Hydrometallurgy 169 (2017) 589–598

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Process development for hydrometallurgical recovery of valuable metals MARK

from sulfide-rich residue generated in a secondary lead smelter
Eunyoung Kima,b,⁎, Joris Roosena,c, Liesbeth Horckmansa, Jeroen Spoorena, Kris Broosa,
Koen Binnemansc, Karl C. Vranckena,b, Mieke Quaghebeura
a
VITO – Flemish Institute for Technological Research, Boeretang 200, B-2400 Mol, Belgium
b
University of Antwerp, Department of Bioengineering, Groenenborgerlaan 171, B-2020 Antwerp, Belgium
c
KU Leuven, Department of Chemistry, Celestijnenlaan 200F, P.O. Box 2404, B-3001 Heverlee, Belgium

A R T I C L E I N F O A B S T R A C T

Keywords: Two routes were investigated to selectively recover lead and minor metals (Cu, Ni, Zn) from a sulfide-rich lead
Oxidative leaching smelter residue, matte. The first route comprises a two-step leaching process that combines Fe(III)-HNO3
Lead recovery leaching with roasting, followed by water leaching. In the first step, the efficiency of Pb leaching was 90% at the
Lead smelting residue optimum condition (L/S ratio 8, 0.5 mol⋅ L− 1 HNO3, 0.15 mol ⋅ L− 1 Fe(III), 25 °C). In the second step, roasting at
Functionalized chitosan-silica
600 °C followed by water leaching at 50 °C selectively leached Ni, Cu, and Zn while fully converting iron sulfides
Ion exchange
Slag
to oxides. One-step oxidative pressure leaching in HNO3 was investigated as an alternative to simultaneously
Industrial process residues leach Pb, Cu, Ni and Zn. At the optimal conditions (130 °C, 60 min, 0.3 mol ⋅L− 1 HNO3, 0.07 mol⋅ L− 1 Fe(III), L/
S ratio 20), Pb, Cu, Zn and Ni leaching were 92, 60, 70 and 66%, respectively, while Fe leaching remained low
(2%). The leachates obtained from both leaching routes were treated by ion-exchange adsorption with
diethylenetriaminepentaacetic acid (DTPA) functionalized chitosan-silica hybrid materials to investigate the
selective recovery of Cu, Zn and Ni. The adsorption order appeared to be in the same order as the corresponding
stability constants for complexes between the respective metal ions and free DTPA: Ca(II) < Zn(II) < Pb
(II) ≈ Ni(II) < Cu(II). This allows not only to selectively recover Cu, Zn and Ni from the leachates, but also to
mutually separate them by using the functionalized resin as a stationary phase in column chromatography. To
avoid adsorbent contamination, Fe(III) and Pb(II) may be removed from the leachates in a pre-treatment step.
Based on these results, the investigated methods can be combined as process steps of two possible routes for the
selective recovery of valuable metals from the studied secondary lead smelting residue. The two-step leaching
process seems to be superior since a more concentrated solution of Cu, Ni, and Zn is produced in the 2nd leaching
step with low capital cost.

1. Introduction
It is estimated that each year worldwide over 500 million recharge-
able lead acid batteries are produced (Vasant et al., 2013). In Europe
and the US, the recycling rate from spent batteries is higher than 98%
(EUROBAT). The recovery of metallic lead from spent batteries usually
takes place by pyrometallurgical processes. For each ton of metallic
lead produced, 100–350 kg of slag is generated that contains approxi-
mately 5% of lead compounds and hazardous minor elements such as
copper, tin, antimony, nickel, and zinc (Shu et al., 2015).
Galena (PbS) is the main lead compound contained in the Pb slag. In
order to recover Pb, leaching of the natural mineral galena has been
investigated by many researchers who proposed different HNO3-based
leaching systems, including HNO3 (Zárate et al., 2012), H2O2-HNO3
(Aydoğan et al., 2007a) and Fe(III)-HNO3 (Pashkov et al., 2002). Also,
chloride systems can leach galena but require high brine concentrations
and elevated temperatures to promote the formation of soluble ionic
complexes to increase the solubility of lead chlorine, i.e. (NaCl-)HCl
(Zhang et al., 2015) or FeCl3-HCl/H2O2-HCl (Baba and Adekola, 2011).
As an alternative, fluorosilicate as a lixiviant (Habashi, 2005) or acetic
acid leaching in the presence of hydrogen peroxide (Aydoğan et al.,
2007b) was reported. Meanwhile, processing of lead batteries has often
been taken up by treating the PbSO4 sludge separately, for which a
number of processing methods mostly based on leaching with NaOH
(Liu et al., 2012) or citric acid (Zárate and Lapidus, 2014) and electro-
winning/precipitation have been developed (Agrawal et al., 2004).
There are few studies aimed at leaching or recovery of lead from
secondary lead smelting slags (Ettler et al., 2004; Smaniotto et al.,

⁎
Corresponding author at: VITO – Flemish Institute for Technological Research, Boeretang 200, B-2400 Mol, Belgium.
E-mail address: key409@empal.com (E. Kim).

http://dx.doi.org/10.1016/j.hydromet.2017.04.002
Received 23 November 2016; Received in revised form 14 March 2017; Accepted 1 April 2017
Available online 03 April 2017
0304-386X/ © 2017 Elsevier B.V. All rights reserved.
E. Kim et al. Hydrometallurgy 169 (2017) 589–598

2009). Table 1
Nitrate-based hydrometallurgical processes have some unique and Chemical composition of the sample.
advantageous characteristics. Nitric acid can produce highly oxidizing
Elements Fe Pb Cu Ni Zn Sn Si S
conditions and is an effective leachant for most sulfides (Shang and
Weert, 1993; Gok and Anderson, 2013). Another important advantage wt% 50 7.04 1.3 0.17 0.48 0.23 3.3 20
of the nitrate system over the sulfate and chloride ones is that NO(g)
reacts readily with oxygen to regenerate nitric acid at high temperature
(> 120 °C) (Gok and Anderson, 2013). Furthermore, the reaction rates 2. Materials and methods
of metal leaching also increase at higher temperatures. Lead slags
contain high concentrations of iron complexes (Fe 35–50 wt%) consist- 2.1. Materials
ing of sulfides and silicates. Especially FeS can cause acid mine drainage
(AMD) because of its rapid oxidation in the presence of water (Chiriţă The lead smelting residue was collected at a lead smelting company.
and Schlegel, 2015). Iron can be also selectively recovered through The residue was produced in a shaft furnace fired with coke and loaded
hydrolysis, which usually yields a Fe(III) precipitate at higher tempera- with a charge composed of lead scrap, iron scrap (flux), and lime
tures. Although no base metal recovery process using the nitrate system (additive). The smelted and molten residue which consists of two
exists at present, the use of nitrate systems in mineral processing layers, i.e., matte (sulfur-rich layer, more dense) and slag (oxides), were
continues to receive attention, especially for the processing of sulfides tapped off into a cone-shaped pot, cooled, turned over and physically
due to its unique advantages (Shang and Weert, 1993). Therefore, separated. The > 15 cm size fraction of the slag phase is reused in the
nitrate-based leaching systems are obvious candidates to achieve process and the remainder of the slag and matte are currently disposed.
optimal recycling of the lead slags. In this study, the disposed matte was used as sample. The matte sample
For the recovery of valuable metals from leachates or wastewater, was taken according to the Flemish standard CMA/1/A.15 (CMA/1/
conventional processes such as solvent extraction, chemical precipita- A.15, 2012). Representative samples for the leaching tests were
tion and electrochemical removal have been applied. These processes obtained after crushing and sieving to a particle size below 125 μm.
have disadvantages, such as contamination of the aqueous phase, The chemical (Table 1) and mineralogical composition (Fig. 1) of the
incomplete removal, production of toxic sludge and high-energy matte sample was determined. The matte mainly consists of iron (50%)
requirements (Barakat, 2011). Recently, numerous approaches have as FeS (troilite) and FeO (wüstite), and lead (about 7%) as PbS (galena)
been studied in view of cheaper and more effective technologies. Ion- and metallic lead phases. Also, it contains minor amounts of PbO
exchange adsorption is considered as a key technology to recover low (litharge), Fe2SiO4 (fayalite) and Fe3O4 (magnetite).
concentrations of valuable metals from large volumes of waste water
(Igwe, 2007; Roosen et al., 2014). A wide variety of ion-exchange 2.2. Leaching
resins, able to sequester metal ions from aqueous solutions, are
commercially available and industrially applied, such as Duolite®, 2.2.1. Roasting
Dowex®, and Amberlite® (Pennington and Williams, 1959; Eldridge, Roasting of the matte sample (< 125 μm) was carried out in an
2000). However, these materials suffer from low loading capacities, alumina crucible, which was placed in a temperature controlled muffle
often show high swelling behavior and they are very expensive (Miller furnace. The sample was heated at a rate of 2 °C ⋅min− 1 to a set
et al., 1981). The high availability of low-cost biosorbents make them temperature between 400 °C to 700 °C and held for 2 h at this
interesting alternatives for metal recovery, provided that modification temperature. Mass change during the reaction was measured by
of the material's structure is straightforward. Chitosan is a linear weighing the sample before and after roasting. Subsequently, the
polysaccharide derived from seafood waste (shrimps, lobsters, crabs) roasted matte sample was leached with water.
and its adsorption behavior has been widely studied in the context of
water purification and metal recovery (Gerente et al., 2007; Guibal,
2.2.2. Atmospheric leaching
2004; Wang and Chen, 2009). The abundant availability of amino and
The atmospheric leaching tests were carried out in a 60 mL
hydroxyl groups enables chemical modification of this biopolymer. This
polytetrafluoroethylene (PTFE) bottle with cap on 2.0 g of the un-
way, its adsorption performance, such as the selectivity, can be easily
roasted or the roasted matte samples with a particle size smaller than
adjusted (Zhao et al., 2013; Roosen and Binnemans, 2014). In analogy
125 μm. A typical experimental procedure consisted of mixing the
with EDTA-modified chitosan-silica, first described by Repo et al.
sample with a predetermined liquid-to-solid mass ratio of reagent in the
(2011), DTPA-functionalized chitosan-silica hybrid materials can be
synthesized and their adsorption performance for Cu, Zn and Ni from
leachate solutions investigated. Hybridization with silica improves the
mechanical properties, the chemical resistance and the porosity (Liu
et al., 2010). By these chemical and physical modifications, functiona-
lized chitosan-silica hybrid materials are expected to become suitable
for use as the stationary phase in chromatography columns, on a larger
scale than laboratory scale.
In this study, we aimed to selectively recover Pb, Cu, Zn and Ni from
a secondary lead smelting residue by investigating and optimizing their
leaching behavior in nitric acid by means of a two-stage and a one-step
leaching process. Furthermore, separation of Cu, Zn and Ni from the
leachates was tested for the first time by ion-exchange adsorption
chromatography with DTPA-functionalized chitosan-silica hybrid ma-
terials. Finally, it was aimed to valorize the iron-rich matrix material
after leaching in view of total recycling of the waste material (near
zero-waste valorization).

Fig. 1. XRD patterns of the matte used in this study.

590
E. Kim et al.
bottle, which was subsequently heated and stirred in a water shaking
bath at 200 rpm for a chosen reaction time. The reagent was either
nitric acid solution in the presence or absence of Fe(NO3)3 (for raw
material) or only water for roasted samples.
2.2.3. Autoclave leaching
Leaching tests were carried out in a 100 mL PTFE-lined, stainless
steel autoclave system (Parr, model 4842), equipped with a digital
temperature control unit to steer the heating power of the external
heating mantle. The reactor was charged with 40 mL of a solution with
a predetermined HNO3 concentration and 2.0 g of matte sample
(< 125 μm) in the presence or absence of Fe(NO3)3. Next, the reactor
was heated to the desired temperature (130 to 180 °C) with an
autogenous pressure built up of 5.8 to 36 bar total pressure with
building up the auto-pressure. The temperature inside the reactor was
measured with a thermocouple, connected to a digital multi-meter. At
the end of the reaction, the heating system was switched off and the
reactor was allowed to cool down to room temperature in the
surrounding air. The oxidation-reduction potential (ORP) was mea-
sured at room temperature after opening the reactor.
2.2.4. Analytical methods
After each leaching experiment, the slurry was filtered by filter
paper (Whatman) of 0.45 μm pore size and the obtained filtrate was
analyzed by inductively coupled plasma atomic emission spectroscopy
(ICP-AES, Thermo Elemental) to determine the amount of metal
extraction. Furthermore, ORP (mVAg/AgCl) of the solution was measured
by a SenTiX ORP 900 electrode. The obtained solid residues and
original sample before leaching were analyzed by X-ray fluorescence
(XRF, Thermo Scientific) and X-ray diffraction (XRD, Philips) in order
to determine the chemical and mineralogical composition, respectively.
2.3. Ion-exchange (IX) adsorption from leachate
2.3.1. Synthesis sorbent material
Both batch and column adsorption experiments were performed
with diethylenetriaminepentaacetic acid (DTPA) functionalized chito-
san-silica hybrid particles. The synthesis of DTPA-chitosan-silica is
described in detail elsewhere (Roosen et al., 2014). Shortly, chitosan
and tetraethyl orthosilicate (TEOS) are combined to obtain a more
stable chitosan-silica hybrid material through hydrolysis and subse-
quent silica condensation reactions. The latter material is then reacted
with the bisanhydride of DTPA to immobilize the organic ligand on the
chitosan-silica polymer matrix, through formation of amide bonds
between the free available amine groups on chitosan and the carboxylic
acid groups on DTPA.
2.3.2. Batch adsorption
Preliminary adsorption experiments were conducted in batch mode.
Functionalized particles were weighed and added to the vials, contain-
ing synthetic metal solution or leachate solution (10 mL). The experi-
mental pH was varied by addition of 1.0 mol⋅ L− 1 HNO3 to decrease, or
0.1 mol ⋅L− 1 NaOH to increase the pH, respectively. Solutions were
stirred at room temperature with a magnetic stirring bar at 500 rpm for
4 h. Next, the particles were separated from the aqueous solution by
filtration, making use of a regenerated cellulose syringe filter with a
pore size of 0.45 μm. The remaining metal-ion concentration of the
aqueous solution was measured using total-reflection X-ray fluores-
cence (TXRF, vide infra). The adsorption efficiency for each metal ion is
expressed as the recovery percentage:
(ci − ce )
%recovery = × 100%
ci
In this expression, ci is the initial metal ion concentration in aqueous
solution (mmol·L− 1) and ce is the equilibrium metal ion concentration
in aqueous solution (mmol·L− 1).
Hydrometallurgy 169 (2017) 589–598
2.3.3. Column separation
The column-chromatography setup was composed of a Büchi
chromatography pump B-688, to control the pressure and the eluent
flow, and a glass Büchi BOROSILIKAT 3.3 column tube N 17988, with
dimensions 9.6 mm × 115 mm (bed volume = 8.3 mL). To pack the
columns, DTPA-chitosan–silica (2.0 g) was soaked in an aqueous HNO3
solution. Then the stationary phase was poured in the column.
Pressurized air was used to ultimately pack the wet resin slurry.
Metal filter frits were mounted at the top and at the bottom of the
column. The pressure maximum was set at 10 bar. Separated com-
pounds were collected with the aid of a Büchi Automatic Fraction
Collector B-684. Each experiment was preceded by thorough washing of
the column with deionized water (50.0 mL), followed by conditioning
of the column with an aqueous HNO3 solution (50.0 mL), set at a
certain pH (pH = 5.00 in the first column experiment and pH = 2.00 in
the second column experiment). Then the leachate sample (5.0 mL) was
loaded and elution was initiated. The flow rate was set at 1 mL·min− 1.
Different column fractions (5.0 mL) were collected in conical tubes. A
decreasing pH gradient was applied during elution by increasing the
HNO3 concentration of the eluent solution. Final stripping of the
column was done with a 1.0 mol ⋅L− 1 solution of HNO3. The distinct
fractions were monitored by ex-situ analysis of the fractions with TXRF.
2.3.4. Analytical methods
Metal-ion concentrations were determined by means of TXRF on a
Bruker S2 Picofox TXRF spectrometer. The sample preparation for a
TXRF measurement consists of mixing the unknown metal ion solution
(100 μL) with a 1000 mg·L− 1 Ga standard solution (100 μL) and water
(800 μL) in an Eppendorf tube. A certain amount of this prepared
solution (5 μL) is put on a small quartz plate, pre-coated with a
hydrophobic silicone solution (10 μL), and dried in an oven at 60 °C.
3. Results and discussion
3.1. Atmospheric leaching
3.1.1. Fe(III)-HNO3 leaching
As a preliminary test, the boundary conditions with regard to nitric
acid and additional oxidants (i.e. ferric ion) concentrations on Pb and
Fe leaching from the matte phase were thoroughly investigated and
optimized in a previous study (Kim et al., 2017). The optimum
temperature for Pb leaching was 25 °C. As the temperature increased,
Pb leaching was decreased due to PbSO4 precipitation, while the
leaching efficiencies of Ni, Cu, and Zn in the tested leaching system
were not significant. The effect of acid concentration and additional
oxidant on metal leaching at 25 °C is presented in Fig. 2. The Pb
leaching increased from 63% to 69% upon increasing HNO3 concentra-
tion from 0.2 mol ⋅L− 1 to 0.5 mol ⋅ L− 1. Furthermore, when
0.15 mol ⋅L− 1 Fe(III) as Fe(NO3)3 in 0.5 mol ⋅L− 1 HNO3 was added as
an additional oxidant the Pb leaching was enhanced to 89% (Fig. 2).
Besides, the leaching efficiency of other metals (Ni, Cu, and Zn) was
around 20 to 30%.
3.1.2. Roasting followed by water leaching
Oxidation of FeS is necessary to decrease the dissolution of iron and
transform the minor valuable metal (Ni, Cu, Zn) sulfides into oxidic
metal compounds that are easily soluble in water or weak acid. In the
second step oxidation is achieved by roasting with subsequent water
leaching to recover Cu, Ni, Zn while keeping Fe in the residue.
3.1.2.1. Roasting. In order to determine the roasting boundary
conditions, matte sample was roasted at different temperatures
(1)
between 400 and 700 °C. Fig. 3 shows the XRD results of the matte
sample treated at different roasting temperatures. As shown in the
figure, the FeS reflections disappeared at 500 °C and reflections of
Fe2O3 appeared, after which the intensities of the Fe2O3 reflections
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E. Kim et al. Hydrometallurgy 169 (2017) 589–598

100
100
0.2mol L-1 HNO3 Pb
80 0.5mol L-1 HNO3 Fe
80 Ni
0.15mol L-1 Fe(III) +
0.5mol L-1 HNO3 Cu

Leaching (%)
Zn
60
Leaching (%)

60

40
40

20
20

0
450 500 550 600 650 700 750
0 Temperature ( C) o

Pb Fe Ni Cu Zn
Fig. 4. Effect of roasting temperature on metal leaching of the matte (leaching
Fig. 2. Leachability of the metals Pb, Fe, Ni, Cu and Zn from matte during atmospheric temperature 50 °C, L/S ratio 10).
leaching at 25 °C (L/S ratio 10).

100

80
Leaching (%)

60

40
Pb
Fe
Ni
20 Cu
Zn

Fig. 3. XRD patterns of the matte as a function of the roasting temperature. 0

20 30 40 50 60 70 80
increased with increasing temperature indicating the formation of a Temperature (oC)
more crystalline phase. The thermal analysis of FeS under oxidative
Fig. 5. Effect of leaching temperature after roasting at 600 °C of the matte (1 h, L/S ratio
conditions was reported by Kennedy and Sturman (1975). This work
10).
also supports that FeS was dominantly converted to FeSO4 with
accompanying formation of Fe3O4, Fe2O3 and FeS2 within the
slightly increased from 32 to 44% and from 46 to 54% with increasing
temperature range between 425 and 520 °C, causing a mass increase.
temperature from 25 °C to 70 °C, respectively.
Oxidation to Fe2O3 is complete at 725 °C. However, the PbS and Pb
phases were transformed into insoluble PbSO4 above 400 °C, inferring
that Pb phases should be leached before the roasting step. 3.2. Oxidative pressure leaching

Aqueous oxidation methods have attracted increasing attention in

3.1.2.2. Water leaching after roasting. As presented in Fig. 4, the
leachability of Ni, Cu, and Zn in water (50 °C, L/S 10) after roasting
was also strongly affected by roasting temperature. Maximum leaching
efficiency was 97% for Cu at 550 °C, 55% for Ni at 650 °C, and 50% for
Zn at 600 °C. The decreased leaching efficiency above 650 °C may be
due to the conversion to insoluble metal oxides or oxysulfates (Dunn,
1997). Taking into consideration the optimal leaching conditions of the
three metals, as well as the minimal leaching of iron, 600 °C is
considered the optimal roasting temperature.
Fig. 5 shows the effect of the water leaching temperature after
roasting at 600 °C. As shown in the figure, leaching of Cu was almost
stable between 76 and 80% indicating that the leachability is not
significantly affected by leaching temperature. For Ni and Zn leaching
view of environmental and economical perspectives (less emission of
gas and lower operating temperature with respect to roasting). The
aqueous oxidation can be operated at elevated temperatures and
pressurized conditions. Furthermore, Fe(NO3)3 self-decomposes at
elevated temperatures in autoclave systems, yielding hematite and
NO(g) with minor NO2(g). The nitrous gases are regenerated under
closed vessel conditions as nitric acid above 120 °C (Shang and Weert,
1993). Compared to atmospheric leaching, the regeneration of HNO3 in
a closed system allows the process to be operated with lower acid
concentrations and higher oxidation power. Oxidative pressurized
leaching in HNO3 was investigated as a possible leaching step.
Generally, as temperature increases (> 100 °C) sulfur oxidation is
enhanced (Mackiw et al., 1966), transforming sulfide minerals into

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E. Kim et al. Hydrometallurgy 169 (2017) 589–598

100 700 100

80 600 80

ORP (mVAg/AgCl)
Leaching (%)

60 500 60

Leaching (%)
Pb
40 Ni 400
40
Cu Pb
Zn Ni
Fe Cu
20 ORP 300 Zn
20
Fe

0 200
0.0 0.2 0.4 0.6 0.8 1.0 0
120 130 140 150 160 170 180 190
-1
HNO3 concentration (mol L )
Leaching temperature (oC)
Fig. 6. Effect of HNO3 concentration of leaching of metals from the matte (L/S ratio 20,
Fig. 8. Effect of temperature on the leaching of metals from the matte (L/S ratio 20,
130 °C, 0.5 h).
0.3 mol ⋅L− 1 HNO3, 0.07 mol ⋅L− 1 Fe(III), 1 h).

sulfate. This results in decreased Pb leaching due to PbSO4 or lead
jarosite precipitation (Zárate et al., 2012). Therefore, it is difficult to
simultaneously recover Pb, and other base metals such as Ni, Cu, and Zn
from sulfide minerals in nitric acid at elevated temperatures.
Leaching with HNO3 in varying concentrations was investigated at
130 °C to find the optimal leaching condition to enhance Pb, Cu, Ni, and
Zn leaching and avoid Fe dissolution at the same time. An autoclave
system was applied to perform tests. As shown in Fig. 6, Zn, Cu, and Ni
show increasing leaching efficiency with increasing HNO3 concentra-
tion from 0.1 up to 0.75 mol ⋅L− 1. However, Pb leaching was maximum
(84%) at 0.3 mol ⋅L− 1 HNO3 then decreased with increasing ORP
(oxidation power) to 83% at 0.5 mol ⋅L− 1 and 55% at 0.75 mol ⋅L− 1.
To enhance Pb leaching, 0.3 mol ⋅L− 1 HNO3 was chosen for further
study.
The effect of Fe(III) ion concentration at 130 °C is presented in
Fig. 7. Lead and copper leaching linearly increased with Fe(III) ion
concentration. The maximum Pb and Cu leaching was 92 and 60%,
100
respectively, at the highest Fe(III) concentration of 0.07 mol ⋅L− 1 Fe
(III). Ni (67%) and Zn (71%) leaching was maximum at 0.05 mol ⋅L− 1
Fe(III) and remained at this level for higher Fe(III) concentrations. It is
noteworthy that the iron leaching was below 3% (< 500 mg⋅L− 1) and
much lower than in atmospheric leaching (Fe 22%). The addition of
0.07 mol ⋅L− 1 Fe(III) was chosen as the optimum condition.
The leaching temperature is also an important parameter. Leaching
of Pb decreases with increasing leaching temperature (Fig. 8), whereas
the leaching of Cu, Ni, Zn was increased to 62, 76, 74%, respectively, at
160 °C and then decreased again. The decreased leaching efficiency at
180 °C may be due to the inclusion of Cu, Ni, Zn in the jarosite crystal
phase. Therefore, 130 °C was selected as the optimum leaching
temperature.
Fig. 9 shows the effect of leaching time. Lead leaching was slightly
increased from 88% to 92% by increasing leaching time from 15 to
60 min and then decreased to 52% at 120 min. For Fe, leaching
100
580

570 80
80

560
ORP (mVAg/AgCl)

Leaching (%)

60
Leaching (%)

60

550

40 Pb 40
Ni Pb
Cu 540 Ni
Zn Cu
Fe
20 20 Zn
ORP
530 Fe

0 520 0
0.00 0.02 0.04 0.06 0.08 0.10 0 20 40 60 80 100 120 140
Fe (III) (mol L-1) Leaching time (min)
Fig. 7. Effect of Fe(III) concentration on the leaching of metals from the matte (L/S ratio Fig. 9. Effect of leaching time on the leaching of metals from the matte (L/S ratio 20,
20, 130 °C, 0.3 mol⋅L− 1 HNO3, 1 h). 130 °C, 0.3 mol⋅ L− 1 HNO3, 0.07 mol⋅ L− 1 Fe(III)).

593
E. Kim et al.
100
Pb
Ni
80 Cu
Zn
Fe
ORP
Leaching (%)
60
40
20
0 150
8 10 12 14 16 18 20 22
L/S ratio
Fig. 10. Effect of L/S ratio on leaching of metals from the matte (130 °C, 0.3 mol ⋅L− 1
HNO3, 1 h).
decreased with time until a minimum of 0.4% at 120 min. For the other
metals, highest leaching efficiency was reached at 30 min (Cu, Zn) or
60 min (Ni) followed by a slight decrease after 120 min. Since the
leaching trends of Cu, Ni and Zn are similar to that of Fe leaching, the
decrease leaching efficiency of these minor metals may be due to co-
precipitation with Fe (e.g. jarosite or oxides). Furthermore, in future
scale-up studies, the cooling conditions of the reactor system require a
more in-depth study since currently the reactor systems were cooled in
air and not quenched. Therefore, the reaction times of the reported
experiments might be somewhat longer than reported. For all metals,
leaching was drastically decreased when the liquid-to-solid (L/S) ratio
was decreased from 20 to 10 (Fig. 10). With decreasing L/S ratio, the
ORP was also drastically decreased indicating the deficiency of oxidants
as shown in Fig. 10. Also, the pH was increased from 2.4 to 4.8 with
decreasing L/S ratio. Therefore, the decrease of leaching efficiency may
be due to the consumption and consequential lack of oxidants and
acids.
Based on the above results, the optimal condition of pressure
leaching to selectively leach Pb, Ni, Cu, Zn is 130 °C, 60 min,
0.3 mol ⋅L− 1 HNO3, 0.07 mol⋅ L− 1 Fe(III), L/S ratio 20.
3.3. Optimal leaching conditions
Two processes were investigated to recover valuable metals from
matte. The first process is a two-step approach combining Fe(III)-HNO3
leaching at 25 °C with roasting at 600 °C, followed by water leaching.
The second process is a one-step oxidative pressure leaching in nitric
acid (autoclave, 130 °C). The two processes are compared in Table 2.
Their total leaching efficiency is similar for Pb (90–92%), whereas Ni
(66%) and Zn (70%) leaching is higher for pressure leaching. On the
contrary, Cu leaching is higher (85%) in the two-step process. In the
2nd leaching step of two-step leaching process Cu, Ni, and Zn could be
more concentrated by 2–3 times compared to the pressure leaching
process due to a lower L/S ratio. The composition of the residues after
metal removal was also compared. In the residue of the two-step
leaching process, which includes roasting, Fe contents were above 60%
which meets the criteria for direct use as secondary iron ore with a very
low S content (1%). In the residue after pressure leaching, Fe and total S
content were 52% and 16%, respectively. Compared to the initial
material (Table 1), Fe content is slightly higher (increase from 50 to
52 wt%) due to precipitation of the Fe(NO3)3 reagent, while around
20% of sulfur goes into solution (decrease from 20 to 16 wt%). After
Hydrometallurgy 169 (2017) 589–598
550 roasting, the composition of the residue from the pressure leaching is
similar to that of the residue from the two-step leaching test. Fig. 11
500 shows the XRD patterns of the pressure leaching residue before and
after roasting. It confirms that the residue after roasting consists of
450 Fe2O3 as a dominant phase with trace amounts of PbSO4 (anglesite),
and can thus also be used as an iron ore.
400
Based on the results shown above, two processes were suggested to
ORP (mVAg/AgCl)
selectively leach Pb, Cu, Ni and Zn from matte and simultaneously
transform the FeS matrix in an Fe-oxide rich material (Fig. 12). Both
350
processes require a roasting step to oxidize the FeS matrix material in
view of total recycling. Meanwhile, the two-step leaching process is
300 superior since a more concentrated solution of Cu, Ni, and Zn (2–3
times higher compared to the pressure leaching process due to
250 difference in L/S ratio) is produced in the 2nd leaching step. Addition-
ally, the 2 stage leaching process requires a lower capital cost for
200 leaching (atmospheric condition, smaller reactor) even if it is a more
complex leaching process (2-step). Also, the leachate of the 1st leaching
step can be reused as leaching agent of in the same 1st step after Pb
removal through PbSO4 precipitation until a certain amount of Cu, Ni,
and Zn has been accumulated in the solution. Then it can be sent to the
separation and purification process to recover Cu, Ni, and Zn.
3.4. Metal recovery from leachate
For both the two-step leachate (Fe(III)-HNO3 leaching and water
leaching after roasting, L1) as well as for the leachate from the one-step
pressure leaching (L2), the recovery of Cu, Zn and Ni was studied. Both
samples were considered interesting for further processing, with the
two-step leachate having a considerably higher concentration of Cu
(1477 mg/L) and the one-step leachate resulting from a more efficient
leaching for Zn (70%) and Ni (66%). Separation of Cu, Zn and Ni was
investigated by the principle of ion-exchange adsorption with DTPA-
functionalized chitosan-silica. The structure of this adsorbent material
is shown in Fig. 13. Prior to recovery by adsorption, lead was removed
from the two-step leachate (L1). The Pb concentration after the first
step (Fe(III)-HNO3) was high enough to allow easy recovery by
precipitation as PbSO4. In the one-step leachate (L2) Pb was not
removed, in order to investigate the possibility of separating lead by
ion exchange, together with the other metals. The resulting composi-
tions of the leachates used in the recovery study are presented in
Table 3.
3.4.1. Precipitation of Fe(III) in a pre-hydrolysis step
Selectivity arises from the immobilization of the organic ligand
DTPA. DTPA shows a different affinity for different metal ions, based on
the stability constant of the complex that is formed between the organic
ligand and the chelated metal ion. By comparison of literature values of
stability constants between free DTPA and certain metal ions, one can
have a good estimation about the relative affinity of the corresponding
metal ions for DTPA-immobilized chitosan-silica particles. Some rele-
vant stability constants reported in the literature are summarized in
Table 4.
From Table 4, it appears that DTPA has the highest affinity for Fe
(III), compared to the other metal ions shown here. As a consequence,
the presence of Fe(III) ions in a leachate sample will hamper the
complexation of the other metal ions present in solution. This competi-
tion effect was confirmed by performing an adsorption experiment from
a synthetic mixture of Fe(III), Cu(II), Ni(II) and Zn(II). It was observed
that the adsorption of Fe(III) caused saturation of the adsorbent and
thus no Cu(II), Ni(II) or Zn(II) ions were removed from solution. To
eliminate the competition with Fe(III), it should either be reduced to Fe
(II) or removed from the solution. By reduction to Fe(II), the stability
constant, and thus affinity, significantly decreases, resulting in a lower
amount of iron adsorbed in favor of the other metal ions. However,
complete removal of iron from solution was considered a better option,
in order to fully prevent any iron from contaminating the available
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E. Kim et al. Hydrometallurgy 169 (2017) 589–598

Table 2
Comparison of two suggested processes for metal recovery from secondary lead smelting residue, matte.

Two-step leaching Pressure leaching

Optimum conditions 1) Fe(III)-HNO3 leaching: 25 °C, 0.5 mol ⋅L− 1 HNO3, 0.15 mol⋅ L− 1 Fe(III), 1 h, L/ 130 °C, L/S ratio 20, 1 h, 0.3 mol⋅ L− 1 HNO3, 0.07 mol⋅ L− 1
S ratio 8 Fe(III)
2) Roasting - water leaching: roasting temperature 600 °C, 50 °C, 1 h, L/S ratio
10

Elements 1st leaching (%) Total leaching (%) Residue (wt%) Leaching (%) Residue (wt%) Residueb (wt%)

Fe 20 26 62 2.1 52 63.5
Pb 89 90 0.7 92 0.4 0.4
Cu 22 85 0.2 60 0.3 0.4
Ni 31 41 0.1 66 0.1 0.1
Zn 22 61 0.1 70 0.06 0.1
S NDa NDa 1 NDa 15.7 0.7
Mass loss (%) 40 12

a
ND: not determined.
b
After roasting of the residue from pressure leaching (roasting temperature: 600 °C for 2 h).

Fig. 13. Chemical structure of DTPA-functionalized chitosan-silica hybrid material.

Fig. 11. XRD patterns of the pressure leaching residues before and after roasting.

peroxide solution were added to the leachate (Morgan and Lahav,

sorption sites. Removing Fe(III) from solution is very easy by hydro- 2007). The new composition of leachate L1 is shown in Table 5.
lysis. By increasing the pH to 3–4, Fe(OH)3 precipitates and can be
easily separated from solution by centrifugation, without affecting the
3.4.2. Metal recovery from leachate L1
concentration of the other ions present in the leachate, since these start
After precipitating Fe from the leachate, adsorption from this
to hydrolyze at higher pH values. Note that also Fe(II) starts to
leachate was investigated. From Fig. 14, it can be observed that the
hydrolyze at higher pH values. In order to make sure that all iron in
sorbent is able to recover Cu and Ni nearly quantitatively from solution.
solution was at the + III oxidation state, some droplets of hydrogen
Ca is not adsorbed, which is in agreement with our aims, as adsorption

Fig. 12. Suggested flow sheets.

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E. Kim et al. Hydrometallurgy 169 (2017) 589–598

Table 3
Leachate composition for metal recovery.

Leachate Fe (mg·L− 1) Pb (mg·L− 1) Cu (mg·L− 1) Ni (mg·L− 1) Zn (mg·L− 1) Ca (mg·L− 1) pH

L1a 2090 4 1477 101 296 104 2.1

L2b 416 717 90 39 54 310 1.8

a
L1: water leaching after roasting at 600 °C from two-step leaching.
b
L2: pressure leaching with Fe(III)-HNO3 at 130 °C.

Table 4 100
Stability constants (log K values) between free DTPA and certain metal ions (Perrin,
6
1979).
80 5

Cumulative breakthrough (%)

Metal ion Fe(II) Fe(III) Pb(II) Cu(II) Ni(II) Zn(II) Ca
Zn
4
Log K 15.97 27.30 19.05 21.53 20.32 18.75
60 Ni

Aqueous pH
Cu
3
pH
Table 5 40
Composition of leachate L1 after pre-hydrolysis to remove Fe. 2

Metal iona Fe Cu Ni Zn Ca pH 20 1
−1
Concentration (mg·L ) 3.9 1340 104 275 96 3.51
0
a
0
Only metal ions with a concentration > 1 ppm are reported.
0 50 100 150 200 250 300
Elution volume (mL)
100
Fig. 15. Column separation experiment with leachate L1. The cumulative breakthrough is
reported as a function of elution volume. A decreasing pH gradient (increasing [HNO3])
80 was applied.

nated. As a consequence, the affinity for the loaded metal ions

60
Recovery (%)

40
20
0
1.8 2.0 2.2 2.4
Equilibrium pH
Fig. 14. Percentage recovery of Cu, Ni, Zn, Sn and Ca from leachate L1 with DTPA-
chitosan-silica, as a function of the equilibrium pH.
of Ca, present in a comparable concentration with Ni, would contam-
inate the resin with unwanted ions. Pb and Zn are partially removed
from solution. At pH = 2.03, a recovery of 84.13% and 77.92% was
obtained for Pb and Zn, respectively. This is due to their lower (and
comparable) affinity for DTPA. Note also for Pb and Zn that adsorption
increases as a function of pH. This has to do with the deprotonation of
carboxylic acid functional groups of DTPA by increasing the pH. An
increase of the negative charge density on the ligand, immobilized on
the chitosan-silica matrix, is in favor of ionic interactions with the
positively charged, free metal ions in solution.
The selective ion exchange observed in the batch adsorption
experiments was exploited in a column-chromatography setup. A
column consists of a solid phase of functionalized material through
which a solution flows. This not only allows to recover metals from the
leachate, but also to separate them from each other. By collecting all
single-element fractions, pure metal solutions can be obtained. A
separation experiment was conducted with leachate L1. After loading
the column with the leachate sample, elution was initiated by applica-
tion of a decreasing pH gradient. In Fig. 15, the breakthrough curves of
Ca, Zn, Ni and Cu are presented. By decreasing the pH, the carboxylic
acid functional groups on the resin become progressively more proto-
decreases and the metal ions are no longer retained on the column.
The order of breakthrough depends on the affinity of the different metal
Pb ions for the resin. The order observed was in agreement with the batch
Ni adsorption experiment: Ca < Zn < Ni < Cu, as was also expected
Cu
Zn
from the corresponding stability constants between the respective metal
ions and DTPA (Table 4).
Ca
In Fig. 15 it is shown that it is possible to separate the mixture in the
metal ions of which it is composed. From the batch adsorption test, it
was observed that calcium has no affinity for the functionalized resin.
2.6
For this reason, it immediately eluted from the column. Even with the
pH of the column set at pH = 5.00, it broke through the column as the
first element. In the time all calcium eluted, the pH had been decreased
to pH = 2.00. The second element that eluted, was zinc, at a
pH = 1.50. It had been fully removed from the resin by the time that
nickel started to elute, at pH = 1.00. Copper started to elute at
pH = 0.50. At this pH, not all nickel had been eluted yet. This is due
to the high affinity of both metal ions for the resin, with the
corresponding values close to each other. Part of the fractions therefore
contained both nickel and copper. Nevertheless, a better control of the
elution pH and further optimization of the experimental parameters
could improve the separation of nickel and copper, so that for these ions
too, pure metal fractions could be obtained. Possible measures that
could be taken to achieve a better separation are the use of a longer
column, a lower flow rate, a slower decrease in pH, etc. The latter was
applied in the next experiment.
3.4.3. Metal recovery from leachate L2
Also for leachate L2, the metal recovery was investigated by the
principle of column chromatography. The resulting chromatogram is
presented in Fig. 16. Compared to the previous separation experiment
(Fig. 15), a slower decreasing pH gradient was applied here. As a result,
breakthrough of the different metal ions occurred more carefully. The
metals Cu, Zn and Ni were separated well from each other. The
possibility of also recovering Pb by ion exchange was investigated.
Unfortunately, it eluted together with Ni. Since the corresponding

596
E. Kim et al.
100
80
Cumulative breakthrough (%)
60
40
Zn
20 Pb
Ni
Cu
0 two-step leaching seems to be superior for getting concentrated
0 50 100 150 200 250
Elution volume (mL)
Fig. 16. Column separation experiment with leachate L2. The cumulative breakthrough is
reported as a function of elution volume. A decreasing pH gradient (increasing [HNO3])
was applied.
affinity values are too close to each other, it seems to be a better option
to remove lead first by precipitation with sulfate, as described above. In
that case, pure solutions of both Zn, Ni and Cu can be obtained from the
leachate originating from the matte.
The performance of the DTPA-functionalized chitosan-silica materi-
al as the stationary phase in a lab-scale chromatography column is
promising. The porosity was found to be sufficient to ensure a fluent
flow (liquid percolation) through the column. Also the ease with which
the column could be desorbed and reused in repetitive separation
experiments was high, thus revealing a high potential use outside of the
laboratory as well. Nevertheless, it is clear that the tested elution setup
results in an average 10-fold dilution of the metal concentration in the
column fractions compared to the initial leachate. It may be considered
to concentrate the leachate feed prior to column separation or to
concentrate the column fractions by evaporation. In both cases, an
economically feasible implementation of this technique for the recovery
of base metals will require further optimization of the elution para-
meters, to increase the metal concentration in the respective column
fractions. During industrial process development, continuous, sequen-
tial column configurations could further improve the final concentra-
tions. Nonetheless, it was shown that separated fractions of Cu, Ni and
Zn could be collected from a leachate of a lead-smelter residue by one
simple column-chromatography cycle. In the presence of the strongly
basic sulfide anion, Cu, Zn and Ni form highly insoluble metal salts,
even at low pH. Hence, by addition of hydrogen sulfide these metal ions
could be precipitated from the diluted column fractions.
4. Conclusions
Two possible routes, two-step nitric acid leaching and one-step
oxidative pressure leaching, were investigated to selectively recover Pb
and other minor metals (Cu, Ni, Zn) from lead smelter residue, matte.
The two-step leaching process consists of Fe(III)-HNO3 leaching in the
first step and roasting, followed by water leaching in the second step. In
the first step, Pb leaching was 90% at the optimum condition: L/S ratio
8, 0.5 mol⋅ L− 1 HNO3, 0.15 mol ⋅L− 1 Fe(III), 25 °C. In the second step,
roasting at 600 °C followed by water leaching at 50 °C selectively
leached Ni, Cu, and Zn with a complete conversion of Fe sulfides to
oxides. In the final residues, Fe content was above 60% which can be
directly used as secondary iron ores in blast furnaces. With the one-step
pressurized leaching in nitric acid, Pb, Cu, Ni, and Zn could be leached
simultaneously without dissolving the matrix materials. At the optimal
condition (130 °C, 60 min, 0.3 mol⋅ L− 1 HNO3, 0.07 mol ⋅L− 1 Fe(III),
L/S ratio 20), Pb, Cu, Zn and Ni leaching were 92, 60, 70 and 66%,
Hydrometallurgy 169 (2017) 589–598
respectively, while Fe leaching was limited to 2%. The pressure
4 leaching would be more economical and environmentally friendly
(i.e. lower SOx emission and operating temperature, and simple
process). In a next stage, it was possible to fully recover the valuable
3 metals Cu, Zn and Ni from the leachates by ion-exchange adsorption.
DTPA-functionalized chitosan-silica was used as the stationary phase in
Aqueous pH
column chromatography to mutually separate Cu, Ni and Zn from each
2 other. Separated fractions were obtained by applying a decreasing pH
gradient. Pb and Fe were removed from the leachates in a pre-treatment
step: Pb by sulfate precipitation and Fe by hydrolysis. The investigated
1 leaching and metal recovery methods can be combined as process steps
of two possible routes for the selective recovery of Pb (90–92%), Cu
(85–60%), Ni (41–66%), and Zn (61–70%) from the studied secondary
0 lead smelting residue. Comparing the two investigated processes, the
300 350 400 solutions of Cu, Ni, and Zn in the 2nd leaching step (2–3 times higher)
and it requires a lower capital cost for leaching (due to atmospheric
leaching condition and smaller reactor sizes) even if it is a more
complex leaching process (2-step).
Acknowledgements
This research project (MaxiVIA) (MIP-ICON, IWT Ref 140639) was
carried out with the support of the Flemish Region - Environmental and
Energy Technology Innovation Platform (MIP) (140639). The work was
also funded by the Research Foundation – Flanders (FWO) and the
Flemish Institute for Technological Research (VITO) (PhD fellowship to
JR). The authors would like to thank Warre Van Dun and Bo Peeraer for
performing ICP-AES measurement and sampling. Furthermore, we
thank Myrjam Mertens also for performing XRD measurements and
analysis.
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