Hydrometallurgy 95 (2009) 82–86

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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 2: Leaching and desulphurisation

of PbSO4 by citric acid and sodium citrate solution
M.S. Sonmez a,⁎, R.V. Kumar b
a
Department of Materials and Metallurgical Engineering, Faculty of Chemistry and Metallurgy, Istanbul Technical University, 34436, 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 that can avoid both smelting and electro-winning, citric
Received 17 December 2007 acid based reagents were reacted with PbSO4, in aqueous media for achieving lead recovery simultaneously
Received in revised form 29 April 2008 with desulphurisation. PbSO4 is the main component in a spent battery paste (accounting for nearly 50% by
Accepted 30 April 2008
weight). Recovery of the two oxides PbO and PbO2, which together account for the remaining 50% of the
Available online 9 May 2008
paste, has been discussed in Part 1 in a separate paper. Leaching of PbSO4 with a solution containing
Keywords:
C6H5Na3O7·2H2O alone was neither effective in removing the sulphate or in synthesising uncontaminated
Spent battery pastes lead citrate. When both C6H5Na3O7·2H2O and C6H8O7·H2O reagents were used together, it was possible to
Leaching/crystallization achieve effective recovery of lead precursor as lead citrate while simultaneously removing sulphur as Na2SO4.
Lead sulphate The lead citrate product was characterised by SEM and XRD analysis. Conditions for achieving a recovery of
Lead citrate 99% of the lead precursor crystallites have been experimentally deduced by varying the concentrations of
Characterisation various reagents, time and temperature of the reaction, and the starting ratio of solid to liquid.
Recycling © 2008 Elsevier B.V. All rights reserved.

1. Introduction Hydrometallurgical approaches for desulphurisation of spent

Given the toxicity of lead, it is important to achieve good recovery
in the recycling of waste batteries. In recent years more than 95% of
scrap lead-acid batteries are recycled in Europe, N. America and Japan
and continue to increase in other parts of the world. Basic stages in
lead-acid battery recycling processes are removal of the battery acid,
separation of the plastic parts, processing of metallic parts and
recycling of battery paste. Either pyrometallurgical or hydro-electro-
metallurgical methods have been used for the treatment of scrap
battery pastes (Habashi, 1997; Prengaman et al., 2001).
The problems associated with the current methods are described
in Part 1 in this Journal (Sonmez and Kumar, 2009). In the most
common approach, the battery paste is charged into smelting fur-
naces (Prengaman, 1980; Forrest and Wilson, 1990). High temperature
(N 1000 °C) is required for decomposing and reducing PbSO4, which is
associated with generation of dilute SO2 gas streams in addition to
lead fumes. New developments in pyrometallurgical processes have
led to recycling in Isasmelt (Ramus and Hawkins, 1993; Ahmed, 1996)
or short rotary furnaces (Forrest and Wilson, 1990; Guerrero et al.,
1997; Lamm, 1998), which use Fe or soda to remove the S in the
furnace by forming FeS–PbS matte or a slag containing Na2SO4.
Disposal of hazardous matte or leachable slag is also expensive and
harmful to the environment (Guerrero et al., 1997).
⁎ Corresponding author. Tel.: +90 212 285 33 99; fax: +90 212 285 34 27.
E-mail address: ssonmez@itu.edu.tr (M.S. Sonmez).
battery paste have attracted much attention recently. These methods
convert S in the paste to soluble sulphates by reacting with reagents
such as NaOH, Na2CO3, K2CO3 or (NH4)2CO3 solutions (Soto and Toguri,
1985; Reynolds et al., 1990; Gong et al., 1992; Prengaman, 1995; Chen
and Dutrizac, 1996 ; Morachevskii et al., 2001; Prengaman et al., 2001).
Dissolution of lead sulphate in waste batteries with ethanolamines
and subsequent stripping with Na2CO3 and NaHCO3 solutions have
also been reported (Begum et al., 1989). A sulphate product (e.g.
Na2SO4) is then crystallized from the remaining solution and can be
sold off as a by-product. The insoluble product (e.g. PbCO3 or Pb
(OH)2) collected in the form of sludge or filter cake is then routed to
the smelter. A substantial amount of sulphur in the lead-bearing
product is often retained and thus the smelter SO2 problem is not
fully abated.
In other developments, smelting is altogether avoided; the
insoluble sludge or filter cake from the hydrometallurgical desulphur-
isation process may be dissolved in strong reagents such as HCl (Diaz
and Andrews, 1996; Andrews et al., 2000), fluoro-boric acid (HBF4)
(Olper, 1993; Olper and Morcutte, 1995) or H2SiF6(aq) (Prengaman,
1995). The solution is then purified by cementation followed by
electro-winning. 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 this study we have provided the outline for dealing with lead
sulphate in the battery paste without recourse to either smelting or
electro-winning. Materials and energy sustainability in the recycling

0304-386X/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2008.04.019
 M.S. Sonmez, R.V. Kumar / Hydrometallurgy 95 (2009) 82–86
Fig. 1. Percentage (%) of lead from PbSO4 that remained in the solution after the
leaching-crystallization reaction for varying β ratios (at constant leaching conditions:
60 min, 250 rpm, 20 °C, S/L: 1/20).
of spent lead-acid batteries will be discussed later. Experimental re-
sults together with other relevant study have given rise to a potentially
new spent battery paste recycling process which is patented and the
details discussed elsewhere (Kumar et al., 2006; Sonmez and Kumar,
2009).
In this study, reaction conditions for desulphurisation of PbSO4
with citric acid and a citrate salt, namely C6H8O7·H2O and/or
C6H5Na3O7·2H2O were investigated. Lead was recovered from the
solution in the form of a lead citrate precursor while sulphur was
converted to Na2SO4 by reacting with C6H5Na3O7·2H2O. Desulphur-
isation ability of citrate for removal of sulphur from flue gases has
been previously reported (Pakalay et al., 1993; Pandey et al., 2005).
2. Materials and methods
Leaching and crystallization experiments were carried out using
lead sulphate PbSO4 (Fisher Scientific), C6H8O7·H2O (Acros Organics)
and C6H5Na3O7·2H2O (Fisher Scientific). The procedure involved
agitating the mixture with a magnetic stirrer at a constant stirring
rate of 250 rpm in a glass beaker. Synthesis conditions were
determined by experimenting with different mol ratios of PbSO4
and the reactants. The volume of the solution used was 50 ml for each
experiment. Reaction temperature of the mixture was monitored by a
contact thermometer.
After allowing the reaction to occur for a specified time, any
remaining solid (both un-reacted starting material and new pre-
cipitates formed) was filtered out. The analysis of the filtrate solution
for lead was performed by ICP-AES (Varian Liberty AX Sequentional
ICP-AES) and calculated as % of lead retained in the solution with
respect to the original amount of lead in the starting lead compound.
Fig. 2. X-ray diffraction of the precipitate obtained from the leaching of PbSO4 with
C6H5Na3O7·2H2O.
83
Fig. 3. Percentage (%) of lead remained in solution from the initial PbSO4, for different
duration and temperature (at constant leaching conditions: β: 0.5, 250 rpm, S/L: 1/20).
X-ray diffraction (XRD) spectra were obtained using Philips X-ray
diffractometer (Cu Kα, 40 kV, 25 mA, calibrated with Si-standard). The
morphology of the material was examined by field emission scanning
electron microscopy (FESEM-JEOL 6340F).
3. Results and discussion
3.1. Desulphurisation of PbSO4 by C6H5Na3O7·2H2O
In Part 1 of this work, leaching of PbO and PbO2 – the other two
main components in lead battery paste – with citric acid solution
followed by crystallization of lead citrate Pb(C6H6O7)·H2O has been
reported (Sonmez and Kumar, 2009). Lead recovery in the form of Pb
(C6H6O7)·H2O crystallites was shown to be greater than 99%. In this
study, the alkaline citrate, C6H5Na3O7·2H2O, has been investigated as a
potential sulphur removing agent to remove sulphate from PbSO4.
nPbSO
Varying ratios of nC H Na O4
2H O ðβÞ, leaching temperature, time of
6 5 3 7 2
reaction and solid/liquid ratio (S/L in g/ml) defined as initial weight of
PbSO4 to the volume of solution were used in the experimental study. It
should be noted that C6H5Na3O7·2H2O is readily soluble in water.
Experimental studies showed that PbSO 4 can dissolve in
C6H5Na3O7·2H2O solution in the leaching-crystallization process. For
example 56% of lead from the initial PbSO4 remained in the solution for a
β ratio of 0.25 after 60 min of leaching at room temperature. The lead
content in the solution was analysed after filtration of the solution.
The proportion of lead that remained in solution decreased to 19.8% for a
β ratio of 1 for the same duration of 60 min at the same temperature of
20 °C (Fig. 1).
Excess amount of C6H5Na3O7·2H2O resulted in a greater transfer of
lead into the solution, and reached a plateau at 20% after a β ratio of
Fig. 4. Percentage (%) of lead remained in the solution from PbSO4 for different duration
(at constant leaching conditions: β: 0.5, 250 rpm, S/L: 1/20, 20 °C).
84 M.S. Sonmez, R.V. Kumar / Hydrometallurgy 95 (2009) 82–86
Fig. 5. Percentage (%) of lead remained in the solution from PbSO4 for different
C6H8O7·H2O ratios (constant leaching conditions: β: 0.5, 250 rpm, S/L: 1/20, 20 °C).
0.5. The amount of lead that was transferred to the solution was
deemed as non-recoverable lead.
The lead compound collected by filtration was analysed by XRD
and the pattern is shown in Fig. 2. Some of the lines appear to match
with PbSO4 but only a small proportion of the initial material may not
have reacted at all. Most (over 98%) of the material therefore refers to
product that has been crystallized from the solution after leaching.
Thus the percentage of lead in the crystal (100% (initial lead) — % lead
remained in the solution) calculated from the lead collected in the
filter paper is used to calculate the recovery of lead in the leaching-
crystallization step. The recovered lead is used as the precursor for
further treatment to produce PbO/Pb for use in a new battery (Kumar
et al., 2006). However the X-ray diffraction lines did not correspond to
the documented Pb(C6H6O7)·H2O (Sonmez and Kumar, 2009) struc-
ture and could not be characterised by existing X-ray diffraction
database.
The proportion of lead that remained in the solution decreased
with increasing time, suggesting that more of the product was
crystallized out with increasing time. As can be seen in Fig. 3, at a
constant value of β of 0.5, the percentage of lead retained in the
solution decreased to 16% as the leaching-crystallization duration was
increased to 120 min, while heating had the opposite effect. The
proportion of lead increased to 33% at 40 °C in 60 min and to 22% after
120 min (Fig. 3). Further increasing the duration beyond 120 min did
not have any significant effect on the proportion of lead recovered by
filtration (Fig. 4).
The precipitate could not be easily filtered and appeared to be gel-
like. Further characterisation is in progress for the precipitate thus
formed. In any event the proportion of lead recovered in the filtrate
was at best 85% and was not considered to be sufficient for
Fig. 6. Change in both pH and temperature during the leaching of PbSO4 with the
solution mixture of C6H5Na3O7·2H2O and C6H8O7·H2O.
Fig. 7. X-ray diffraction of the precipitate obtained from the leaching of PbSO4 with
C6H5Na3O7·2H2O and C6H8O7·H2O.
practical application. It is important that the recovery is increased to
98% and beyond.
3.2. Simultaneous leaching-crystallization and desulphurisation of PbSO4
by C6H5Na3O7·2H2O and C6H8O7·H2O
The effect of C6H8O7·H2O addition together with C6H5Na3O7·2H2O
on the recovery rate was investigated. When 1 mol of C6H8O7·H2O was
added to a leaching solution containing 2 mol of C6H5Na3O7·2H2O for
each mol of PbSO4, proportion of lead that remained in the solution
with respect to the initial lead from the sulphate, decreased to 2.3%
from a value of 20% (when no C6H8O7·H2O was present), otherwise
under identical conditions (Fig. 5). During the reaction with the
combined reagents there was no significant change either in pH or in
temperature (Fig. 6). This has shown that either there was no net
consumption of acid or that there was a buffering effect from the
combined acid/salt despite crystallization reaction leading to the
consumption of the C6H5Na3O7·2H2O. X-ray diffraction of the pre-
cipitate after leaching and crystallization of PbSO4 with the solution
mixture of C6H8O7·H2O and C6H5Na3O7·2H2O was quite different from
both Pb(C6H6O7)·H2O (produced from lead oxides, see Sonmez and
Kumar, 2009) and the powder produced from the leaching of PbSO4
with C6H5Na3O7·2H2O alone (Fig. 7). The structure did not match any
pattern in the available database.
X-ray diffraction, of product obtained after reacting for 30 min
when equi-molar concentration of each of the chemical was used, is
shown in Fig. 8. The diffraction pattern consists of both un-reacted
PbSO4 and a certain amount of converted product with lines
corresponding to the lines shown in Fig. 7.
Fig. 8. X-ray diffraction of the precipitate obtained from the leaching-crystallization of
PbSO4 with C6H5Na3O7·2H2O and C6H8O7·H2O after 30 min (◊ — Lead citrate, ♦ —
PbSO4).
 M.S. Sonmez, R.V. Kumar / Hydrometallurgy 95 (2009) 82–86
Fig. 9. Percentage (%) lead remaining in solution from the initial lead in PbSO4, for
0.5 mol C6H8O7·H2O addition with increasing temperature (constant leaching condi-
tions: β: 0.5, 60 min, 250 rpm, S/L: 1/20).
Increased temperature led to a decrease in recovery of lead and
resulted in an increase in the solubility of lead (Fig. 9). On the other
hand, lead solubility in the solution was reduced by increasing the S/L
ratio from 1/20 to 1/5 (Fig. 10), with a lead recovery of over 99%.
The addition of C6H8O7·H2O to the solution in the molar ratio of
PbSO4:C6H5Na3O7·2H2O:C6H8O7·H2O as 1:2:0.5 produced a reasonably
good rate of reaction and the reaction was completed in less than
60 min. The filtration of the lead product was efficient and easily
achieved. Recovery was calculated as outlined above at a respectable
99% under the above conditions.
The SEM image of the product was also different with respect to
those obtained from the PbO and PbO2 (Sonmez and Kumar, 2009),
where the plates were smaller and flatter while containing several
cracked pieces as debris in the morphology (Fig. 11). Assuming this
product was a citrate like lead compound, thermal analysis was
carried out to decompose the product to PbO in nitrogen. From the wt
change of 38% in the 170–350 °C range, the stoichiometry was
deduced to be [3Pb.2(C6H5O7)]·3H2O in contrast with the citrates from
PbO and PbO2, where the corresponding wt change was 50% in
accordance with the stoichiometry ([Pb(C6H6O7)]·H2O. Accordingly,
the leaching-crystallization reaction with PbSO4 can be described as:
3PbSO4 þ 2½Na3 C6 H5 O7 :2H2 O→½3Pb:2ðC6 H5 O7 Þ:3H2 O þ 3Na2 SO4 þ H2 Oð6Þ
The spent aqueous solution containing Na2SO4 can be subjected to
the documented process for crystallizing Na2SO4 by evaporation/
crystallization and centrifugation as a useful by-product for the
chemical industry (Prengaman et al., 2001).
In order to demonstrate the applicability of the process to a mixed
paste, 10 g of battery paste (chemical composition: PbSO4: 68.7%, PbO:
11.3%, PbO2: 11.0%, Pb metal: 7.8%, remaining: impurities) was leached
Fig. 10. Lead content of the solution for 1 mol C6H8O7·H2O addition for different S/L
ratios (constant leaching conditions: β: 0.5, 60 min, 250 rpm, 20 °C).
85
Fig. 11. SEM image of the precipitate obtained from the leaching of PbSO4 with
C6H5Na3O7·2H2O and C6H8O7·H2O (×14,000).
with a solution containing 6 mol of C6H8O7·H2O, 2 mol of H2O2 and
2 mol of C6H5Na3O7·2H2O. Excess C6H8O7·H2O, and H2O2 were added
for achieving the decomposition of PbO and PbO2 in scrap battery past
as discussed in Part 1 (Sonmez and Kumar, 2009). The experiment was
carried out for 60 min using 1/5 of S/L ratio at room temperature. After
the experiment the mixture was filtered. Filtrate solution contained
1.84% of dissolved lead with a recovery of lead citrate of over 98%. The
lead citrate crystals were uncontaminated (over 99.9% purity) that can
be useful as the precursor from which PbO/Pb can be generated by a
process of combustion–calcination at relatively low temperatures
(b400 °C) for direct use in the preparation of lead pastes for new
batteries. The energy requirements are met from the energy generated
by the combustion of the organic precursor. C6H8O7·H2O and
C6H5Na3O7·2H2O are produced from biological sources and is available
at relatively low cost as industrial chemicals in food industry. Thus as
source of energy, they are regarded as C-neutral. The reaction
conditions for converting lead citrate compounds to micron to nano-
sized PbO (or even Pb and PbO2) are discussed in another paper being
prepared.
4. Conclusion
According to the experimental results combined C6H8O7·H2O/
C6H5Na3O7·2H2O reagents may be used as environmentally acceptable
desulphurisation–crystallization agents. X-ray diffraction of the
precipitate after the leaching of PbSO4 with a solution mixture
of C6H8O7·H2O and C6H5Na3O7·2H2O was different from both Pb
(C6H6O7)·H2O, produced with lead oxides and the powder produced
from the leaching of PbSO4 with C6H5Na3O7·2H2O alone. Using
thermal analysis, the stoichiometry of the precipitate was deduced
to be [3Pb.2(C6H5O7)]·3H2O in contrast with the citrates from PbO and
PbO2, where the corresponding stoichiometry of [Pb(C6H6O7)]·H2O
was deduced by both thermal analysis and X-ray diffraction. The
application of the method to a mixed waste has been demonstrated.
Results in this work are used to underpin the development of a
new process that can be used for recovering lead from lead battery
pastes.
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