“INOVAÇÃO TECNOLÓGICA: Os novos

rumos da Engenharia Mecânica e

Industrial.”

FUNDAMENTALS OF PYROMETALLURGICAL OPERATIONS IN LEAD-ACID BATTERY

RECYCLING

Leonardo Henrique Gomes(1) (henrique.leonardo@ufpr.br / leonardohgomes.ufpr@gmail.com),

Maria José Jeronimo de Santana Ponte(1) (mponte@ufpr.br), Irineu Antônio Schadach de Brum(2)
(irineu.brum@ufrgs.br), Haroldo Araújo Ponte(1) (hponte@ufpr.br), Elan Gabriel Forteski(1)
(elangabriel@ufpr.br),
(1)
Universidade Federal do Paraná (UFPR); Setor de Tecnologia
(2) Universidade Federal do Rio Grande do Sul (UFRGS); Setor de Tecnologia

RESUMO: A produção de chumbo secundário no Brasil está ligada às indústrias do ramo metalúrgico,
mais especificamente nas recicladoras de baterias chumbo-ácido. O processo de reciclagem é dividido em
algumas etapas como a moagem, a fundição e o refino, onde os fornos ou reatores utilizados são do tipo
revérberos rotativos; e todas as operações pirometalúrgicas (ustulação, redução, separação chumbo/matte
e a formação de escória) visam o melhor aproveitamento energético e a menor quantidade de impurezas no
produto final e também no seu resíduo, a fim de tornar o processo sustentável sem agredir o meio
ambiente. Este trabalho teve como objetivo, abordar os aspectos gerais e fundamentais relacionados às
operações pirometalúrgicas da reciclagem de baterias chumbo-ácido e a metodologia de trabalho consistiu
em uma revisão da literatura relacionada ao tema central, na qual foram verificadas algumas
condições operacionais para o melhor entendimento do processo como um todo. Os resultados obtidos
através da avaliação do comportamento termodinâmico de diversos elementos constituintes do processo
pirometalúrgico, mostraram os parâmetros fundamentais de controle do processo para uma produção
otimizada de chumbo secundário.

PALAVRAS-CHAVE: Reciclagem de chumbo, meio-ambiente, simulação termodinâmica.

FUNDAMENTALS OF PYROMETALLURGICAL OPERATIONS IN LEAD-ACID BATTERY

RECYCLING

ABSTRACT: The production of secondary lead in Brazil is linked to the metallurgical industry, more
specifically in lead-acid battery recyclers. The recycling process is divided into a few stages such as
grinding, smelting and refining, where the furnaces or reactors used are of the rotary reverb type; and
all pyrometallurgical operations (roasting, reduction, lead/matte separation and slag formation) aim for the
best use of energy and the least amount of impurities in the final product and also in its residue, in order
to make the process sustainable without harming the environment. The objective of this work was to
approach the general and fundamental aspects related to the pyrometallurgical operations of lead-acid
battery recycling and the work methodology consisted of a literature review related to the central theme,
in which some operational conditions were verified for a better understanding of the process as a whole.
The results obtained through the evaluation of the thermodynamic behavior of several constituent
elements of the pyrometallurgical process, showed the fundamental process control parameters for an
optimized production of secondary lead.

KEYWORDS: Lead Recycling, global environment, thermodynamic simulation.

STATEMENT OF RESPONSIBILITY

The authors are solely responsible for this work.

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Mecânica e Industrial
 1. INTRODUCTION

The Lead is a versatile metallic resource that is extremely important for national and
international industrial development, as well, for the global economy, whereas it is directly associated
with the metallurgical industry and energy storage for renewable energy’s (AGRAWAL et al.,
2004).
The battery recycle process has gradually become the main source of lead in several regions
of the world, and that will continue to be inserted in the global market that is still expanding
(ELLIS et al., 2010). Secondary lead production, in developed countries, large exceeds that of
primary lead, and recycled lead globally represents just over 2/3 of the world's refined lead
production. Generally, unserviceable lead-acid batteries are the primary resource of secondary
lead, that represent more than 85% in the total amount of secondary lead (INTERNATIONAL et al.,
2012). one time that, discard of used lead is not an option, the recyclize of used lead-acid batteries
has proven to be of utmost importance in order not to harm human health and the environment
(CHEN, et al., 2014; ARMAND, et al., 2008).
Nowadays, most of these secondary recyclize lead industries are based on pyrometallurgical
methods. As an incensement this demand is constantly, its results in a large backlog of
unserviceable batteries. efforts must be made to improve the industries infrastructure and processes
to solve the technical challenges and improvements in the traditional smelting method (ZANG,
2013; ZHU, et al., 2013).
As a traditional methodology, the most common method used to start recyclize of
unserviceable lead-acid batteries is the grinding process, and subsequently by the pyrometallurgical
route (ZANG, 2013). The basic flow of recyclize these batteries based on the casting method has
not changed significantly over a long period of time, furthermore, the development of new furnaces
and reactors, also the improvement of pretreatment equipment for the pyrometallurgy process has
been studied and improved in recent years (INTERNATIONAL et al., 2012; YANG, et al., 2011).
The recyclize process as divided into stages such as milling, melting, and refining.
The furnaces or reactors used are of the rotary reverb type. All pyrometallurgical operations
(roasting, reduction, lead/material separation, and slag formation) aim for the best use of energy and
the lowest amount of impurities in the final product, in order to make the process sustainable
without harmed the environment.

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 This work aims to address the general and fundamental aspects related to the
pyrometallurgical operations of lead-acid battery recycling and the work methodology consisted of
a literature review related to the central theme, in which some operational conditions were
verified for a better understanding of the process as a whole.
Thus, the contribution of this study is associated with the processes and fundamentals of
pyrometallurgical operations, specifically the stages or steps of Roasting, Reduction,
Lead/Matte Separation and Slag Formation, which are fundamental to the lead recycling process.
Considering that the study was conducted to deepen the theoretical knowledge of the process steps,
it is also of fundamental importance to understand the use of energy and the lowest number of
impurities in the final product in order to make the process more sustainable without harming the
environment.

2. STATE OF THE ART

The recycling of lead from lead-acid batteries within the smelting industry makes use of the
separated material and some inputs, as will be seen at the follow.
The raw material is battery-specific scrap contain paste and grid and, as already mentioned,
is composed mostly of lead (Pb). As a reductant, solid carbon in the forms of anthracite coal and
petroleum coke (charcoal is not suitable) is usually used. It has the function of reducing the lead
present in the form of oxides PbO2 and PbO to metallic Pb (oxygen eliminates the sulfur from
PbSO4 by transforming it into oxides).
Based on the literature and some processes, some adapted flowcharts are presented that
according to Gomes (2019), Moraes (2011) and Espinosa et al. (2004), show in a schematic way
the various groups of processes and steps in a logical sequence and the interaction between them,
as shown below in Figure 1.

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 Figure 1. Industrial battery recycling flowchart. Fonte: GOMES (2019).

According to Espinosa et al. (2004), (Ellis et al. (2010) and Moraes (2011), the
recycling process begins with mechanical processing that essentially involves unit operations
aimed at the physical separation or concentration of materials from battery scraps.
The batteries are broken/crushed in hammer mills, after which the material is passed to a
sinking/flotation operation. This hydrodynamic separation step is used to separate the lead from the
separators and the coating material in two different streams. The housing material is polypropylene
(PP), and segregation can be accomplished through the density difference between the materials.
Since the density of PP is lower than that of water, while the density of lead is much higher than that
of water, this (floating) step is effective in achieving almost complete quantitative segregation. The
polymers are subsequently cleaned and sent for recycling to extruders for use in new battery cases
or for alternative uses. The lead and paste, a combination of the PbO2 , PbO, PbSO4 and lead metal
from the active material, are removed from the bottom of the float operation and sent to storage for
water removal prior to smelting. A typical flow chart for secondary lead recycling is shown in
Figure 2 (ESPINOSA et al., 2004).

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 Figure 2. Simplified flow process diagram for secondary lead smelting. Fonte:
ESPINOSA et al. (2004).

In the milling process four distinct procedures are performed: (a) the battery scrap and the
plastic scrap are ground, separated, washed and removed; (b) the process sludge (negative plate
paste, grid and the metallic lead from the negative plate) is separated and sent to the casting sector
in an appropriate location; (c) the polypropylene (PP) is ground, packed in bags and sent to the
extrusion sector; (d) the acid effluent generated during the battery scrap grinding process is pumped
to the Effluent Treatment Plant. This processing, also represented schematically in Figure 3, begins
with grinding in a hammer mill (1). After this step, the crushed materials are carried by a water flow
that takes them to a sieve (2) where the first separation step takes place: the pulp discharged from
the battery, of smaller granulometry, is separated from the rest. Next, the crushed grate is separated
from the plastic material, through the density difference, in a hydraulic separator (3).
The plastic portion of the battery, housing, and separators goes to a second sieve (4) where a
paste is again obtained. In a second hydraulic separator (5) the polyethylene separator and the
polypropylene housing are obtained. The two streams containing the discharged paste are mixed in
tanks with agitation (6) and the resulting stream passes through a filter-press (7), producing the paste
and a liquid effluent that goes to treatment (GOMES, 2019).

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 Figure 3. Lead acid battery recycling process flowchart. (1) hammer mill; (2) first sieve;
(3) first hydraulic separator; (4) second sieve; (5) second hydraulic separator; (6) stirring tank; (7)
filter-
press. Fonte: GOMES (2006).

In general, conventional pyrometallurgical processing is essentially a mechanism

for concentrating metals into a metal phase and rejecting foreign materials into a phase called
slag, where they include the processes of incineration, melting, pyrolysis, sintering, high
temperature gas phase reactions, and other steps such as roasting, reduction, separation, and slag
formation (ELLIS et al. 2010).
As advantages of pyrometallurgical processes can be cited is that it accepts any type of
battery scrap, usually requires no pretreatment and the process is performed in a few steps.
As disadvantages can be cited the generation of toxic gaseous emissions when not managed
properly, loss of metals by volatilization, generation of large amounts of slag, and low recovery rate
of some metals (ZANG et al. 2016).
Citing batteries specifically, pyrometallurgy is a smelting process most commonly used
for recycling lead-acid batteries and is characterized by the use of high temperatures for
processing materials, however, it is associated with high energy consumption (BERNARDES
et al., 2004); (ESPINOSA et al., 2004).

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 After mechanical processing, already in the smelter, the steps of roasting, reduction,
lead/matte separation and the slag formation step occur (GOMES, 2019).
Some industries have been adapting their processes to remove sulfur before smelting, as
presented in Figure 4, a fact that can contribute in reducing the temperature during the smelting
process, thus reducing the production cost (ELLIS et al. 2010 and ZANG et al. 2016).

Figure 4. Schematic of the pyrometallurgical process. Fonte: ELLIS et al. (2010) e ZANG
et al. (2016)

In the smelting process, the residues from the grinding process: the paste from the negative
plate, the grid and the metallic lead from the negative plate, are chemically reduced and melted
down. The product obtained is "melted lead" which is sent to the refinery.
The material of the metal grid and lead of the battery poles and connections is composed of
lead-alloy and may have a concentration of other elements of up to 12%. Some types of alloys can
be Pb-Sb and Pb-Ca. Other elements that are part of the alloy are As, Sn, Se and Ag. Elements
such as Cu, Zn, Cd and S can be found as impurities.
The discharged paste consists of the material that made up the battery paste that was
attached to the grid. In its composition, what predominates is lead sulfate, PbSO4, however,
significant amounts of lead dioxide (PbO2) and lead oxide (PbO), as well as a small fraction of
metallic lead, are present. The follow reactions (01, 02 and 03) illustrate the production of
PbSO4 in the

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discharge of the negative and positive plates along with the overall reaction with the reverse
reactions characterizes the charging process.

Pb + SO42- - 2e- ↔ PbSO4 (01)

PbO2 + 4H+ + SO42- + 2e- ↔ PbSO4 + 2H2O (02)
PbO2 + Pb + 2H2SO4 ↔ 2PbSO4 + 2H2O (03)

A characterization of the discharged paste, by X-ray diffraction analysis, revealed PbSO4

and PbO2 in larger amounts along with smaller amounts of basic lead sulfate (Pb2O(SO4)) and
metallic lead. Two crystalline forms of PbO2, tetragonal and orthorhombic, were detected. At no
time were PbO, Pb2O3 and Pb3O4. The material presented itself as particles ranging from small
to several hundred micrometers. Most of the particles form a compact matrix of PbSO4 that
contain small inclusions of metallic Pb or PbO2. Around 75% of the area of the paste corresponded
to PbSO4 and 0.5-1% to metallic Pb and the largest occurrence of the metal was as inclusions in
PbSO4. The highest occurrence of PbO2 happened in interstitials and corresponded to 15% of the
studied area. The occurrence of metallic lead does not appear to be occasioned by the battery
grid waste material; rather, its morphology suggests that the metal is formed by the electrochemical
reduction of PbSO4 (CHEN, et al., 1994).
The separator is the last material obtained from the process of discharged batteries that is
introduced as raw material in smelting furnaces. Although it may contain some amount of lead in its
ashes, metallic Pb not properly separated and ground grid, its main function in the reduction furnace
is to provide an energy contribution, due to the predominance of carbon in its composition
(GOMES, 2019).
The residue (lead slag) is sent to the hazardous waste landfill. Besides these, there is also
lead dust, obtained from the gas filtration process of the reduction process. The lead dust can
be reintroduced into the smelting process. Dependent on the lead content in the slag, if it is too high,
it can also be returned to the smelting process.
The refining process is where the purified 'melted lead' from the furnaces is added with the
alloying metals presented in the form of ingots according to the standard specified by the customer.
The lead can also be of external origin coming directly to this sector of the industry. To finish
the recycling process, polypropylene (PP) is extruded and processed (crushed from grinding) into
pellets that are packed in bags for marketing.

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 3. GENERAL DISCUSSION

The pyrometallurgical process for melting lead waste is carried out in a rotary furnace, where
the heat required for the reactions is obtained through the combustion of a fuel. After the waste is
melted down, two layers are formed that are perfectly identified due to the difference in density
between them: a lower layer formed by the lead and an upper layer by the slag.
Due to the presence of metallic sulfides, eventually a third layer may appear, intermediate
between the liquid lead and the slag, called matte.
For the formation of slag, the material added to the process is iron. It acts as one of the sulfur
collectors by fixing it and forming iron sulfide (FeS) besides serving as a receptor for
impurities present in the raw materials. After slag formation, there is the melting stage and the most
common material used as a flux is sodium carbonate (Na2CO3). It has the function of lowering the
melting point and decreases the viscosity of the slag. Limestone and silica can also be used as a
fluxing agent. In addition to this function, sodium carbonate is also an important element in fixing
sulfur.
The recycling process itself can be simplistically imagined as the reduction of the lead
oxides obtained from the sulfate roasting by the carbon of solid reductants (of low reactivity)
and the capture of sulfur by sodium (added to the process in the form of sodium carbonate),
according to Reaction (04) described below:

PbSO4 (s) + Na2CO3 (S) + C (S) → Pb (l) + CO (g) + CO2 (g) + Na2SO4 (04)

This reaction, although simple, already highlights the non-existence of SO2 in the gas
emissions and the obtainer of raw lead in the liquid state - because of the high temperature, around
800°C to 1000°C. The furnace charge is heated by the flame from the combustion of natural gas or
other gaseous fuel (directly and by reverberation of the heat in the refractories of the rotary furnace).
For a better understand of the process, it can be divided into phases which are: Roasting
Phase; Reduction Phase; Lead/Matte Separation Phase; Slag Formation Phase. These stages will be
seen in detail in the sequence (GOMES, 2019).

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 3.1 Roasting or Sintetrization Step

This process can be explained by means of Figure 5, which is a simplified Kellogg diagram
(predominance area diagram). Whereas displayed, from lead sulfate (contained in the batteries), a
state of thermodynamic equilibrium must be obtained such that both the partial pressure of oxygen
and the partial pressure of SO2 at equilibrium are low to reach the area where liquid lead are stable.
The graph shows the situation of the predominance area diagram (Kellogg diagram) for the
temperature of 890°C. It can be seen that the sulfate from the scrapped battery, by gradually losing
sulfur (by oxygen supply, i.e., by roasting), gradually becomes an oxide. The process can be
followed in the diagram as a compound (PbO)x(PbSO4) in which the ratio of PbO to
PbSO4 increases significantly towards PbO. It can also be seen that it is possible to reduce
PbO to lead by the
elimination of oxygen (oxide reduction process).

Figure 5. Predominance area diagram (Kellogg diagram) for lead (schematic), 890°C.
Fonte: GOMES (2019).

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 Another study was performed to exemplify the understanding of the behavior of the
components present in the slag during the roasting process. Figure 6 (a) shows that the oxidation
rate of PbS at a temperature above 550°C is dramatically increased after complete oxidation occurs
at about 800°C. However, the complex structure of the Pb2Sb2O7 oxide is not actually
effectively converted into its water-soluble form from roasting. Thus, an "extra step" of roasting is
required to separate the Pb and Sb. Figure 6 (b) shows that the PbO2 from the first roasting
step can be completely sulfated at 300°C (KIM et al., 2021).
The sulfation process at high temperatures releases the Pb and Sb from the oxide complex
structure, producing Pb sulfate and Sb oxide. In Figure 6 (c), the experiment was conducted to
consider single-step roasting to mix with H2SO4 in the first phase. The result shows that Pb and Sb
are released at about 500-600°C. However, SOx gases are generated at 200°C, which means that
extra gas scrubbing treatment is needed to reduce the emission of hazardous gases. Related
chemical reactions in roasting are listed as follows:

PbS + 2O2→PbSO4 (05)

PbSO4→PbO + SO3 (06)
Pb2Sb2O7 + 2H2SO4→2PbSO4 + Sb2O5 + 2H2O (07)
PbSO4 + Na2CO3→PbCO3 + Na2SO4 (08)

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 Figura 6. HSC modelling of the roasting of the LD: (a) Pb phase change, (b) breaking the
complex oxide structure of Pb2Sb2O7, and (c) H2SO4 roasting at 0–1000°C (Condition: (a) 1 kmol
of PbS: O2, (b) 1 kmol Pb2Sb2O7: 1.5 kmol H2SO4 (c) 1 kmol PbS: 2 kmol H2SO4). Fonte: KIM
et al., (2021).

3.2 Reduction Step

The reduction of oxides by carbon is called, in metallurgy, carbothermic reduction.

The carbon used as to reduced agent in the carbothermic reduction processes is obtained
from the

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devolatilization of coal or wood produces coke or charcoal, respectively. The devolatilization of
coal or wood occurs by a pyrolysis process through heating in specific ovens.
The coke inside the reduction furnace reacts with CO2 producing carbon monoxide accord to
the Boudouard reaction:
CO2 (g) + C (coque) → 2CO (g) (09)

The Boudouard equation allows the determination of the partial pressures of CO2 and CO that these
gases reach, in the equilibrium state, around a reductant particle. From these pressures the CO2/CO
ratio can be calculated for all temperatures. This quotient can be seen in Figure 04 as a function of
1/T. With the line marked by the Boudouard reaction, it can be seen that at low temperatures the
atmospheres generated are little reduces, but their reduced power increases accord with the
temperature.
In other form, one reduction reaction of a generic oxide by CO giving CO2 and the metal
is represented by:
MeO (s) + CO (g) → Me + CO2 (g) (10)
It has its equilibrium constant given by the equation:
K = (pCO2 / pCO) (11)

If the quotient of the pressures for the Boudouard reaction is lower than the quotient of the
pressures for the equilibrium oxide-metal, the oxide can be reduced carbothermically.
By observing Figure 04, it is showed that the lead oxide will be easily reduced by CO, where
is considered that lead is a relatively noble metal (it is, together with copper and nickel, in the
upper part of Figure 7).

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 Figure 7. Logarithm of the CO2/CO ratio of the atmosphere, in the equilibrium state
containing gas, metal, and oxide, as a function of the inverse of temperature. Fonte:
ROSENQVIST
(2004).

According to Ellis et al. (2010) the carbothermal reduction of PbO2 and PbSO4 can
be accomplished through pyrometallurgy with the production of SO2 and the capture of sulfur
(S) through SO2 scrubbing.
Battery paste consisting of a mixture of lead oxides and sulfates is carbothermically
reduced according to the following reactions cited below in a furnace/reactor. The basics of this
process can be seen in Figure 8 from the Ellingham diagram that outlines the thermodynamics of the
process over a wider temperature range.

PbO2 + Heat → PbO + ½ O2 (12)

PbO + C → Pb + CO (13)
PbSO4 + 4Pb → 4PbO + PbS (14)

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 Figure 8. Ellingham diagram of secondary lead smelting. Fonte: ELLIS et al., (2010).

The Ellingham diagram indicates that a temperature greater than 1500 °C would be required
to reduce PbSO4 to form lead, PbS, and SO2, if not driven by the Le Chatelier principle. Calcium
oxide (CaO) is very important to eliminate SO2 from the PbSO4 input in the furnaces/reactors. A
sufficient amount of CaO must be added to eliminate sulfur as SO2. Adding excess carbon does
not help to produce more lead from PbSO4, because carbon promotes the formation of PbS
according to the reactions shown below.

2PbO + Pbs → 3Pb + SO2 (15)

CaO + PbS → PbO + CaS (16)
CaS + 3PbO → CaO + SO2 (17)
CaS + 3/2 O2 → CaO + SO2 (18)

On the other hand, it produces matte (PbS) and a slag with high lead content. The
Ellingham diagram below, Figure 9, shows that PbS is stable over the entire temperature range
from 500 to 2000 °C.

PbSO4 + 4C → PbS + 4CO (19)

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 Figure 9. Ellingham diagram showing the PbS–FeS matte. Fonte: ELLIS et al., (2010).

3.3 Lead-Matte Separation Step

The material from Step 1 is basically liquid lead with a high sulfur content. The addition of
iron from scrap produces a Pb-S-Fe triple alloy; at accord to the Information obtained with the
help of thermodynamics, at 1200°C, the addition of an excess of iron to the system causes a
separation of the original phase into two others, that is: there is a “miscibility gap” in the
ternary diagram, represented in Figure 10.
The existence of this gap is very important, because it contributes to the extractive
metallurgy of secondary lead, related that one the liquids is lead itself (with low levels of S and Fe,
which impurify it), while the other collects these elements, and is called matte (despite the name, it is
the same liquid phase, but with a different composition).

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 Figure 10. Fe-S-Pb ternary diagram at 1200 °C show the solubility gap region.
Fonte: ARNOUT et al. (2011).

3.4 Slag Formation Step

The newly formed matte in the previous stage, due to the high density of the liquid lead,
floats on it. In this position, with the rotative movement of the furnace, increase the possibility
to that contact with oxygen, which will be absorbed and come to constitute na important part
of its composition (GOMES, 2006).
As more oxygen is offered, saturation is reached and a new phase comes into the system -
slag. The two phases, with the oxygen content dependence, can coexist, but, under a large oxidation
conditions the matte phase will disappear completely, afford the slag phase evolution on their space
(GOMES 2019).
Slag management is an extremely important issue because at temperatures above 1200°C,
slag becomes a universal solvent and often serves as a "sink" for residual contaminants, which
prevents these contaminants from accumulating in the refinery. The slag also forms a layer on top of
the metal, preventing further oxidation of the underlying metal. The iron used in this step is often
obtained from post-consumer sources and can bring significant amounts of metals common to

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extractive metallurgy for example, nickel, chromium, copper, tin, zinc, which will need to be
removed in subsequent steps in the refining industry (ELLIS et al., 2010).

4. CONCLUSIONS

The roasting step was described in a simplified way accord to the literature review with the
use of a generic diagram. In this step, the control of the addition of oxygen and carbon, for the
removal of sulfur, contained in PbSO4, and the reduction of lead, is a very important step in the
process. This sulfur is captured by the use of Na2CO3. However, some of the sulfur will form the
matte phase by its combination with iron and lead.
The matte phase recently-formed in the previous step, because of the high density of the
liquid lead, floats on top of it. In this position, with the rotating movement of the furnace, the
possibility of it been exposed and coming into contact with oxygen increases, which will be
absorbed and come to constitute an important part of its composition. As more oxygen is offered to
the system, oxygen saturation is reached in the matte, and a new phase comes into existence in the
system - slag. The two phases, therefore, depends on the oxygen content, can coexist. Over
time, with the consumption of the solid reductant (carbon that is no longer supplied to the system),
the conditions inside the furnace become oxidizing. In the limit case, under very oxides conditions,
the matte phase disappears, leaving in its place only the slag phase, which may contain lead.
The matte phase, with significant lead content, will compose part of the process waste causing
environmental problems and loss of efficiency of the lead recycling process.
The reduction of the sulfur content in the matte phase (miscibility gap), presented in the Pb-
S-Fe ternary diagram, can be optimized by the insertion of iron to the system. Thus, at the
conversion time of the matte phase into slag, there could be a significant reduction of the lead
content in the final process residue.
The analysis of the thermodynamics of the reactions involved in the recycling process of
lead-acid batteries, show that the fundamental issues of the secondary lead production process,
as proposed in this work, have been addressed, thus presents critical steps and procedures to
be optimized in the pyrometallurgical process.

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ACKNOWLEDGMENT

This study was funded in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível
Superior - Brazil (CAPES) - Finance Code 001.
Department of Mechanical Engineering, Federal University of Paraná (UFPR).
Department of Metallurgical Engineering (DEMET) and Center of
Computational Thermodynamics for Metallurgy (NTCm) of the Federal University of Rio Grande
do Sul (UFRGS).
Nestor C. Heck (in memoriam), a Full Professor at the Federal University of Rio Grande do
Sul.

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