
The effect of pH on metal extraction in the presence of
Fe
20 4 MnO2 is shown in Figure 9. It can be seen that by increasing
pH from 1 to 2, the iron recovery decreased from approxi-
0 0 mately 3% to approximately 0.45% but zinc recovery was
0.5 1 1.5 2 2.5 3
pH not affected. Therefore the optimum pH was determined to
be pH ¼ 1.5–2.
Figure 9. Effect of pH on metal extraction: T ¼ 75  C, As the results show, adding either H2O2 or MnO2
S/L ¼ 1/7, t ¼ 120 min, [MnO2] ¼ 5 g kg–1. decreased the iron content of the solution significantly

N.O.A : Fe3O4 N.O.B : Fe3Zn10

: Fe1.6SiO4 : Fe2(OH,SO4)4.88
: FeZn10.98
CPS
CPS

20 30 40 50 60 70 80 90 100 110 120 20 30 40 50 60 70 80 90 100 110 120

2q (degree) 2q (degree)

: FeO : Fe(OH)3
O.H.A O.H.B
: Fe(OH)3 : Fe2SiO4
: Fe2SiO4 : FeO(OH)

: Fe2O3
CPS
CPS

20 30 40 50 60 70 80 90 100 110 120 20 30 40 50 60 70 80 90 100 110 120

2q (degree) 2q (degree)

: FeO : Fe2O3
O.M.A O.M.B
: (Fe,Mn)2SiO4 : Fe1.6SiO4
: FeO(OH)
CPS
CPS

20 30 40 50 60 70 80 90 100 110 120 20 30 40 50 60 70 80 90 100 110 120

2q (degree) 2q (degree)

Figure 10. XRD pattern of the solid phases formed during leaching at different conditions (N.O.: non oxidative, O.H. and
O.M.: oxidative in the presence of H2O2 and MnO2, respectively, A: solids remained on the filter paper, B: solids settled down
during leaching).
170
Zn
Zn
100
Zn Fe
Metal extraction (%)
80
60
40
20
Fe
0 H2O2 oxidant
Fe
MnO2 oxidant
Figure 11. Metal extraction at optimum non oxidative and
oxidative leaching conditions.
after leaching. Two reasons may be responsible for this
reduction in iron content. First, it may be due to the effect
of oxidizers on the dissolution of iron. Second, it may be due
to the different iron species which formed in the oxidative
condition in comparison with the non-oxidative condition.
The results of XRD analysis to determine the iron com-
pounds formed are discussed in the following section.
Determination of iron compounds: In order to
have a better understanding of the effect of oxidizers in
diminishing the iron recovery, XRD was performed on the
solid leach residues to determine the different iron com-
pounds which were formed at non-oxidative and oxidative
conditions, respectively. These results are shown in
Figure 10.
For each investigated leaching condition, many com-
pounds were detected; however, as iron elimination was
important, the following discussion is focused on iron com-
pounds only. As shown in Figure 10, different iron com-
pounds were formed at different conditions. Iron silicate
exists under oxidative as well as non-oxidative conditions.
Iron oxide was formed as magnetite at N.O. condition and
as hematite and wuestite at O.H. and O.M. conditions,
respectively. This is because different oxidative potentials
applied at different conditions. In comparison with N.O. con-
dition, some compounds have disappeared and new com-
pounds have been formed in oxidative conditions. Iron and
zinc compounds (Fe3Zn10 or FeZn11) exist in the N.O. con-
dition and therefore may limit the reduction in iron content,
because they undesirably decreased the zinc content of the
leach liquor, reducing the leaching efficiency. It is worth
noting that these iron/zinc compounds were not detected in
oxidative conditions. On the other hand, iron hydroxide
(Fe(OH)3) and iron manganese silicate ((Fe,Mn)2SiO4)
compounds were found in O.H. and O.M. conditions,
respectively. These compounds together with goethite
(FeO(OH)), which was formed at both oxidative conditions,
Waste Management & Research 29(2)
were probably responsible for iron elimination during oxida-
tive leaching conditions in comparison with non-oxidative
condition.
According to Figure 11, the amount of metal extracted
was compared for both oxidative and non-oxidative opti-
mum conditions. It can be seen that although zinc recovery
was approximately 96% in the non-oxidative leaching condi-
tion, iron recovery was also high, at approximately 70%.
However, by using either hydrogen peroxide or manganese
Non-oxidative
dioxide as oxidants, iron recovery was significantly reduced,
especially in the case of MnO2, which diminished it to less
than approximately 0.4%. It should be mentioned that to
compare the two oxidizer reagents, there are some more
parameters that should be taken into account; such as, the
toxicity of the reagents, their price and availability, etc.,
which are not discussed here.
Conclusions
1. The optimum conditions in non oxidative leaching of zinc
residues were as follows: temperature ¼ 75  C; S/L
ratio ¼ 1/7; Leaching time ¼ 120 min; pH ¼ 1.5. At this
condition, the percentages of Zn and Fe extracted were
96 and 70%, respectively.
2. The optimum conditions for H2O2 oxidative leaching were
as follows: [H2O2] ¼ 100 mL kg–1; Leaching time ¼ 3 h;
pH ¼ 1. The percentages of Zn and Fe extracted were
90 and 5%, respectively.
3. The optimum MnO2 concentration and the favored pH
were estimated to be 5 g kg–1 and pH ¼ 1.5–2, respectively.
The percentages of Zn and Fe extracted under this condi-
tion were 80 and 0.4%, respectively.
4. Iron zinc compounds were detected by XRD under non-
oxidative conditions; however, they were not detected
under oxidative conditions, allowing iron extraction to
decrease, along with sufficient zinc extraction. Both oxi-
dants, H2O2 as well as MnO2, decreased the iron recovery
significantly by formation of iron hydroxide or iron man-
ganese compounds, respectively.
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