Hydrometallurgy 153 (2015) 170178

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

Cleaning of high lead-bearing zinc leaching residue by recovery of lead

with alkaline leaching
Mehmet ahin, Mehmet Erdem
Department of Environmental Engineering, Frat University, 23279 Elaz, Turkiye

a r t i c l e

i n f o

Article history:
Received 29 November 2014
Received in revised form 23 February 2015
Accepted 7 March 2015
Available online 10 March 2015
Keywords:
Zinc leaching residue
Cleaning
Lead recovery
Pressure leaching
Kinetics
TCLP

a b s t r a c t
In the hydrometallurgical zinc production processes, huge quantities of solid leaching residues containing different metallic compounds threat the environment are continuously generated around the world. Due to increasing
demand of metals and the depletion of high grade natural resources, these types of wastes are gaining great importance in the metallurgical industries. In this study, cleaning of zinc leaching residue, containing 19% Pb in the
form of anglesite, by recovering of lead with alkaline leaching was investigated. For this purpose; the effects of
NaOH concentration, leaching time and temperature on the Pb recovery from the residue were studied. Under
the optimum conditions using NaOH concentration of 11%, L/S ratio of 5, temperature of 100 C, and leaching
time of 60 min, the leaching ratio of Pb reached up to 99.6%. Kinetic analysis of the experimental data showed
that the leaching was ash layer diffusion controlled with activation energy of 2.78 kJ/mol. Pb could be effectively
separated from the pregnant leach solution with chemical precipitation by Na2S and CO2. TCLP and EU Directive
EC/2003/33 tests applied to the remaining leach residue showed that it was environmentally stable and nonhazardous waste, respectively.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Zinc is commonly produced from its ores in the combined systems
consist of roastingleachingelectrowinning processes in worldwide.
In these processes, ZnO-rich calcine is rst produced from the concentrates and then zinc in the calcine is leached with hot sulphuric acid
solution. A pregnant leach solution and a solid leach residue are obtained after liquidsolid separation by rotary lter. The pregnant solution is
puried and zinc is won by electrolysis.
Zinc leaching residues contain signicant amounts of precious metals
such as lead, silver, cadmium and unextractable zinc. Zinc and lead usually
occur together in a variety of minerals. Therefore, zinc production residues contain important amount of lead. These residues are generally
stockpiled in many plants to recover these precious metals in the future
(Turan et al., 2004). The leach residue is also classied as a hazardous
waste due to the presence of signicant amounts of leachable heavy
metals (zverdi and Erdem, 2010). Due to increasing demand of metals
and the depletion of high grade natural resources, these types of secondaries and wastes are gaining great importance in the metallurgical
industries. In order to recover metallic values from these types of secondaries/wastes, a lot of researches have been made (Abdel Basir and
Rabah, 1999; Banza et al., 2002; Barakat, 1999; Kinoshita et al., 2004;
Kul and Topkaya, 2008; Lai et al., 2008; Li et al., 2008, 2009, 2010;

Corresponding author.
E-mail address: merdem@rat.edu.tr (M. Erdem).

http://dx.doi.org/10.1016/j.hydromet.2015.03.003
0304-386X/ 2015 Elsevier B.V. All rights reserved.

Morgan and Lee, 1997; Rossini and Bernardes, 2006; Shen and
Forssberg, 2003; Silva et al., 2005; Turan et al., 2004). Hydrometallurgical processes are widely used technology in today's production of base
and valuable metals. Therefore, it has also received extensive attention
by researchers interested in recovering metals from secondaries/
wastes. In the hydrometallurgical processes, different lixiviants such
as sulphuric acid (Abdel Basir and Rabah, 1999; Asadi Zeydabadi et al.,
1997; Huang et al., 2007; Kul and Topkaya, 2008; Li et al., 2010; Luo
et al., 2010; Nagib and Inoue, 2000; Ruen et al., 2008), hydrochloric
acid (Abdel Basir and Rabah, 1999; Nagib and Inoue, 2000), nitric acid
(Ioannidis et al., 2006; Zrate-Gutirrez et al., 2010), caustic soda
(Jarupisitthorn et al., 2003; Nagib and Inoue, 2000; Santos et al., 2010;
Xia and Pickles, 1999a, 1999b; Xia and Picklesi, 2000; Zhao and
Stanforth, 2000), brine (Andrews et al., 2000; Guo et al., 2010;
Raghavan et al., 1998, 2000; Turan et al., 2004), ammonia, ammonium
carbonate, ammonium chloride, and some carboxylic acids (Jha et al.,
2001) are generally used. Acidic leach solutions, caustic soda and
brine solution have been found to be very effective lixiviant for the
leaching of lead and zinc. Although high leaching yields can be obtained
in the acidic leach solutions and brine solutions, they are not applicable
due to releasing of the important amount of impurities and chloride
ions, which is affected seriously the quality of zinc powder and the current efciency in electrowinning of zinc (Zhao and Liu, 2011). Caustic
soda is the most suitable lixiviant in this respect for the amphoteric
lead and zinc. In the caustic soda leach process, lead and zinc are selectively dissolved in sodium hydroxide solution rejecting nonamphoterics
in the residue.

M. ahin, M. Erdem / Hydrometallurgy 153 (2015) 170178

The process has been attempted for the dissolution of zinc from different sources such as iron and steel making dusts (Dutra et al., 2006; Frenay
and Hissel, 1984), electric arc furnace dust (Xia and Pickles, 1999a, 1999b;
Xia and Picklesi, 2000), smithsonite ZnPb ores (Zhao and Stanforth,
2000), and y ash generated from municipal incineration plants (Nagib
and Inoue, 2000). In these researches, atmospheric leach processes have
been widely applied and readily soluble constituents have been leached
out. Particularly, Nagib and Inoue (2000) have been reported that the alkaline leaching of y ash generated from municipal incineration plants is
a potentially feasible method for simultaneous detoxication and metal
recovery. Santos et al. (2010) reported that 74% of zinc was extracted
from zinc silicate ore by leaching with 6 M NaOH in 4 h. Zhao and
Stanforth (2000) studied the production of zinc powder by alkaline treatment of smithsonite ZnPb ores that could obtain 85% of both Zn and Pb
recovery using 5 M NaOH at over 95 C. Xia and Picklesi (2000) found that
95% zinc recovery from zinc ferrite in the electric furnace was achieved by
8 M microwave NaOH leaching. Jarupisitthorn et al. (2003) also studied
the kinetics of zinc leaching from electric arc furnace dust by NaOH.
They achieved the recovery of 77% Zn with 1.54 M NaOH in 60 min.
In recent years, the hydrometallurgical processes carried out at elevated temperature/pressure have become great interest for recovery
of valuable compounds with low solubility (Azimi and Papangelakis,
2010; Havlik et al., 2004; Huang et al., 2007; Jin et al., 2009; Langov
and Matsek, 2010). These processes improve the mass transfer of the
leach solution into solid particle and thus, accelerate the dissolution kinetics by the effects of temperature and pressure. Particularly, cleaning
of high lead-bearing zinc leaching residue by recovery of lead with alkaline leaching has not been investigated. Starting from this point, in this
study, the application of pressure leaching technique in the recovery of
whole lead from the zinc leaching residue by selective NaOH leaching
was studied. The effects of parameters including the initial NaOH concentration, leaching time and leaching temperature on the leaching efciency and the leaching kinetics, separation of lead from the leach
solution and pollution potential of the leach residue were investigated.
2. Materials and methods
2.1. Materials
As described in our previous papers, the zinc leaching residue (ZER)
used in the study was obtained from inkur Plant located in Kayseri,
Turkey. It was dried at room temperature for ten days and then subjected to sieve analysis. Sieve analysis showed that about 76% of the ZER
was smaller than 150 m (100 mesh). The sample was sieved to obtain particles smaller than 75 m (200 mesh) prior to use. The chemical and mineralogical compositions of the residue were determined.
Chemical analysis shows that the ZER contains 19.02% Pb, 12.25% S,
7.98% Zn, 6.19% Ca, 6.74% Si, 5.44% Fe and 1.85% Al as major elements.
The major mineralogical phases in the residue were determined to be
gypsum [CaSO4.2H2O], anglesite [PbSO4], massicot [PbO], quartz [SiO2],
maghemite [Fe2O3], hercynite [Al2FeO4] and franklinite [ZnFe2O4]
(zverdi and Erdem, 2010).

171

it was placed in the reactor. The reactor content agitated continuously at

a 700 rpm constant speed was heated up to predetermined temperature. After achieving the desired temperature, the required reaction
time was started. The temperatures being used and the corresponding
pressures are given in Table 1. After the reaction was completed, the reactor was removed from the heater mount and was rapidly watercooled to 70 C. The reactor content was ltered by vacuum ltration.
The leach residue was then washed three times with 50 ml 50 C distilled water and then the wash solutions were added to the main pregnant leach solution. The solutions were analyzed for dissolved metal
ions, while the solid leach residues were subjected to mineralogical,
chemical and particle size analyses.
2.2.2. Separation of the lead from pregnant leach solution
In order to separate lead dissolved from the pregnant leach solution,
two chemical precipitation methods with sodium sulde (in the form of
PbS) and carbon dioxide (in the form of PbCO3) were applied. For this
purpose, while different weight ratios of sodium sulde to the lead
were tested to precipitate whole lead ions in the leach solution, carbon
dioxide gas was bubbled through the pregnant leach solution diluted
with 1/3 distilled water to reduce the alkalinity. Mineralogical compositions of the solid materials precipitated were determined by X-ray
diffractometer.
Each experiment was performed in duplicate and arithmetic averages calculated from the values varied within 5% were taken into
account.
2.2.3. Determination of the pollution potential of the leach residue
The toxicity characteristic leaching procedure (TCLP) (USEPA, 1990)
and the European Directive EC/2003/33 test methods were applied to
determine the potential release of contaminants from the leach residue.
For the TCLP, pH of the leach residue was rst determined and the extraction solution was selected depending on the pH measured. Then,
the leach residue was extracted at a liquid to solid ratio (L/S) of 20 in
capped polypropylene bottles on a rotary tumbler at 30 2 rpm and
23 2 C for 18 2 h. For the European Directive EC/2003/33 (EC,
2003), the leach residue was treated with water at L/S of 2 and 10 l/kg
in capped polypropylene bottles at 25 2 C for 24 h. After both extractions, the liquids were separated from the solid residue by ltration
through a 0.45 m glass ber lter and the ltrates were analyzed.
2.3. Methods of analysis
Philips PW-2404 electron X-ray uorescence spectroscopy and
Shimadzu XRD-6000 X-ray diffractometer were used for the determination of chemical and mineralogical compositions of the samples, respectively. In addition, all solid samples were digested by microwave
digestion unit (CEM MarsX Press) for chemical analysis. Perkin Elmer
AAnalyst 800 was used to determine the metal ion concentrations in
the solutions. Particle size of the samples was measured by using
Malvern Master Sizer 3000.
3. Results and discussion

2.2. Experimental procedure

3.1. Leaching reactions
2.2.1. Leaching experiments
Leaching experiments were conducted in a 500 ml stainless steel SS
316Tl high pressure reactor (Berghof BR 500). The reactor is equipped
with a PTFE insert, thermal sensor with immersion tube, gas and liquid
sampler, manometer, vent valve and stirrer. All sides of the reactor are
lined with PTFE. Agitation and heating are provided by a stirrer shaft
in the reactor interior by means of a magnetic clutch and heater block
mount, respectively. The temperature and agitation speed were controlled with a PID controller.
About 40 g of the ZER was mixed in 200 ml NaOH solution having desired concentration in the PTFE insert prior to each experiment and then

The ZER used in the study contains mainly of gypsum [CaSO4.2H2O],

anglesite [PbSO4], massicot [PbO], quartz [SiO2], maghemite [Fe2O3],
hercynite [Al2FeO4] and franklinite [ZnFe2O4]. In the hydrometallurgical
recovery processes, different lixiviants such as sulphuric acid (Abdel
Table 1
Leaching temperatures and corresponding pressures being used for the experiments.
Temperature, C
Pressure, bar

85
0.9

100
1.0

125
3.4

150
5.1

175
7.5

M. ahin, M. Erdem / Hydrometallurgy 153 (2015) 170178

172

Basir and Rabah, 1999; Asadi Zeydabadi et al., 1997; Huang et al., 2007;
Kul and Topkaya, 2008; Li et al., 2010; Luo et al., 2010; Nagib and Inoue,
2000; Ruen et al., 2008), hydrochloric acid (Abdel Basir and Rabah,
1999; Nagib and Inoue, 2000), nitric acid (Ioannidis et al., 2006;
Zrate-Gutirrez et al., 2010), caustic soda (Jarupisitthorn et al., 2003;
Nagib and Inoue, 2000; Santos et al., 2010; Xia and Pickles, 1999a,
1999b; Xia and Picklesi, 2000; Zhao and Stanforth, 2000), brine solution
(Andrews et al., 2000; Guo et al., 2010; Raghavan et al., 1998, 2000;
Turan et al., 2004), ammonia, ammonium carbonate, ammonium chloride, and some carboxylic acids (Jha et al., 2001) are generally used.
Acidic leach solutions are commonly used for the leaching of metal
values. Although high leaching yields can be obtained in the acidic
leach solutions, releasing of the important amount of impurities together with metal values is a disadvantage. In order to eliminate this disadvantage, selective leaching with proper chemicals that can extract the
only desired metal is preferred. In this study, NaOH solution was used
as lixiviant for lead recovery depending on its amphoteric properties.
Lead founds mainly of anglesite [PbSO4] and massicot [PbO] crystalline
forms in the ZER. The dissolution reactions of lead minerals from the
ZER with NaOH may be represented as follows:

PbSO4s 3NaOHaq PbOH3 aq SO4 aq 3Naaq

PbOs NaOHaq H2 Ol PbOH3 aq Naaq :

1
2

The other constituents such as Zn, Si and Al compounds in the ZER

together with lead also react with NaOH according to Eqs. (3)(5) and
consume additional NaOH.
ZnFe2 O4s 2NaOHaq Na2 ZnO2aq H2 Ol Fe2 O3s

SiO2s 2NaOHaq Na2 SiO3aq H2 Ol

Al2 O3s 2NaOHaq 2NaAlO2aq H2 Ol

Fig. 1. Effect of NaOH concentration on the leaching of Pb from the ZER [liquid/solid ratio:
5, contact time: 60 min, stirring speed: 700 rpm, leaching temperature: 100 C].

such as steel mill electric arc furnace dusts and leaching residues of
roasted zinc sulde concentrates, is refractory oxide and has low solubility (Langov et al., 2009; Zhao and Stanforth, 2000). In some research
related zinc recovery from the zinc ferrites, it has been reported that the
zinc ferrites are very stable and have low solubility in most alkaline solutions (Elgersma et al., 1992; Havlik et al., 2005; Nagib and Inoue, 2000;
Xia and Pickles, 1999a; Youcai and Stanforth, 2000; Zhao and Stanforth,
2000). The ndings are consistent with results of these related researches. In addition, dissolutions of silica and aluminum from the ZER
were negligible levels. While 1.09% of silica dissolved from the ZER,
much lower aluminum dissolution (0.22%) was detected due to insoluble crystalline form of hercynite (Twardowska et al., 2004).
3.3. Effect of leaching time
The effect of leaching time on the extraction of lead was investigated
in the range from 15 to 90 min depending on NaOH concentration. All

The compounds in the ZER mentioned above are dissolved in NaOH

solution while other impurities remain in the solid residue.
3.2. Effect of NaOH concentration
The stoichiometric amount of NaOH required to recover lead from
the ZER was calculated to be 0.4275 g-NaOH/g-ZER by taking into account both main lead reactions (Eqs. (1), (2)) and other side reactions
(Eqs. (3)(5)) that consumed additional NaOH. This value correspondences 8.55% (w/v) NaOH for a reactor content. Some preliminary
leaching experiments were performed on the basis of the a stoichiometric amount of NaOH under the conditions of liquid/solid ratio of 5, contact time of 60 min, stirring speed of 700 rpm and temperature of
100 C. In these experiments, about 37% Pb could be leached from the
ZER. This leaching percentage shows that a stoichiometric amount of
the NaOH is insufcient to extract the whole lead in the residue under
the investigated conditions. In order to obtain effective leaching yields,
higher stoichiometric amounts of NaOH in the range of 1015% were
studied. The results are given in Fig. 1, which shows that the leaching
yield increased signicantly with the increasing NaOH concentration.
Leaching yield of lead increased from 79.47% to 99.6% with an increase
in NaOH concentration from 10% to 11%. Similar trend has been observed by Jarupisitthorn et al. (2003) who investigated kinetics of zinc
leaching from electric arc furnace dust by sodium hydroxide.
Zinc also dissolved from the ZER under the investigated conditions
and dissolution yields partly increased with the increasing NaOH concentration. However, the leaching yields of zinc (maximum 30%) were
lower than those of lead (Fig. 1). This situation can be attributed to
the fact that the zinc in the residue was found in the form of franklinite
(zinc ferrite). Franklinite, which is a major form of Zn in some wastes

Fig. 2. Effect of leaching time on the leaching of Pb from the ZER [liquid/solid ratio: 5, stirring speed: 700 rpm, leaching temperature: 100 C].

M. ahin, M. Erdem / Hydrometallurgy 153 (2015) 170178

173

3.5. Kinetic analysis

The leaching of lead from the ZER in the NaOH solutions includes
heterogeneous reactions represented by Eqs. (1) and (2). The shrinking
core model can be used to describe the leaching kinetics of the uid
solid heterogeneous reaction system. The model considers that the
leaching process is controlled either by the diffusion of reactant through
the solution boundary layer, or through a solid product layer (generally
called as ash layer) or by rate of the surface chemical reaction by assuming that the solid particle retains its initial spherical shape. The rate of
the process is controlled by the slowest of these sequential steps.
Eqs. (6)(8) of the shrinking core model given as follows can be used
to describe the leaching kinetics when the diffusion of NaOH through
the solution boundary layer, the solid ash layer, and the surface chemical reaction is the rate-controlling step, respectively (Levenspiel, 1972).
n

3:b:kd :NaOH =:r o Kd :t

2=3

131

1=3

11

6
2

21 6:b:Deff :NaOH=:r o KD :t
n

b:ks : NaOH =:r o KR :t

7
8

where, is the fractional conversion, b is stoichiometric coefcient, ks is

the chemical reaction rate constant, [NaOH] is the sodium hydroxide
concentration, n is the reaction order with respect to NaOH, is the

Fig. 3. Effect of temperature on the leaching of Pb from the ZER [liquid/solid ratio: 5, NaOH
concentration: 11% (w/v), stirring speed: 700 rpm].

the experiments were conducted under the conditions of 700 rpm

stirring speed, 100 C temperature and 5:1 liquid/solid ratio and
NaOH concentration in the range of 8.5515%. The results are presented in Fig. 2. Leaching time affects the extraction of lead signicantly. An increase in the leaching time from 15 to 45 min led to a
rapid increase in the leaching yield of lead. The lead extraction
reaches a maximum value (99.6%) after 60 min at the higher NaOH
concentration of 10%. It has been determined that the leaching yields
were increased with the increasing leaching time, but reaction rates
were slow for lower NaOH concentration of 11%. Therefore, considering energy consumption, it can be stated that the 60 min leaching
time and 11% NaOH concentration are the best in achieving an effective lead cleaning by leaching.

3.4. Effect of temperature

The leaching yields versus temperature are given in Fig. 3. The
data clearly demonstrate that the temperature has a pronounced effect on lead extraction. The leaching yields of lead markedly increased with the increasing temperature and reached a maximum
at 100 C; however, it was observed that the leaching yields of zinc
partly increased under the same conditions. Rising temperatures
help improve the leaching rates and shorten leaching time. Nearly
99.6% Pb was extracted in 60 min at 100 C in 11% NaOH solution. It
can be found that a high enough temperature is necessary to activate
the reagent and accelerate the reaction of hydroxyl ions with lead in
the alkaline leaching. Thus, the appropriate leaching temperature
was chosen as 100 C and all further experiments were carried out
at this temperature.
Under the investigated conditions, it has been observed that the
maximum leaching yield of zinc was about 37% at 175 C. This low dissolution ratio of zinc can be attributed to its franklinite form, which cannot be easily dissolved by NaOH, in the ZER again.

Fig. 4. Shrinking core model for leaching of Pb from the ZER at different temperatures.

174

M. ahin, M. Erdem / Hydrometallurgy 153 (2015) 170178

molar density of ZER, ro is the initial radius of the particle, Deff is the effective diffusion coefcient, Kd and KD are the kinetic parameters for diffusion controls through the solution boundary layer and solid ash layer,
respectively, KR is the kinetic parameter for surface reaction control and
t is the leaching time.
When the leaching process is controlled by diffusion through the
solid ash layer, a plot of 13(1 )2/3 + 2(1 ) versus time is a
straight line with a slope of KD. Similarly, if the surface chemical reaction
is the rate-controlling step, a plot of 1 (1 )1/3 versus time gives a
straight line with a slope of KR (Levenspiel, 1972). In the case of high
stirring speed, the diffusion through the solution boundary layer is generally neglected. Fig. 4 shows that the plot of fraction of lead leached
versus time does not t with a straight line, therefore, the diffusion
through the solution boundary layer could not be rate determining in
the leaching system. But, there is a good t between the experimental
data and Eqs. (7) and (8), indicating that the leaching kinetics of lead indeed can be described by the shrinking core model with the ash layer

diffusion control together chemical reaction. The highest values of the

correlation coefcient R2 for linearity of the plots are obtained for both
mechanisms.
In order to determine the activation energy, the Arrhenius equation
was applied to the data obtained from each temperature for lead
leaching. According to the Arrhenius equation, a plot of log K versus 1/
T for the K values determined from Eqs. (7) and (8) is a straight line
where the slope is (Ea/R). Depending on the activation energy value,
it can be decided that the heterogeneous reaction mechanism is chemical or diffusion-controlled. The activation energy values higher than
40 kJ/mol indicate chemical reaction-controlled processes whereas the
values lower than 20 kJ/mol indicate the diffusion-controlled processes
(Levenspiel, 1972). Activation energy (Ea) values for Pb leaching were
calculated to be 3.552 and 2.78 kJ/mol from the data KR and KD values, respectively. Although the leaching data of Pb t well both of Eqs. (7) and
(8) (Fig. 4), depending on the activation energy values, it can be stated
that the diffusion-controlled mechanisms control the Pb leaching from

Fig. 5. XRD patterns of the precipitates obtained from chemical precipitation with (a) Na2S and (b) CO2.

M. ahin, M. Erdem / Hydrometallurgy 153 (2015) 170178

the ZER. Xia and Pickles (1999a) and Terry and Monhemius (1983) reported the same nding.
Ash lm diffusion-controlled mechanisms are generally shown as heterogeneous reactions in which a liquid contacts with a solid containing
large amount of impurities. In these systems, since the impurities remain
as nonaking ash, solid particles remain unchanged in size during the reaction. In order to verify this situation, zinc plant residue used in the study
and the leaching residue were subjected to particle size analysis. Mean
particle sizes of the ZER and the solid leaching residue were found to be
27.431 and 28.056 m, respectively. Almost unchanged particle sizes
also conrm the presence of an ash layer on the particle surface and
thus the leaching process is controlled by the ash layer diffusion control.

175

3.6. Separation of Pb from pregnant leach solution

Zinc and lead usually occur together in a variety of minerals. The dissolution properties of lead and zinc are similar due to their amphoteric
properties and they dissolve in alkaline and acidic solutions. Therefore,
the selective and quantitative separation of lead from zinc is an important step in the effective use of the metal sources. In order to separate
lead from zinc in acidic and alkaline solutions, cementation process
using zinc powder and sulde precipitation process with sodium sulde
are usually applied, respectively (Youcai and Stanforth, 2000). In this
study, almost 99.6% lead and 30% zinc dissolved from the ZER under
the investigated conditions and a pregnant leach solution containing

Fig. 6. XRD patterns of the ZER and leach residue remaining in the alkaline pressure leaching.

176

M. ahin, M. Erdem / Hydrometallurgy 153 (2015) 170178

30.16 g/l lead and 4.8 g/l zinc was obtained. In order to recover lead
from the alkaline pregnant leach solution, two chemical precipitation
methods with sodium sulde and carbon dioxide were applied by taking into account the solubility product coefcients of lead compounds.
In the rst method, lead was precipitated selectively by the addition of
sodium sulde to the pregnant leaching solution. The solubility constants of ZnS and PbS are 2 10 23 and 1 1028, respectively, and
PbS is much less soluble than ZnS. Therefore, lead can be preferably precipitated prior to zinc. It has been determined that 99.85% lead can be
precipitated when the mole ratio of sodium sulde to the lead is over
1.50. The precipitate was identied mineralogically as mainly of galena
[PbS] and minor amount of wurtzite [ZnS] by XRD analysis (Fig. 5(a)).
Chemical analyses showed that the precipitate contains 85.16% Pb and
1.09% Zn. In the second method, carbon dioxide was blowed from the
leach solution until the lead concentration dropped at almost constant
value. For this purpose, the leach solution was rst diluted with 1/3 distilled water to reduce the alkalinity. The initial lead concentration value
of 20.92 g/l decreased to 51 mg/l after 75 min gas supply and then it did
not change. Under this condition, 99.76% lead in the leach solution could
be recovered by precipitation. XRD analysis showed that the precipitate
obtained from the leach solution is in the form of sodium lead carbonate
hydroxide [NaPb2(CO3)2OH] (Fig. 5(b)). It has been determined that the
precipitate contains 76.27% Pb and 4.3% Zn. The two lead minerals recovered from the pregnant leach solution by precipitation are also raw
materials for lead production. Since they have economic value, they
can be used in lead metallurgy.
3.7. Characterization of the leaching residue
The chemical and mineralogical compositions of the leach residue
before and after leaching were examined. The results of XRD analysis
carried out to determine mineralogical compositions are presented in
Fig. 6. The XRD analysis shows that lead-containing massicot [PbO]
and largely anglesite [PbSO4] minerals disappear while the less soluble
zinc-containing franklinite [ZnFe2O4] minerals predominate after the
leaching. The chemical analysis of the leach residue showed that it contains 0.87% Pb and 11.35% Zn. The chemical analysis almost conrms the
results of XRD analysis. After cleaning by pressure alkaline leaching, it
was determined that 19.02% Pb and 7.98% Zn content of the ZER were
changed to 0.87% and 11.35%, respectively.
3.8. Pollution potential of the remaining leach residue
Lots of anthropogenic waste materials are not environmentally safe
and geochemically stable. Hence, the contaminants can release at the
different stages of waste exposed to environmental conditions. The
systematic approach in evaluating the leaching behavior of contaminants
from waste materials is based on general geochemical principles such
as pH and redox-dependent precipitation/dissolution, liquid phase
complexation and sorption (Eighmy and van der Sloot, 1994). Some
short- and long-term leaching tests containing these properties such as
TCLP (USEPA, 1990), SPLP (synthetic precipitation leaching procedure)
(USEPA, 1994), MEP (multiple extraction procedure) (USEPA, 1986) and
ASTM (American Standard Test Methods) (ASTM Method D-3987)
(American Society for Testing and Materials, 1995a), D-4793 (American
Society for Testing and Materials, 1995b), D-4874 (American Society for
Testing and Materials, 1995c), D-5284 (American Society for Testing
and Materials, 1995d) and the European Directive EC/2003/33 (EC,
2003) are commonly used to evaluate the risk of disposal of solid waste
to the environment in the waste management. In this study, TCLP
(USEPA, 1990) and the European Directive EC/2003/33 regarding the acceptance of wastes at landll were applied to evaluate the pollution potential of the residue. The results are presented in Table 2.
TCLP is the most commonly used method in evaluating metal mobility in a sanitary landll. The test tries to simulate a worst-case scenario
where the waste is co-disposed with municipal solid waste. In the test,

either a sodium acetate buffer solution having a pH of 4.93 0.05 or an

acetic acid solution having a pH of 2.88 0.05 is used depending on the
pH of the waste. If the waste is highly alkaline, a different extraction solution at pH 2.88 0.05 is used. Extraction solution with pH 4.93 was
used in this study. TCLP test showed that the concentration of the Pb
was about 4 mg/l, and the Cd concentration was below the detection
level. Since these concentration values are below the threshold values
of 5 mg/l for Pb and 1 mg/l for Cd, it can be stated that the cleaning residue is environmentally stable.
TCLP test has been also applied to ZER by zverdi and Erdem. They
have determined that the concentrations of lead and cadmium leached
from the ZER exceeded the US EPA's toxicity characteristic thresholds.
Thus, it has been reported that the ZER is a solid waste having longterm pollution potential and would need to be managed as a hazardous
waste (zverdi and Erdem, 2010). When both TCLP test results are compared, it can be stated that the cleaning process with alkaline leaching is
an effective method to improve the stability of ZER. Similar process has
been proposed by Nagib and Inoue (2000) for simultaneous detoxication and metal recovery of y ash generated from municipal incineration plant.
The wastes are classied according to the European Directive EC/
2003/33. The classication of examined wastes is based on the EU Directive regarding the acceptance of wastes at landlls. When a waste is
going to be disposed in a landll, the compliance with this directive is
required. The limit values of various contaminants in the leachates of
wastes acceptable at landlls for inert wastes, non-hazardous wastes
and hazardous wastes are tabulated in the directive. For the EU Directive
EC/2003/33, two different water-to-solid (L/S) ratios were tested. The
obtained metal concentrations in leachates were compared with criteria
dened by the European Union for waste disposal in landll (Table 2).
Taking into account the heavy metal leachate concentrations, the
leach residue can be classied as non-hazardous waste.
4. Conclusion
The results of this study demonstrated that the alkaline leaching process was efcient to the recovery of lead from the ZER and to the cleanup
of the ZER. In the process, 99.6% Pb could be leached under the conditions
of 11% NaOH concentration, 60 min leaching time and 100 C leaching
temperature. It was found that the diffusion-controlled mechanism
governed the leaching kinetics and the activation energy value was
2.78 kJ/mol. The dissolved concentrations of the impurities such as Si
and Al were negligible levels. It was also found that during the pressure
leaching process, the alkaline insoluble Fe and Ca in the ZER remain in
the residue. Therefore, it can be stated that the proposed process consists of a hydrometallurgical treatment of the zinc leaching residue
based on selective leaching of Pb without destroying the impurities.

Table 2
Pollutant concentrations released from the leach residue by TCLP and European Directive
EC/2003/33 tests.
TCLP
Component

Pb

Zn

Cd

Released concentrations from the leach residue, mg/l

TCLP limit values, mg/l

3.98
5

2.41

UDLa
1

EC 2003/33
Liquid/solid ratio

L/S = 2

Component

Pb

Zn

Released concentrations from the

2.27
0.54
leach residue, mg/l
Limit values, Inert waste
0.2
2
mg/l
Non-hazardous waste
5
25
Hazardous waste
25
90
a

UDL: under the detection limit.

L/S = 10
Cd
UDL

Pb
a

0.03
0.6
3

2.63
0.5
10
50

Zn

Cd

0.31 UDLa
4
50
200

0.04
200
5

M. ahin, M. Erdem / Hydrometallurgy 153 (2015) 170178

177

Fig. 7. A schematic ow-sheet of the process proposed for cleaning of zinc leaching residue by recovery of lead with alkaline leaching.

99.8% and 99.7% Pb could be recovered from the pregnant leach solutions in the form of galena [PbS] and sodium lead carbonate hydroxide
[NaPb2(CO3)2OH] by chemical precipitation with Na2S and CO2, respectively. Although the ZER is a hazardous waste, it has been determined
that the remaining residue after the pressure leaching is environmentally stable and has non-hazardous waste properties by TCLP and the
European Directive EC/2003/33, respectively. Consequently, it can be
stated that the cleaning process with alkaline leaching is an effective
method to improve the stability of ZER. A schematic ow-sheet of the
proposed process is shown in Fig. 7.
Acknowledgments
This study was nanced by the Scientic and Technological Research
Council of Turkey (TUBITAK) under the project number of 109Y262.
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