Hydrometallurgy 95 (2009) 53–60

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

Leaching of waste battery paste components. Part 1: Lead citrate synthesis

from PbO and PbO2
M.S. Sonmez a,⁎, R.V. Kumar b
a
Department of Materials & Metallurgical Engineering, Faculty of Chemistry & Metallurgy, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey
b
Department of Materials Science and Metallurgy, University of Cambridge, United Kingdom

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

Article history: In this study, as part of developing a new process which can avoid smelting and electro-winning, citric acid
Received 30 October 2007 based reagents in aqueous media were reacted with PbO and PbO2. These two oxides are important
Received in revised form 24 April 2008 components in the spent lead-acid battery paste and together account for up to 50% of the paste by weight.
Accepted 26 April 2008
PbSO4, the main component in a spent battery paste accounting for the remaining 50%, is dealt with in Part 2
Available online 3 May 2008
in a separate paper. Reaction between PbO and C6H8O7·H2O or PbO2 with a mixture of C6H8O7·H2O and H2O2
Keywords:
yielded lead citrate, Pb(C6H6O7)·H2O, which was characterised by XRD, SEM and FT-IR analysis. Optimal
Spent battery pastes synthesis conditions were determined by investigating the effect of time, temperature, concentration, and
Leaching/crystallisation the starting Pb oxide/water ratio. The optimal condition for leaching a mol of PbO at room temperature
Lead citrate (20 °C) was found to be: 1 mol of (C6H8O7)·H2O solution; 1/3 as the starting PbO/water ratio and 15 min of
Characterisation reaction time. Pure citrate product, Pb(C6H6O7)·H2O was rapidly crystallized from the solution, in the leaching
Recycling process. Leaching of PbO2 required the use of a mild reducing agent. For each mole of PbO2, the optimum
condition at 20 °C was found to be: a solution containing 4 mol of C6H8O7·H2O and 2 mol of H2O2; 1/5 as the
starting solid PbO2/water ratio; and 60 min of reaction time. The product, as with PbO, was pure Pb
(C6H6O7)·H2O compound. The remaining lead content of the filtrate solution was 0.017% and 1%
corresponding to recoveries of 99.98% and 99% of lead as citrate, after the leaching/crystallization/filtration
process with PbO and PbO2, respectively. Asymmetric stretching vibrations between 1599 and 1662 cm− 1,
whereas symmetric vibrations between 1520 and 1327 cm− 1 for lead citrate synthesised from PbO and
asymmetric stretching vibrations between 1600 and 1642 cm− 1 as well as symmetric vibrations between
1517 and 1326 cm− 1 for the product obtained from PbO2 revealed the strong IR adsorptions associated with a
carboxylate structure. XRD data was identical to the well documented crystalline Pb(C6H6O7)·H2O compound
from both the oxides. SEM revealed the formation of plate/sheet like morphologies. The difference in the
column size of the Pb(C6H6O7)·H2O formed from the two lead oxides can be related to difference in the rate of
the respective reactions.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction criticism, especially due to SO2 emission from the need to decompose
PbSO4 at elevated temperatures of N1000 °C, and lead emissions from
Lead compounds have attracted scientific interest not only for their fuming at these high temperatures. Given the environmental concerns
coordination properties and stereochemistry, but also for their toxicity in recent years, hydro-electrometallurgical processes have been
effect on human beings (Harrison and Steel, 1982; Kourgiantakis et al., developed recently. One of the basic problems during hydro-
2000; Burford et al., 2004). Separately, lead-acid batteries constitute electrometallurgical treatment methods is the low solubility of lead
the single most consumption of lead at over 70% of all the lead compounds in solvents as well as inefficient desulphurisation in the
produced (Prengaman, 2000). Considering the much publicized toxic aqueous solution.
properties of lead, efficient recycling or recovery from waste materials, In the most common approach, the battery paste is charged into
is a critical necessity for ecological reasons. smelting furnaces (Prengaman, 1980; Forrest and Wilson, 1990). New
Either pyrometallurgical or hydro-electrometallurgical methods developments in smelting technology have led to recycling in
have been used for the treatment of scrap battery pastes (Habashi, processes such as Isasmelt (Ramus and Hawkins, 1993; Ahmed,
1997; Prengaman et al., 2001). While pyrometallurgical methods still 1996) or short rotary furnaces (Forrest and Wilson, 1990). The paste
comprise over 90% of the recovery technology, they are under severe material contains a large proportion of sulphur in the form of sulphate
which results in the well documented SO2 problems and all that this
⁎ Corresponding author. Tel.: +90 285 33 99; fax: +90 212 285 34 27. entails (Harrison, 2000). Decomposition of PbSO4 requires the use of
E-mail address: [email protected] (M.S. Sonmez). relatively high temperatures (Habashi, 1997). High temperature

0304-386X/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2008.04.012
54 M.S. Sonmez, R.V. Kumar / Hydrometallurgy 95 (2009) 53–60

Given the serious problems encountered in the smelting route for

recycling lead lead-battery paste, several research, pilot scale and
commercial methods using hydrometallurgical approach have been
developed. Hydrometallurgical methods have been used to remove S
in the paste as soluble Na2SO4 (aq) or (NH4)2SO4 (aq) using Na2CO3
(aq), NaOH (aq) or (NH4)2CO3 (aq) solutions (Prengaman and
Raymond. 1980; Reynolds et al., 1990; Gong et al., 1992; Prengaman
et al., 2001). Na2SO4 is then crystallized from the remaining solution
and can be sold off as a by-product. The insoluble product PbCO3 or Pb
(OH)2 collected in the form of sludge or filter cake is then routed to the
smelter. A number of new plans are under development for future
application. Despite extensive effort, it has not yet been possible to
avoid the retention of a substantial amount of sulphur in the lead-
bearing product and thus the smelter SO2 problem is not fully abated.
In order to evade the use of smelting altogether, the insoluble
Fig. 1. Lead content and pH change of the solution after filtering for different initial α sludge or filter cake from the above hydrometallurgical desulphurisa-
ratio (constant leaching conditions: 60 min, 250 rpm, 20 °C). (Region A: pure
tion process may be dissolved in fluoroboric acid (HBF4) (Olper, 1993).
Pb(C6 H6 O 7 )·H 2O, Region B: contaminated Pb(C6 H6 O 7 )·H 2O).
While PbCO3 or Pb(OH)2 are soluble in HBF4, the other important
constituent of the paste PbO2 is not and has to be reduced in the
solution to Pb(II) by using H2O2(aq). Both PbO and Pb are soluble
however. The solution is then purified by cementation followed by
electro-winning. In this variation a large number of steps are required
making the process expensive. Electro-winning process is capital
intensive and is often only suitable for large scale operations which in
turn entail large scale movement of battery waste materials.
In another variation of the hydrometallurgical/electro-winning
method, both PbCO3 and PbO2 are converted to PbO by a calcination/
reduction step. PbO is then solubilised in H2SiF6(aq) from which Pb is
electro-won (Prengaman, 1995). More expensive and even more
complex process involve the use of leaching in stages with HCl, NaCl
and Ca(OH)2 solutions so that S is removed as gypsum, while Pb is
transferred as PbCl2 from which Pb is electro-won using an energy
Fig. 2. Lead content of the solution after filtering as a function of leaching duration
(leaching conditions: α: 1, starting PbO/water ratio: 1/5, 250 rpm, 20 °C).

Fig. 4. Lead content of the solution after filtering for different starting PbO/water ratios
(constant leaching conditions: 15 min, α: 1, 250 rpm, 20 °C).

Fig. 3. Lead content of the solution after filtering for different leaching temperatures
(constant leaching conditions: 15 min, α: 1, starting PbO/water ratio: 1/5, 250 rpm).

process also generates significant amounts of hazardous lead lead-

bearing fumes, dust and slag. When Fe is used to fix S in the paste,
hazardous FeS–PbS matte is also produced. Disposal of lead lead-
bearing waste products is not only expensive but also harmful to the
environment. Smelting processes are energy intensive, generate NOx
and have high operating costs. Utilization of Na2CO3 as a high
temperature sulphur fluxing agent produces either Na2SO4 (in the
slag) or FeS–Na2S soda matte. While SO2 gaseous emission problem is
abated, water leachable hazardous waste products are produced. It
must be noted that for a number of environmental and cost factors,
the smelting capacity in many industrial countries are being relocated Fig. 5. Lead content of the solution after filtering for different temperatures and starting
to newly industrial countries. PbO/water ratios (constant leaching conditions: 15 min, α: 1, 250 rpm).
 M.S. Sonmez, R.V. Kumar / Hydrometallurgy 95 (2009) 53–60 55

must be maintained. There has been a recent tendency to ship a

significant proportion of lead wastes across continents to sustain
recycling in order to minimise any local environmental costs. This
practice may not be sustainable in the long run. An environmentally
sound process that can be operated on a small scale as well as in large
plants will be in demand.
In this paper we are reporting that the lead can be converted to a
crystalline salt, Pb(C6H6O7)·H2O (lead citrate), which in turn can form
the precursor for extracting lead from lead-waste materials. In this
paper, lead oxides PbO (lead monoxide) and PbO2 (lead dioxide),
present as important components in spent lead lead-acid battery
pastes, are considered The principle is also relevant for treating lead
oxides in paints, monitors and solders. Leaching/crystallization
behaviour of PbSO4 – the major component in the lead-battery
waste – is reported in Part II (Sonmez and Kumar, 2009).
Fig. 6. Lead content of the solution after filtering for different initial C6H8O7·H2O and
H2O2 amounts per mol of PbO2 (leaching condition: 60 min, 250 rpm, starting PbO2/
water ratio: 1/50, 20 °C). (Region A: pure Pb(C6H6O7)·H2O, Region B: contaminated Pb
2. Materials and methods
(C6H6O7)·H2O).
Analytically pure and commercially available chemicals were used to
model the components in a spent battery paste. Leaching experiments
were carried out by using lead oxide (PbO, Acros Organics), lead dioxide
(PbO2, Fisher Scientific) and citric acid monohydrate (C6H8O7·H2O, Acros
Organics) as starting materials. During the leaching/crystallization
experiments with PbO2, hydrogen peroxide (H2O2, Aldrich) 27.5%
solution in water was used for reducing the dioxide.
Leaching procedure was carried out by stirring the mixture with a
magnetic stirrer at a constant stirring rate of 250 rpm in a glass beaker.

Fig. 7. Lead content of the solution after filtering for different starting PbO2/water ratio
ratios (constant leaching conditions: 60 min, 250 rpm, 4 mol of C6H8O7·H2O and 4 mol
of H2O2 for 1 mol of PbO2, 20 °C).

Fig. 9. Lead content of the solution after filtering for different leaching durations — all data
correspond to Region A (constant leaching conditions: 250 rpm, starting PbO2/water ratio:
1/50, 4 mol of C6H8O7·H2O and 4 mol of H2O2 per mol of PbO2, 20 °C).

Fig. 8. Lead content of the solution after filtering for different temperatures — all data
correspond to Region A (constant leaching conditions: 60 min, 250 rpm, starting PbO2/
water ratio = 1/50, 4 mol of C6H8O7·H2O and 4 mol of H2O2 for per mole of PbO2).

intensive diaphragm electrochemical cell (Diaz and Andrews, 1996;

Andrews et al., 2000).
It is quite clear that despite the availability of excellent recycling
infrastructure for the lead battery, there is a need for a simpler and a
more benign route in the face of tougher legislations and cost
competitiveness. It is attractive to invent a cost effective process that Fig. 10. Lead content of the solution after filtering for different initial H2O2 amounts
does not involve smelting or electro-winning. Most importantly, (constant leaching conditions: 60 min, 250 rpm, starting PbO2/water ratio: 1/50, 4 mol
despite stringent legislations, the successful record for lead recycling of C6H8O7·H2O for 1 mol of PbO2, 20 °C).
56 M.S. Sonmez, R.V. Kumar / Hydrometallurgy 95 (2009) 53–60

Leaching/crystallization experiments were carried out in order to op-

timize the mol ratio of the reactants, the temperature and the duration of
the process. Leaching/crystallization efficiencies of PbO with C6H8O7·H2O
and PbO2 with the mixture of C6H8O7·H2O plus H2O2 were calculated from
the lead content of the filtrate solution. Recovery of lead as uncontami-
nated Pb(C6H6O7)·H2O was calculated from the experimental data.

3. Results and discussion

3.1. Lead citrate synthesis from PbO

One of the three main components of the scrap battery paste, PbO,
(others being PbO2 and PbSO4) was leached with an aqueous solution
of C6H8O7·H2O. Lead citrate was rapidly crystallized in the solution.
Fig. 11. pH and temperature change during the leaching of PbO2 (4 mol of C6H8O7·H2O The reaction can be represented by the following Eq. (1).
and 2 mol of H2O2 for 1 mol of PbO2).

PbOðsÞ þ C6 H8 O7d H2 OðlÞ →PbðC6 H6 O7 Þd H2 OðsÞ þ H2 OðlÞ ð1Þ

Synthesis conditions were determined by experimenting different
mol ratios of the lead compounds and the reactants. Reaction
Leaching and crystallization behaviour of PbO in C6H8O7·H2O solution
temperature of the mixture was monitored by a contact thermometer. nPbO
The analysis of the filtrate solution for lead was performed by ICP- was optimized by considering initial nC6 H8 O7 H2 O (α) ratio; leaching duration;
AES (Varian Liberty AX Sequentional ICP-AES). The X-ray diffraction leaching temperature; S/L ratio, defined as initial wt of PbO/initial wt of
(XRD) spectra were obtained using Philips X-ray diffractometer (Cu water; and the pH of the solution. At α=1, and a PbO/water ratio of 1/3, the
Kα, 40 kV, 25 mA, calibrated with Si-standard). The raw materials and concentration of citric acid is 1.5 M. As the ratio of PbO/water is decreased
the end products were characterised by FT-IR (Tensor 27, Brukel from 1/3 to say 1/5, the starting concentration of citric acid is corres-
Optics). The morphology of the material was examined by field pondingly decreased to 0.9 M. The precipitation of pure lead compound
emission scanning electron microscopy (FESEM-JEOL 6340F). was the main objective of the experiments. Any contamination of the

Fig. 12. Comparison of X-ray diffraction analysis of Pb(C6H6O7)·H2O a) created from Kourgiantakis et al. (2000), b) produced from PbO-leaching conditions: α: 1, starting PbO/water
ratio: 1/3, 250 rpm, 20 °C, 15 min, and c) produced from PbO2-leaching conditions: solution containing 4 mol of C6H8O7·H2O and 2 mol H2O2, starting PbO2/water ratio: 1/5, 250 rpm,
20 °C, 60 min, data in b and c, correspond to materials in region A.
 M.S. Sonmez, R.V. Kumar / Hydrometallurgy 95 (2009) 53–60 57

citrate product is not desirable, especially as this represents incom- insufficient C6H8O7·H2O during the leaching process (Fig. 1, Region B).
plete reaction of the lead oxides. It must be noted that the regions of pure Although lead content of the solution was decreased when α ratio was
Pb(C6H6O7)·H2O precipitate and regions of contaminated Pb(C6H6O7)·H2O, increased, at α ratio greater than 1, non-reacted PbO remained in the
as deduced from XRD, are clearly separated and marked in the relevant precipitate even after 60 min. Furthermore increasing the initial PbO
figures as Region A and Region B, respectively. The XRD results will content with respect to the initial C6H8O7·H2O amount resulted in higher
hereafter be discussed in the text. pH values of filtrate solution due to consumption of the acid. It should be
As α ratio is increased together with an increase in PbO/water ratio noted that for maximising recovery of lead in the form of citrate it is
(from 1/20 to 1/2), lead content of the solution is found to decrease due to important to minimise the lead content in the solution and simultaneously

Fig. 13. FT-IR spectra of Pb(C6H6O7)·H2O produced from both a. PbO and b. PbO2.
58 M.S. Sonmez, R.V. Kumar / Hydrometallurgy 95 (2009) 53–60

maximise the formation of Pb(C6H6O7)·H2O product. As long as the filtrate ture, duration, relative concentrations of the reagents and pH were
consists of only Pb(C6H6O7)·H2O (with negligible retained/unreacted PbO), investigated to optimise the leaching process.
lower lead content in the filtrate solution will correspond to a higher PbO2 could not be effectively leached and precipitated with citric acid
recovery. It is also easier for recycling and or even disposing (but by itself. Although the lead content of the solution was increased up to
not recommended) the spent liquor containing lower levels of lead. Pure 3.5% after filtering but the filtrate mainly contained PbO2 with a very
Pb(C6H6O7)·H2O precipitation could be achieved up to the bordered line as small amount of Pb(C6H6O7)·H2O. When only H2O2 solution was used for
shown in Fig. 1 (Region A). It can be seen from Fig. 1, that the optimal reacting with pure PbO2, filtrate remained as unreacted PbO2 after
condition for the leaching is realized for α=1 corresponding to a minimum filtering with a small amount of (0.005% of Pb) in the solution at both
lead content in the filtrate solution. 20 °C and 40 °C even after 60 min. Results reported by Ferracin et al.
Complete precipitation conversion was not achieved and (2002), on the reaction between PbO2 and citric acid showed that very
unreacted PbO particles remained in the precipitate up to 15 min of long leaching duration was needed for achieving any significant
leaching as indicated by Region B in Fig. 2. The amount of lead in the solubility.
filtration solution was 0.14 wt wt.% after 15 min. The product can re- H2O2 was effective as a reducing agent and assisted leaching with
dissolve as shown by the higher lead content in the solution for longer C6H8O7·H2O resulting in precipitation of Pb(C6H6O7)·H2O. The sug-
leaching durations (0.5% for 60 min) due to the dissolution of recently gested reaction is as follows:
formed Pb(C6H6O7)·H2O particles (Fig. 2, Region A). In order to
maximise recovery of lead from the solution, it is important to PbO2 þ C6 H8 O7d H2 O þ H2 O2 →PbðC6 H6 O7 Þd H2 O þ O2 þ 2H2 O ð2Þ
optimise the duration of leaching and crystallization. Thus it can be
noted that excessive leaching duration is counter-productive for It was found that combined with the assistance of H2O2, a minimum
recovery of Pb(C6H6O7)·H2O. By decreasing the duration, the recovery concentration of 4 mol of C6H8O7·H2O per mol of PbO2 was required to
was further enhanced from 99.5 to 99.85%. fully leach PbO2 and precipitate uncontaminated Pb(C6H6O7)·H2O
There was no significant effect of leaching temperature on both the product (Fig. 6). (XRD data of pure Pb(C6H6O7)·H2O formed from PbO2
precipitation and lead content of the filtration solution as shown in Fig. 3 are shown in Fig. 12c and further discussed in Section 3.3). For the
for the leaching time of 15 min. Lead content of the solution increased up best condition in Fig. 6, the calculated lead recovery as uncontaminated
to 0.18% at 40 °C reflecting the very small increase in dissolution with Pb(C6H6O7)·H2O is about 97.2%. Initially a large amount of water was
temperature. The product was pure Pb(C6H6O7)·H2O under all the used relatively to the reagent (S/L = 1/50), thus the reagents were dilute.
conditions in this experiment (XRD data for pure Pb(C6H6O7)·H2O from Subsequently, the relative amount of water was decreased and S/L ratio
PbO are shown in Fig. 12b and discussed in Section 3.3). of 1/5 was found to produce better recovery for uncontaminated
Lowest lead content of the solution (0.017%) after filtration was Pb(C6H6O7)·H2O. A relatively high H2O2/PbO2 molar ratio (N2) was
achieved by leaching with a starting PbO/water ratio of 1/3 (Fig. 4), also required to produce uncontaminated Pb(C6H6O7)·H2O precipitate.
together with maximum recovery of 99.98% as pure Pb(C6H6O7)·H2O Uncontaminated Pb(C6H6O7)·H2O was obtained after all the experi-
product. Uncontaminated Pb(C6H6O7)·H2O was formed for the range ments in Fig. 7. When the starting PbO2/water ratio was increased to 1/5
of S/L ratios shown. Addition of too much water can decrease the for a more concentrated solution, lead content of the solution was
reactivity by diluting the citric acid, while too little water can be decreased to 1.5% indicating improved lead recovery at 98.5%. With
detrimental for providing the leaching media. increasing starting temperature the lead content of the solution
Marginally increasing dissolution behaviour was also observed for increased to 4.8% for the experiment at 40 °C (Fig. 8), with a lower
different starting PbO/water ratios similar to Fig. 3 when the leaching recovery of 95.2%. This may be related to an enhanced solubility
temperature was increased up to 40 °C as shown in Fig. 5. Thus a lower at elevated leaching temperatures. In order to achieve uncontaminated
temperature (room temperature) and a S/L ratio of 1/3 is preferred for Pb(C6H6O7)·H2O, under the following leaching condition: a temperature
optimal leaching and crystallization leading to a maximal recovery of of 20 °C; stirring rate of 250 rpm; starting PbO2/water ratio of 1/50; 4 mol
uncontaminated Pb(C6H6O7)·H2O product. of C6H8O7·H2O and 4 mol of H2O2 per mol of PbO2, as specified in Fig. 9,
the minimum reaction time was found to be approximately 60 min. The
3.2. Lead citrate synthesis from PbO2 region A corresponding to time N60 min is required for forming pure Pb
(C6H6O7)·H2O from the leaching solution, while region B at b60 min is
PbO2 is relatively a difficult compound to dissolve in aqueous media. the contaminated region. Recovery is slightly increased with increasing
It was found necessary to reduce this with a reducing agent such as H2O2. time as can be calculated from the lead in solution data shown in Fig. 9.
PbO2, was leached by C6H8O7·H2O and H2O2, to precipitate lead citrate, Fig. 10 showed that when the initial H2O2 amount was increased, lead
Pb(C6H6O7)·H2O. The parameters, relative amounts of H2O2, tempera- content of the solution was decreased accompanied by an efficient

Fig. 14. SEM images of Pb(C6H6O7)·H2O produced from both a. PbO (×4000) leaching conditions: — α: 1, starting PbO/water ratio: 1/3, 250 rpm, 20 °C, 15 min and b. PbO2 (×4300)-
leaching conditions: solution containing 4 mol of C6H8O7·H2O and 2 mol H2O2, starting PbO2/water ratio: 1/5, 250 rpm, 20 °C, 60 min.
 M.S. Sonmez, R.V. Kumar / Hydrometallurgy 95 (2009) 53–60 59

precipitation of Pb(C6H6O7)·H2O. Although complete consumption of metric vibrations between 1520 and 1327 cm− 1 for the precipitate
H2O2 is expected from stoichiometry for 1 mol of H2O2 per mol of PbO2 synthesised from PbO (Fig. 13a) and asymmetric stretching vibrations
the Pb(C6H6O7)·H2O product was not pure as revealed by X-ray between 1600 and 1642 cm− 1 as well as symmetric vibrations
diffraction analysis. Pure Pb(C6H6O7)·H2O without any contamination between 1517 and 1326 cm− 1 for the product obtained from PbO2
was obtained only at a minimum of 2 mol of H2O2 was reacted with (Fig. 13b) belong to COO−group. These results are compatible
4 mol of C6H8O7·H2O for each mol of PbO2 (Region A). The corresponding with carboxylate structures (Bellamy, 1980; Lin-Vien et al., 1991;
recovery is calculated as 99%. Kourgiantakis et al., 2000).
Both C6H8O7·H2O and H2O2 had an effect of dissolving lead into the Small variation in morphology of Pb(C6H6O7)·H2O was revealed by
solution effectively followed by rapid precipitation of Pb(C6H6O7)·H2O. SEM analysis between the two different starting materials, PbO
Thus the combination of reagents is required to assist simultaneous (Fig. 14a) and PbO2 (Fig. 14b). Pb(C6H6O7)·H2O synthesised from both
reduction and leaching. Pure Pb(C6H6O7)·H2O was obtained after the PbO and PbO2 had similar shape except for the size of columns
filtration when only with the use of excess of C6H8O7·H2O (4 mol) averaging at 70 and 40 μm respectively. The difference between the
and H2O2 during leaching (Region A in Figs. 6–10). Lead content of sizes of the particles can be related to kinetic behaviour of the
the solution increased to more than 3.5% when a very large excess reactions. It is suggested that the bigger size of Pb(C6H6O7)·H2O
for example 6 mol of C6H8O7·H2O and 6 mol of H2O2 were used synthesised from PbO was produced in only 15 min duration probably
during leaching (Fig. 6). While the exact optimum values have not controlled by diffusion, on the other hand with a longer period up to
been ascertained, it is clear from Fig. 6 that 4 mol of C6H8O7·H2O and 60 min chemically controlled reaction promoted the leaching — pre-
2–4 mol of H2O2 at S/L ratio of 1/5 can lead to pure Pb(C6H6O7)·H2O cipitation of Pb(C6H6O7)·H2O from PbO2. Much of the time may be
product for leaching at room temperature in N60 min with a negligible associated with the slower reduction and leaching reaction rather
amount of lead remaining in solution after filtering the precipitate. then the precipitation of the citrate itself.
Although 1 mol of each starting reactants for the conversion of PbO2
seem to be sufficient according to the Eq. (2), excess C6H8O7·H2O and 4. Conclusion
H2O2 are required for the complete and efficient leaching and
precipitation. The reason for this excess citric acid and H2O2 usage Leaching of pure PbO with 1 mol of C6H8O7·H2O solution per mol
required is perhaps related to the temperature increase of the leaching PbO for 15 min at 20 °C, with 1/3 as the ratio of starting PbO/water
solution at the beginning of the reaction. As shown in Fig. 11, exothermic resulted in the crystallization of pure Pb(C6H6O7)·H2O crystals. The
reaction taking place in the initial stages of leaching results in a amount of lead remaining in the solution was 0.017% after crystal-
temperature increase of more than 40 °C within the first 3 min. This lization, corresponding to an excellent recovery of 99.8%.
increase was followed by a gradual decrease with time. Oxygen The leaching of pure PbO2 with 4 mol of C6H8O7·H2O and 2 mol
evolution was observed which can be ascribed to the reducing effect H2O2 solution per mol of PbO2 for 60 min at 20 °C, with 1/5 as
of H2O2. pH of the leaching media also increased rapidly in the first few the starting PbO2/water ratio, also resulted in the precipitation of
minutes followed by a gradual decrease following similar trend as Pb(C6H6O7)·H2O compound at an acceptable recovery of 99%.
shown by the temperature changes. pH of the leaching media was still Experimental results for leaching–crystallization of Pb(C6H6O7)·H2O
very acidic at 0.8 after 60 min, due to excess C6H8O7·H2O/H2O2 ratio. by reacting the PbO and PbO2 (and PbSO4 reported in Part 2 by Sonmez
The reaction sequence can be considered as reduction of PbO2 by H2O2 and Kumar, 2009) with C6H8O7·H2O have shown that lead can be
followed by leaching of PbO. Reduction can be considered as the slower recovered effectively as lead citrate crystals. The lead citrate precursor,
and the rate determining reaction, given the increased time required for can be readily converted to PbO (containing some Pb) for directly
PbO2 in contract with PbO. H2O2 in contact with PbO2 is a mild reducing making lead lead-battery pastes with controllable degree of metalliza-
agent and may necessitate the use of excess H2O2 to sustain the reduction. tion by a combustion–calcination process (Kumar et al., 2006, 2007).
This is a matter of ongoing investigation. Thus when in-situ PbO is formed Energy for such a process is derived from the organics embodied in the
it must come in contact with C6H8O7·H2O for leaching to proceed. It is not precursor material. By controlling the calcinations process, it is also
fully clear what role the increase in temperature has on leaching and possible to obtain variation in the microstructure from nano- to micro-
crystallization reactions, but the need for excess citric acid requirement scale, nano-powders are attractive for future development work in
also is being further explored. Furthermore a side reaction between advanced lead lead-acid batteries. A full process using the principles
C6H8O7·H2O and H2O2 that can result in the formation of peroxy-acid outlined in this paper is currently being commercialised.
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