Resources, Conservation and Recycling 52 (2007) 368–380

Technological improvements in
automotive battery recycling
M.A. Kreusch a,∗ , M.J.J.S. Ponte b , H.A. Ponte c ,
N.M.S. Kaminari a , C.E.B. Marino c , V. Mymrin a
a Federal University of Paraná, Laboratory of Environmental Technology (LTA),
PO Box 19011, Zip-Code 81531-990 Curitiba, PR, Brazil
b Federal University of Paraná, Department of Mechanical Engineering,

PO Box 19011, Zip-Code 81531-990 Curitiba, PR, Brazil

c Federal University of Paraná, Department of Chemical Engineering,

PO Box 19011, Zip-Code 81531-990, Curitiba, PR, Brazil

Received 31 October 2005; received in revised form 13 April 2007; accepted 9 May 2007
Available online 3 July 2007

Abstract

Recycling of automotive batteries for the recovery of secondary lead is extremely important in
Brazil, for the country does not possess large reserves of this metal. Lead is one of the most widely
used metals in the world, but it is highly toxic, posing risks for humans and for the environment
if not utilized or treated adequately. Industrial waste containing lead in Brazil are classified by the
Brazilian Residue Code (NBR—10004:2004) as hazardous. The lead recycling process employed
by the recycling industry in Brazil is the pyrometallurgical process in a rotary furnace. This process
consists of four stages: (1) grinding of the battery to separate plastic, electrolyte and lead plates;
(2) lead reduction in a rotary furnace; (3) separation of metallic lead from slag; and (4) refining
of recycled lead. The purpose of this work is to propose process improvements aimed primarily at
increasing production output by reducing the loss of lead in slag and particulates, thereby providing
a healthier work environment in line with Brazilian environmental and labor laws.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Lead recycling; Environmental laws; Automotive batteries; Lead slag

∗ Corresponding author. Tel.: +55 41 33613424; fax: +55 41 33613197.

E-mail address: makjoy2000@yahoo.com.br (M.A. Kreusch).

0921-3449/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.resconrec.2007.05.004
 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380 369

1. Introduction

Lead recycling in Brazil is a crucial activity in view of the country’s minor lead ore
reserves, which have not been exploited since 1995, but whose lead content is low. Both
commercially and industrially, this metal is highly important. Lead production in Brazil
today consists of secondary lead obtained through recycling, and appears in a very small pro-
portion of about 0.63% in worldwide production. The demand for lead is supplied through
imports of primary lead from countries such as Peru, China and Venezuela (DNPM, 2001).
Although the environmental problems associated with lead are critical at an environmen-
tal level, the consumption of this metal shows a constant upward trend, since it is not yet
economically feasible to substitute the lead used in a variety of applications, especially
in the batteries, for any other metal (Jost, 2001). Lead–acid batteries are among the most
frequently recycled products in the US, with a reported collection and recovery rate of 99%
(Higgins et al., 2007). In 1998, 63% of the lead used in the production of US goods (1.12
million metric tonnes) was secondary (recycled) lead (Higgins et al., 2007). The annual pro-
duction of automotive batteries in Brazil is approximately 15 million units (Ferracin et al.,
2002), from which ca. 150,000 tonnes of lead can be recovered. With the new Brazilian gov-
ernment regulations named Conselho Nacional de Meio Ambiente (CONAMA) Resolution
number 257/99, for collection and recycling of exhausted batteries, most of the producers
of lead–acid batteries established the goal of increasing the use of lead yielded from the
recycling of practically 100% of these batteries. Nowadays, lead recovery from exhausted
batteries is carried out by the pyrometallurgical route, which may cause environmental
problems like the emission of considerable amounts of dust containing lead particulate and
sulphur oxides into the atmosphere (Valdez, 1997).
Lead is the world’s most commonly recycled metal on an industrial scale, with about
80% of all the lead produced worldwide applied in the fabrication of automotive batteries.
More than 95% of the batteries used in the US and Europe are recycled. Fig. 1 compares the
refining of primary lead with the production of secondary lead, showing the growth of lead

Fig. 1. Comparison of annual lead production by mining (primary lead) and by recycling (secondary lead)
(1000 tonnes).
370 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380

recycling from 1980 to 1998, and an estimate of this growth from 1998 to 2006 (Winckel
and Rice, 1998).

1.1. Worldwide lead production and consumption

According to estimates by the International Lead Zinc Study Group—ILZSG (2004), the
worldwide production of primary and secondary metallic lead, i.e., the mined mineral and
the mineral obtained by recovery of scrap metal, respectively, reached 6.7 million tonnes
in 2003, with Asia and America being the largest producers (ILZSG, 2004).
Brazil’s apparent consumption of lead in 1999 reached a total of 94,400 tonnes (DNPM,
2001), while worldwide consumption in 2003 amounted to almost the entire production of
that year, the main consumers being the United States, Asia and Europe (ILZSG, 2004).

1.2. Principal uses of lead

Lead was one of the first metals worked by humans since 3500 BC (Lund, 1971). Lead
is present in a variety of alloys and its composites are prepared and used on a large scale by
industry (ATSDR, 2004; Parmeggiani, 1983). In addition, by means of these alloys, these
materials are used for the production of batteries, pigments, roll extrusion, ammunition,
cables, gasoline additives, and others (U.S.EPA, 1998).
The use of tetraethyl lead (additive) has been banned in Brazil since 1978, and has been
replaced with ethanol. Some countries still used this additive in gasoline, which is found in
considerable quantities in the biosphere (Winter, 2004).

1.3. Lead toxicity

Although both natural and anthropogenic processes are responsible for the release
of lead into the environment, anthropogenic contamination is predominant (ATSDR,
2004). A large amount of lead where the produced is present in the form of
environmental contamination (Bellinger and Schwartz, 1997). The impact caused by
mining and foundry activities can persist for a long time in the environment (WHO,
2004a,b).
A concentration of lead of less than 10 ␮g/dl is considered acceptable by the WHO (World
Health Organization), the CDC (Center for Disease Control) and the ACGIH (American
Conference of Governmental Industrial Hygienists). The ACGIH also recommends this
limit for pregnant women (FAO/OMS, 1994).
Table 1 lists the biological parameters that limit the exposure of workers to lead in
the work environment. These parameters indicate the need for alterations in the process
and in the environment, and/or removal of the worker from areas exposed to this heavy
metal (Kreusch, 2005). Acceptable levels of lead are regulated for food and water through
Directive # 16 of the National Environmental Commission (CONAMA).
The lead recycling process in Brazil has grown steadily over the years. In addition to
preserving the environment, the recycling of this element ensures its increased life cycle.
Recycled lead maintains the same physicochemical properties as primary lead and has
become the raw material of this metal (Jolly and Rhin, 1994). There are basically three
 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380 371

Table 1
Occupational biological parameters
Biological parameters Exposition levels

I II III IV
Lead in the blood ≤40 40–60 60–70 >70
(␮g/100 ml)
Lead in piss (␮g/l) ≤70 70–120 120–400 >400
Individual measures Annual control Quarterly control Removal of the Removal of the
exposition source work
and examination for
the displayed ones
Ambient measures None Control of the Necessary to improve the
work environment technological conditions of the work
environment
Source: FAO/OMS (1994); Kreusch (2005).

methods for battery recycling: separation of components through unity operations of mining
treatment, pyrometallurgy and hydrometallurgy (Jolly and Rhin, 1994).
The pyrometallurgical process is composed of four stages: (1) grinding of the battery
to separate plastic, electrolyte and lead plates; (2) lead reduction in rotary furnace; (3)
separation of metallic lead from slag; (4) refining of recycled lead.
According to Jost (2001), the main sources of environmental impact caused in the stages
of the recycling process are:

1. Grinding of the battery to separate plastic, electrolyte and lead plates:

• Dust contaminated with lead and acid electrolyte.
• Particulate lead.
• Contaminated waste.
2. Lead reduction in a rotary furnace:
• Lead-contaminated scraps.
• Lead-contaminated dust (from filters).
• Emission of SO2 .
• Emission of chlorinated compounds.
• Production of slag.
3. Separation of metallic lead from slag and refining:
• Emission of lead vapors.
• Emission of SO2 .
• Production and removal of a fine, dry dust with a high percentage (%) of lead and
other metals.
• Release of chlorine gas (Cl2 ).

The pyrometallurgical process for recovering lead involves redox reactions at high temper-
atures (1000 ◦ C).
Lead metal scrap is composed of metallic lead, oxides and lead sulphate. The reduction of
metallic scrap into metallic lead requires the addition of carbon and iron as reducing agents,
with all the components subjected to high temperatures (Machado, 2002). Two reactions
372 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380

occur simultaneously:
PbO + C ↔ Pb0 + CO (1)
PbO2 + 2CO ↔ Pb0 + 2CO2 (2)
The lead oxides (PbO and PbO2 ) react with carbon (C—reducing agent), resulting in the
formation of metallic lead (Pb0 ) and carbon gases.
In a third reaction, lead sulphate (PbSO4 ) reacts with metallic iron (Fe0 —reducing agent),
forming metallic lead (Pb0 ) and iron sulphate (FeSO4 ), according to the following chemical
reaction:
PbSO4 + Fe0 ↔ Pb0 + FeSO4 (3)
The generated residues are proceeding mainly from incomplete reactions that occur inside
the furnace due to the variation of temperature of about 650–1000 ◦ C as is presented in
Eqs. (1–3), insufficiency of the reducing agent (iron or carbon) and inadequate homog-
enization of raw materials. The process of reduction of the lead consists in isolating the
metallic lead of the mixture of some gotten substances of the scrap: metallic lead, lead
oxide (PbO), lead sulphate (PbSO4 ) and other metals, as for example Ca, Cu, Ag, Sb, As,
and Sn.

1.4. Brazil’s environmental laws

Brazil’s environmental laws are very strict and highly detailed. In addition to municipal,
state and federal laws, there are decrees, resolutions, government directives and codes. The
main code that deals with hazardous solid waste is the NBR 10004:2004 standard, which
follows the standard of the Brazilian Association of Technical Standards (ABNT) (ABNT,
2004).
In the literature it is reported that on average about 300–350 kg of slag for each ton of
produced metallic lead are generated, and about 5% of this slag is lead composites (Kreusch,
2005).

2. Materials and methods

2.1. Materials

The recycling of automotive batteries generates residues whose chemical composition

contains a certain percentage of lead, usually in the form of oxides and sulphates. The
purpose of this work is to propose process improvements aimed primarily at increasing
production output by reducing the loss of lead in slag and particulates. Samples of slag and
particulates were collected to determine the materials’ chemical composition, as well as
operational data used in the battery recycling process, such as:
• What raw materials are used to obtain secondary lead;
• Chemical reactions of the process.
 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380 373

Fig. 2. Battery recycling flowchart.

2.1.1. Flowchart of the automotive battery recycling process

Fig. 2 shows a flowchart of the automotive battery recycling process.
The flowchart indicates several points in the process where the operation can be improved,
avoiding waste and loss of lead in slag and particulates.

2.2. Methods

2.2.1. Stages of the battery recycling process

Battery recycling consists of various stages, as indicated in the flowchart (Fig. 2), each
with its own objectives, i.e., selection of recyclable battery material, separation of lead from
other metal and contaminants to minimize the emission of solid and atmospheric pollutants.
The raw materials used in the battery recycling process are battery plates (±4500 kg);
iron swarf (650 kg); charcoal (300 kg); sand (200 kg); baghouse particulates (10 kg). The
pyrometallurgical process in a lead recycling furnace should operate with the following
chemical reactions:

PbSO4 + 2C ↔ PbS + 2CO2 (4)

PbS + Fe0 ↔ Pb0 + FeS (5)

Eqs. (4) and (5) demonstrate that initially the lead presents in the sulphate form and after of
the first stage of the reaction that occurs in the presence of the reducing agent (charcoal) in a
temperature of about 650 ◦ C. The lead is present in the form of sulphide where it is reduced
in one second stage of the reaction (iron swarf) in a temperature of about 1000 ◦ C. The ideal
temperature so that the reaction occurs adequately and almost all the PbS is reduced to the
metallic Pb0 around 900 ◦ C.
374 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380

2.2.2. Experimental methodology

Technical visits were made to the battery recycling plant, where the following informa-
tion was initially collected: operational data on the process, particulate samples, and slag
samples.
The company records its operational data on a standard sheet containing the following
information: total execution time of the process, and the quantity, in kilograms, of battery
plate, iron swarf, charcoal, sand, and lead ingots utilized. The only really heavy raw material
is the battery plates, for the remaining material is placed in a standard container.
The particulates were collected as follows. A sample of particulates (about 500 g)
emitted in the lead recycling process was taken from a baghouse. This sample was pre-
pared for chemical analysis X-ray fluorescence (XRF) at LAMIR—Minerals and Rock
Laboratory.
Samples of slag from the recycling process were collected during 3 days from three
different lead slag ladles, one on each day. These samples were cut into three portions,
i.e., lower, intermediary and upper portion. The slag was broken down into small pieces
and ground to remove a representative sample, then pulverized in a tungsten carbide mill
prior to preparing pellets, which were chemically analysed by XRF at the aforementioned
laboratory.

3. Results and discussion

The results of the chemical analysis of the particulate by XRF revealed that the main
chemical component was lead, which accounted for 82.28%, as shown in Table 2.

Table 2
X-ray fluorescence analysis of the particulate
Element (%)
Pb 82.28
Cl 9.55
Fe2 O3 2.85
K2 O 1.53
SiO2 0.65
Sn 0.61
Zn 0.54
P2 O5 0.42
CaO 0.36
Sb 0.34
Nd 0.22
As 0.21
Zr 0.19
Br 0.18
Se 0.04
Al2 O3 0.03
Rb 0.01
Total ∼100.00
 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380 375

Fig. 3. Emission of particulates proceeding from the rotary furnace.

The high percentage of lead (82.28%) in the particulate, identified by XRF analysis
and shown in Table 2, indicates that the lead recycling process employed by the recycling
plant operates deficiently, for this lead is not being recycled. All this particulate (Fig. 3) is
collected in the baghouse, but only a small portion of this material (about 10 kg) is used in
the process. According to Brazilian legislation (CONAMA resolution # 316, of 29 October
2002), the maximum permissible atmospheric emission of lead is 7 ␮g/Nm3 .
The Fig. 4 shows the overall average of the main chemical elements found in the slag
samples analysed here.
The Fig. 4 presents the main joined chemical elements in the slag samples analysed by
the method of XRF and identifies the fact that the extreme amount of iron indicates that the
lead recycling process operates in an inadequate manner therefore this element indicates
that the process of reduction inside the rotating oven does not occur completely, causing an
extreme loss of lead for the slag. Some factors can be also influencing the stage of reduction
as, for example temperature, viscosity, quality and amount of used raw materials as vegetal
coal and iron.

Fig. 4. Analysis of slag from the battery recycling process.

376 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380

Fig. 5. Slag as resulted in processing recycling lead.

The high percentage of iron, oxygen and sulphur found in the generated slag demonstrates
clearly that Eqs. (4) and (5) do not occur completely inside the furnace and consequently
the reduced lead does not finish if incorporating the same one causing a loss of material
which will be discarded.
The reactions do not occur due to the following factors such as temperature less than ideal
temperature, insufficiency of reducing agent in this case the carbon source and presence of
excess iron.
In accordance with the studies carried through in the recycling company, some aspects
in the process of recycling of the automotives batteries can be identified that are:

• Great variation in the production income.

• Loss of lead for the slag (Fig. 5).
• Economic and ambient damage.

The Fig. 6 shows secondary lead production data (kg) from the recycling plant corre-
sponding to the recycling of used battery plates (kg) during the period of January through
September 2004, while Fig. 7 indicates the production output during the same period.

Fig. 6. Balance of secondary lead production from recycled battery plates—January to September 2004.
 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380 377

Fig. 7. Secondary lead production volume—January to September 2004.

The Fig. 6 indicates that the number of used battery plates varies considerably, which
leads to an unbalanced process and, hence, to variations in the production of secondary
lead.
The Fig. 7 illustrates the significant instability in the production output of secondary
lead, which varies from 53.53% to 67.47%. We also found that there was a drop in the
output of secondary lead.
This strong variation results from the following factors:

• The only really heavy raw material is the battery’s lead plate, which varies in each
production batch.
• The sand, charcoal and swarf are placed in a standard container and are not weighed. As
a result, there is a substantial loss of these raw materials used in the battery recycling
process, particularly of swarf and charcoal, for these materials do not have a constant
granulometry and are moreover stockpiled in the open air.
• The premixture of the components used in the recycling process is not homogeneous,
another factor that compromises the process.
• Neither the temperature nor the chemical reaction inside the furnace are properly con-
trolled.
• The process of pouring the melted lead into ingot molds requires improvements to reduce
spillage onto the floor.

Several proposals for improving the process have been put forward, e.g., weigh all
the raw materials utilized, improve the homogenization process, control the temperature
of the process, cover the swarf and charcoal storage areas, improve the exhaust system,
and briquette the particulates, which have a high lead content. The lack of control of the
processing temperature leads to the assumption that the loss of energy is substantial. High
levels of iron in the process require high temperatures to melt the metallic lead, as indicated
in Fig. 4. Moreover, lower viscosities reduce the melt time. The properties established in the
378 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380

Fig. 8. Comparison of secondary lead produced and slag generated in 2004.

melting of the lead would also be improved, and less lead would be lost in the slag, according
to the diagram proposed by Lewis and Beautement (2002) (ABNT, 2004) with the use of
Na2 CO3 to work at a lower temperature and a better viscosity. With the implementation of
some of these suggestions in the process, an improvement of about 70% would be achieved
in the output of secondary lead.
Based on the average quantity of lead produced during the test period depicted in Fig. 8,
400 kg of slag are generated for each ton of lead. Thus, the process employed by the recycling
plant studied here generates 14.3% more slag than the maximum limit determined by the
literature, and 33.3% more slag than the minimum limit established by the literature.
Fig. 9 reveals a very substantial disproportion in the quantity of secondary lead produced
and the amount of slag generated. The best result achieved is 73% of secondary lead and
27% of slag, while the worst result is 53% of secondary lead and 47% of slag. Of the

Fig. 9. Percentage of secondary lead produced and slag generated in 2004.

 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380 379

16 samplings taken at the recycling plant, the overall average results were as follows:
production of secondary lead – 60.05% and generation of slag – 39.95%. The poor quality
of the charcoal used in the process may also strongly influence the quantity of lead produced
if it is not used proportionally to the other raw materials, thus generating larger quantities
of slag.

4. Conclusions

This work enabled us to draw several conclusions about the production, consumption
and recycling process of battery plates to extract secondary lead. The slag produced in the
lead recycling process and the emissions of particulates are responsible for most of the
world’s lead-related environmental degradation. Production yields of secondary lead vary
greatly because the process is inefficiently operated, lacking in such basic requirements as
an adequate procedure and standardization, technology and technical know-how. However,
a major part of these problems can be solved by adopting the improvements proposed here,
particularly insofar as it concerns a standardization of the operating system, improving
the yield and rendering it more homogeneous. With support for research and the help of
recycling plants, a hazardous industrial waste can be transformed into a raw material for
the production of a new product, thereby meeting environmental and labor laws.

Acknowledgments

The authors would like to acknowledge the Federal University of Paraná (UFPR) and
the Laboratory of Environmental Technology (LTA).

References

ABNT—Associação Brasileira de Normas Técnicas. Rio de Janeiro. NBR 10004:2004—Resı́duos Sólidos, Rio
de Janeiro; 2004.
ATSDR, Toxicologia do Plomo, 1995, online http://www.atsdr.cdc.gov/es/plomo, 18 July 2004.
Bellinger D, Schwartz J. Effects of lead in children and adults. In: Steeland K, Savitz DAA, editors. Topics in
environmental epidemiology. New York: Oxford University Press; 1997. p. 314–49.
DNPM, Sumário Mineral, 2001, online http://www.dnpm.gov.br/sm2001.html, 10 May 2003.
FAO/OMS. Documento de Trabajo sobre el Plombo. 26a Reunion del Comite Del Codex sobre Aditivos Contam-
inantes de los Alimentos. Febrero; 1994.
Ferracin LC, Chaccon-Sanhueza AE, Davoglio RA, Rocha LO, Caffeu DJ, Fontanetti AR, Rocha-Filho RC,
Biaggio SR, Bocchi N. Hydrometallurgy 2002;65:137–44.
Higgins CJ, Matthews HS, Hendrickson CT, Small MJ. Lead demand of future vehicle technologies. Transport
Res D 2007;12:103–14.
ILZSG, Statistic Lead and Zinc, 2003; online http://www.ilzsg.org/ilzsgframe.htm, 18 July 2004.
Jolly R, Rhin C. The recycling of lead–acid batteries: production of lead and polypropylene. Resour Conserv
Recycl 1994;10:137–43.
Jost M. Technical guidelines for the environmentally sound management of lead–acid battery wastes; 2001.
Kreusch MA. Avaliação com Propostas de Melhoria do Processo Industrial de Reciclagem do Chumbo e Indicação
de Aplicabilidade para a Escória Gerada, Thesis, UFPR, Curitiba, Paraná, Brazil, p. 128; 2005.
380 M.A. Kreusch et al. / Resources, Conservation and Recycling 52 (2007) 368–380

Lewis AE, Beautement C. Prioristing objectives for waste reprocessing: a case study in secondary lead refining.
Waste Manage 2002;22:677–85.
Lund. Industrial Pollution Control Handbook. MacGraw-Hill Inc; 1971.
Machado IP. Avaliação Ambiental do Processo de Reciclagem de Chumbo, Thesis, Unicamp, Campinas, São
Paulo, Brazil; 2002. p 144.
Parmeggiani L. Encyclopaedia of occupational health and safety, v. 2. 3rd ed. Geneva: International Labour Office;
1983. p. 1200–9.
U.S.EPA. Locating and estimating air emissions from sources of lead and compounds. EPA – 454/R-98-006, index
of/ttnchiel/efdocs/. Lead I.pdf. U.S. Environmental Protection Agency; 1998.
Valdez H. Lead battery markts and recycling in Mexico and South America. J Power Sources 1997;67:219–23.
WHO. Human exposure to lead. In. Human Exposure assessurent series; 2004a.
WHO. World Health organization. Linkage methods for environment and health analysis-general guidelines.
Headlamp project WHO; 2004b.
Winckel JW, Rice DM. Lead market trends—technology and economics. J Power Sources 1998;73:03–10.
Winter M. Web Elements, Univ. Sheffield; 1998, online http://www.shef.ac.uk/ (chem/webelements, 18 July 2004.