Fundamentals of The Recycling of Lead-Acid Batteries: Dr.-Ing. Heino Vest (2002)

Fundamentals of the Recycling of Lead-Acid Batteries
Information & Knowledge Management
Fundamentals of the Technical Information

! Energy / Environment (E)
Water / Sanitation (W)
Recycling of
"
" Agriculture (A)
" Foodprocessing (F)
Lead-Acid Batteries
" Manufacturing (M)
This module is available in:
! English (e)
" French (f)
" German (g)
Dr.-Ing. Heino Vest (2002) " Spanish (s)
" Other(s): ...........................
File: E017e_LeadAcidBatteries.pdf / doc
Batteries are used whenever electrical project). If we consider China alone, the
energy is needed, but there is neither a most populous country of the world, which
direct connection to the public electricity currently starts to introduce private car
grid nor a generator-based stand-alone transport, it is obvious that high growth
supply. Batteries store electrical energy as rates in the consumption of starter
chemical energy. During discharge, the batteries must be expected in the future,
chemical energy is re-converted into especially in developing countries.
electrical energy. Depending on the Returning used lead batteries to the
battery system, this process is either recycling loop has a long tradition. Thanks
irreversible or reversible. There are two to the compactness of a battery, its high
types of batteries: 'primary batteries' and lead proportion (>95%) and relatively high
'secondary batteries'. metal prices, it has been worth while for
Lead-acid batteries are called ‘secondary consumers to return their own or collected
batteries’ or accumulators since they are car batteries to the scrap trade or
rechargeable. They again can be divided secondary smelters. The return rate of
into starter and industrial batteries. Starter spent batteries was thus already high in
and industrial batteries are used to provide times when catchwords such as resource
large quantities of energy (e.g. to start a conservation and environmental
car, operate electric vehicles, as energy protection, recycling, closed-loop materials
storage medium for solar applications, as management etc. did not yet play a role.
short-term emergency power source, etc.). Even today, the success of lead battery
Units generally weigh from a few recycling in developing countries
kilograms to one ton. continues to be determined largely by the
In the lead-acid battery sector, starter potential earnings of scrap collectors and
batteries have by far the largest share. In traders. In industrialised countries,
1995, approx. 96 million units were statutory requirements to take back spent
produced worldwide (source: Battery batteries have compensated for the loss of
Council International). An annual economic incentives in spent battery
production growth rate of < 2% is return.
expected. Especially in developing In most European countries, battery
countries, where the number of cars is retailers are under obligation to take back
growing over-proportionately, high growth spent batteries. Lead batteries also come
rates in the use of lead-acid batteries are from repair workshops, the reprocessing of
to be expected. Studies carried out in scrap car bodies and at municipal
Botswana indicate that the number of collection centres. In Germany, for
batteries used in the automobile sector will example, this well functioning and effective
grow by 40-50% over the period from 1995 collection system has led to a return rate
to 2005 (source: GTZ waste management of more than 95% for starter batteries and
1
gate Information Service / gtz, PO Box 5180, 65726 Eschborn, Germany
Phone: +49 (0)6196 / 79-3093, Fax: +49 (0)6196 / 79-7352, Email: gate-id@gtz.de, Internet: http://www.gtz.de/gate/
almost 100% for industrial batteries. In Older types of batteries have a hard
developing countries, too, return rates of rubber casing and PVC (polyvinylchloride)-
up to 80% can be achieved where buying- separators instead of casings and
up structures for spent batteries are in separators from PP. In some developing
place. In Zimbabwe (source: Central countries (e.g. Zimbabwe) these types of
African Batteries) for example, the entire batteries are still produced and in use.
demand for local battery production is
covered by recycling of used batteries.
Composition of a 12V-44Ah-210 A-starter
battery in a hard rubber casing
1. Battery scrap – raw material for lead containing components 58,8%

hard rubber 17,7%
recycling sulphuric acid 26,2%
separators (PVC) 2,3%
----------
The major source of raw material for lead 100,0%
recycling are starter batteries from motor total weight approximately 15 kg
vehicles. Modern car batteries consist of a
PP (polypropylen)-casing, plates (grids Composition of a modern 12V-44Ah-210 A-
and paste), connectors/poles and bridges, starter battery in PP-casing
and PP-separators as insulators between
lead containing components 63,9%
the plates (Fig 1). Paste consists of Pb, PP-components 5,0%
PbO2 and PbSO4. The electro-chemical sulphuric acid 28,6%
separators (PP, PVC, cellulose 2,5%
reactions which take place during charge ----------
and discharge of a lead acid battery are: 100,0%
total weight approximately 13-14 kg
charging:
2PbSO4 + 2H2O → PbO2 + Pb + H2SO4
discharging: Tab. 1: Battery composition
PbO2 + Pb + H2SO4 → 2PbSO4 + 2H2O
Fig. 1: Design of a starter battery
2
Therefore, recyclers have to be aware that components of an accumulators like lead,

batteries in hard rubber casing and PVC- plastics, acids, etc. are at first separated
separator will come in with battery scrap. and then processed individually, or the
acid is extracted first and the batteries are
Depending on the type of battery, its size processed as a whole. In the first case,
and design, the material composition of a recycling materials are recovered from all
starter battery varies. Table 1 compares components of a battery. In the second
an old type of battery in hard rubber case, only lead is recovered (partially also
casing with a modern type of battery. The residual battery acid), whereby organic
lead-bearing components of a battery are: components are consigned to energy
recycling. In view of the high pollution
Grid metal, poles, bridges 44% control standards implemented in
Pb 96-98%
secondary lead smelters of industrialised
Sb 2-4% countries, modern lead recycling does not
(Ca) <0,5% pose a significant health hazard to the
Paste 56%
local population or the environment.
PbSO4 60%
PbO (PbO2) 19% In developing countries spent lead
PB 21%
batteries are recycled both in industrial
100%
facilities and by informal small enterprises.
Industrial recycling smelters use both the
Tab. 2: Approximate composition of Pb- grid metal and the lead-containing paste to
bearing components of a starter produce secondary lead. The informal
battery sector, in contrast, often only uses the
metallic parts of old batteries (grids,
The grids of old types of batteries have a terminals, bridges) to produce articles
higher Sb (antimony)-content (~4%) than such as solders or weights for fishing nets.
the modern maintenance-free batteries The other parts of the battery are simply
(~2%), which instead add Ca(calcium) dumped in the environment.
<0,5% to their grid alloy.
Even industrial recycling facilities in
developing countries employ many manual
2. Recycling of lead-acid batteries techniques due to cheap labour. Batteries
are often broken up, emptied, separated
2.1 General considerations and charged to the furnaces by hand. The
lead extracted is refined and cast into
As already mentioned, lead-acid battery ingots manually. This creates a potential
recycling has a long tradition, especially in hazard for the workers, the surrounding
industrialised countries. The battery and population and the environment (soil,
scrap trade takes back spent batteries free ground, water resources, etc.) in general.
of charge or even pays the metal value.
Because the metallic fraction of a battery Some secondary smelters also buy up
consists largely of lead, metallurgical pre-sorted battery fractions, e.g. grids and
reprocessing of battery scrap was never a lead paste without casings and separators,
serious problem. Recently it has been in addition to complete batteries. The lead
rather the stricter environmental smelters thus save several processing
requirements that have caused problems stages and do not have to deal with casing
for secondary lead smelters and made and separator wastes. They are therefore
lead recycling less economically viable. willing to pay a higher price for the
material supplied. This practice is very
Lead recovery from spent accumulators harmful in environmental terms. Through
can take two basic routes. Either the the dispersed pre-sorting activities, lead-
3
containing residues and wastes arise in form of coal) and iron (in the form of iron
many places and it becomes impossible to swarf). Impurities are collected in the slag
control their proper disposal. which requires for example soda ash as
liquidifying and slag forming constituent.
The product of the smelting operation is
2.1 Metallurgical aspects of lead crude lead, which needs subsequent
recycling from battery scrap refining, and soda slag as residue. Since
soda slag is water soluble and therefore
As described before, the lead bearing raw hazardous when brought to landfills,
materials extracted from lead-acid battery modern lead recycling plants use silica
scrap are: slag (fayalite slag), which is water
insoluble. It requires, however, a much
Pb(Sb) metal from grids, terminals higher furnace operation temperature of
and bridges approximately 1400°C.
PbO (PbO2) lead oxides, part of the paste
PbSO4 lead sulphate, part of the The refining of crude lead takes place in a
paste refining kettle at temperatures between
400 and 550°C. If only battery scrap is
used for lead production, two subsequent
While the first component needs only refining steps are required:
melting, the two other components have to
be converted by chemical/metallurgical 1. Removal of Cu which might have
processes to obtain lead metal, which entered the melts through copper
takes place in the furnace. wires.
2. Removal of antimony originated from
The first type of chemical reaction the former grid metal to produce pure
converts PbO (PbO2) into Pb through a lead
reduction process:
While the removal of Cu is done in adding
2 PbO + C → 2 Pb + CO2 elementary sulphur, Sb can be removed
PbO2 + C → Pb + CO2 by selective oxidation or by adding sodium
nitrate (NaNO3). The lead in the kettle is
The second type converts PbSO4 into stirred and a dross formed. The impurities
PbS, again through a reduction process: are now removed from the melt by
skimming of the dross formed. It is obvious
PbSO4 + 2 C → PbS + 2 CO2 that the success of the refining has to be
controlled by chemical analysis. The
Finally PbS is converted into Pb through refined metal is cast into ingots for
the following reactions: shipment, sale or further manufacturing.
PbS + Fe → Pb +FeS
or 2.3 Technical steps in battery recycling
PbS + 2 PbO → 3 Pb + SO2
PbS + PbO2 → 2 Pb + SO2 In developing countries lead-acid battery
scrap is normally processed in rotary drum
furnaces using liquid fuel as energy
The above mentioned chemical reaction source. Lead bearing feed materials are
are sum reaction. That means that there either whole battery packs (grids and
are intermediate steps in between. The paste) where the separators have been
reactions take place in the melting furnace removed or two separate fractions
at high temperature (900-1200 °C) and
need additives, which are – carbon (in the
4
Fig. 2: General flow sheet of a semi- they do not need to go through the whole
mechanised battery scrap recycling PbO/PbSO4 into lead metal. They only
need to be molten at some 500°C (low
temperature melt), refined and cast into
a) grid metal only and b) paste and other ingots. Thus, energy and time are saved.
fines
The flow sheet in Fig. 2 shows a semi- 2.3.1 Dismantling of battery cases
mechanised process option for small to and feed preparation
medium scale battery recycling in
developing countries. In this option grids Used batteries are emptied by hand and
and paste are separated and individually the acid is collected in plastic barrels. If
processed. Since the grids (2/5 of the total the full barrels are kept motionless for
material) are already in the metal stage, some time, solid impurities will settle at the
metallurgical process of converting bottom of the barrels. This process of
sedimentation may be assisted by adding
some flocculent. The purified acid is then
5
decanted and packed for sale. Possible hammer mill (Fig. 3) and fed to a grinding/
customers for the recycled acid is the washing drum for separation.
mining and metallurgical industry which
uses acid in various leaching operations. In both cases, the slurry is pumped
The remaining battery sludge is continuously or batchwise to
neutralised with lime. After passing sedimentation tanks, where the solids
through a filter press the filter cake may be settle at the bottom. The clarified liquid is
charged together with the fine fraction into returned back to the grinding operation,
the melting and reduction furnace. while the sludge at the bottom of the tanks
passes a filter press or is left to sun-dry.
In a next step the tops of the acid-free The filter or sun dried cake is the main
batteries are cut off by a guillotine shear feed for the melting and reduction
and the grid packs are removed from the operation which will produce almost pure
battery case. They are fed to a perforated lead.
grinding drum, which rotates in a water
basin. By moving the feed in the drum an The second fraction – the coarse material
autogenous grinding process starts which (basically grids and separators) – leaves
separates the grids from the separators the grinding drum at its lower end.
and, more important, the paste from the Separators and grids are separated from
grids. At the same time the perforation of each other by hand sorting using a slow
the drum acts as a sieve. The fines are moving transmission belt (Fig. 4). The
separated and carried away by the water. metal fraction is the main feed for the low
A bit of lime added to the water neutralises temperature melt producing a PbSb-alloy.
the acidic solutions and prevents the drum
from massive corrosion.
Fig. 4: Hand sorting of coarse feed

fraction
Fig. 3: Hammer mill crushing whole Empty battery cases and covers with the
Batteries attached poles, bridges and remaining grid
parts are charged to a wet hammer mill,
Instead of this labour intensive method where metal parts and remaining paste
whole batteries may be crushed in a are separated from the plastic. The output
6
of the mill passes a perforated drum, temperature the combustion air should be
where solids and slurry are separated. preheated.
While the solids (metal and plastic parts)
are hand sorted, the slurry with the fines is Depending on the temperature and the
added to the slurry obtained from the amount of feed material in the furnace, the
grinding drum. The solid metal parts reaction time will be 2-3 h. Due to the
supplement the feed of the low difference in specific weight the molten
temperature melt. lead produced settles at the bottom part of
the furnace. When enough lead has
The plastic residues of the dismantling accumulated, it is tapped into a mobile
operation either have to be dumped (in the ladle and transported in liquid stage to the
case of PVC-separators) or can be used refining kettle.
as fuel (PP, cellulose, hard rubber) in
cement factories. In this case it is With less PbO/PbS in the slag and more
important that no lead remains in the Pb-metal produced the viscosity of the
plastic product. slag increases. This hampers the
separation of the small Pb-droplet from the
slag. To overcome this problem either
2.3.2 Melting and reduction operation more soda ash has to be added or the
of paste and battery fines temperature in the furnace must be
increased. Both solutions have negative
The filter or sun baked cake of paste is effects. While the first measure increases
charged to a short rotary drum furnace the amount of slag which finally needs to
(Fig. 5) where the charge is melted be discarded, the second measure leads
together with slag forming constituents to higher energy consumption and
(soda ash = Na2CO3) and reaction evaporation of lead into the off-gas.
additives (Fe-swarf, coal). The ratio of the
feed materials Pb-fines : Fe-swarf : Soda It is more advisable to tap the lead before
ash : coal is approximately 10:2:1:0,5. The the optimum of recovery is achieved and
energy needed for the process is obtained to leave the remaining lead-rich slag in the
from the burning of the coal within the furnace for a second or third cycle with
furnace and by an additional burner new feed material.
running on heavy fuel oil, paraffin,
Fig. 5: Rotary drum furnace for battery

diesel, waste engine oil, etc. To save scrap recycling
energy and to achieve a higher furnace
7
After a number of production cycles the Zn, Sb, As) is formed and skimmed off.
amount of slag in the furnace will be too This de-copperisation step should be
large to continue the operation. By adding carried out at least two times to secure the
a bit more coal and fresh soda ash a slag refining result.
wiith a low Pb content (<9% Pb) can be
achieved which is then tapped from the
furnace together with the finally produced
lead. While the lead metal is forwarded for
refining the slag has to be dumped.
Off-gas and flue dust from the operation is

sucked of and treated in the off-gas
cleaning system.
2.3.3 Melting of grids, terminals and

bridges
The coarse fraction of the crushed battery

scrap is fed to a crucible furnace, melting
kettle or rotary drum furnace. By adding a
bit of soda ash the charge is melted and
stirred for some while. During this
operation insoluble impurities will settle on
top of the melt and join the soda ash slag,
which is skimmed off at the end of the Fig. 6: Refining of crude let in a kettle
melting operation. Gases and flue dust
from the process are soaked away and
passed over to the gas cleaning system. The de-copperised lead still contains a
large amount of antimony (and maybe
The melt is cast into ingots or transferred some Sn, As). All of these elements can
in liquid stage to the refining kettle. be removed by oxidation. For that purpose
air or oxygen-enriched air is blown into the
melt and stirred. The different oxides
2.3.4 Refining of crude lead formed settle at the surface and can be
skimmed off. The oxidising process is
First, the lead tapped from the furnace has completed when mainly lead oxide is
to be cleaned from residual oxides and formed.
slag. For that purpose a bit of pitch and
saw dust is added. After stirring for a while Instead of oxidising the impurities by
the impurities settle at the surface and are injecting air, sodium nitrate (NaNO3) can
skimmed off (Fig. 6). be added. Here again a dross containing
the impurities (and lead) is formed, which
Crude lead originating from battery scrap is skimmed off afterwards. All refining by-
is normally alloyed with copper and produced or residues should be processed
antimony (with traces of Ca, Sn, As, Zn). to recover lead and other valuables
In order to remove the unwanted elements components.
two further refining operations have to be
carried out. The refining processes and the purity of
By adding sulphur to the lead melt and the refined lead are monitored by chemical
after stirring for some time, a Pb/Cu2S- analysis.
dross (and if present with minor parts of
8
The off-gases of each of the processes wet gas cleaning system which consists of
are collected and fed into the central gas a venturi washer and a wet scrubber.
cleaning system of the plant.
The task of the venturi washer is the
collection of the fine dust particles. Water
2.3.5 Gas cleaning system and off-gas is mixed under high turbulence
and gas/water spray velocity, forming a
Due to the lack of environmental fine slurry, which is pumped to a
legislation and monitoring, and due to lack sedimentation tank.
of funds industrial operations in developing
countries often have very poor emission The more or less dust free off-gas
control and off-gas cleaning systems. afterwards enters a wet scrubber. Here,
Because of the hazardous potential of the the main task is the removal of the SO2-
majority of the elements and compounds gas of the off-gas. By adding lime to the
which are involved in lead smelting and scrubber liquid, the SO2 in the off-gas will
refining (Pb, Sb, As, SO2, etc.), a certain react with the lime water forming gypsum.
gas cleaning standard must be achieved The gypsum is insoluble in water and
and should be compulsory. precipitates. Again, the fine slurry of the
second scrubber is pumped into a
Therefore, all fumes, gases and dusts sedimentation tank. The clean gas leaves
which are generated during the different the whole process via the main chimney.
production steps should be collected and In the sedimentation tank small amounts
treated in a central gas cleaning system. A of lime and flocculent neutralise the slurry
standard off-gas treatment system and assist the sedimentation of the fines.
normally consists at least of a hot dust
chamber and/or hot cyclone, a venturi
washer and a wet scrubber (Fig. 7).
Fig. 7: Off-gas cleaning system of a lead

recycling furnace in Zimbabwe The sludge passes a filter press producing
a filter cake. The extracted water is re-
From the furnace the hot gases pass circulated to the scrubbers while the filter
through a hot dust chamber and/or a hot cake is fed back into the melting and
cyclone where most of the coarse dust reduction furnace.
particles are separated from the gas
stream. From there the off-gas feed into a
9
3. Environmental considerations - inadequate removal of gases and

vapours during the smelting and
As already mentioned, the potential health refining process
and environmental risk involved when - absent or inadequate flue gas
processing battery scrap is very high. treatment
Depending on the level of mechanisation • use of water-soluble soda slag without
and environmental standards, the the corresponding landfill design that
following environmental hazards can arise: would prevent leaching and dust
formation
• soil and groundwater contamination by • open storage of slag and ashes of the
acid spilled when batteries are emptied refining process
• wind dispersal of lead dust if crushed • open tipping of residues and wastes
battery scrap is stored without such as battery casings and PVC
protection separators.
• substantial atmospheric emissions
(e.g. lead-containing dust, soot, SO2, Workers, too, are exposed to raised levels
chlorides, dioxins, etc.) when battery of harmful substances in such facilities.
scrap is smelted due to: This generates considerable health risks if
- processing the entire battery appropriate precautionary measures are
including its organic parts (casing, not taken (respiratory equipment, washing
PVC separators in older battery facilities, separate eating and resting
types) rooms, regular examinations, etc.).
References and further information: Internet addresses:
• www.wrf.org.uk (World Resource

• Vogler, J.; Foundation)
Work from Waste;
IT-Publications, 1983 • www.recyclers-info.de (Recyclers Info
ISBN 0-903031-79-5 Germany)
• Nickel, W.; • www.ens-news.com (Environmental

Recycling Handbuch; News)
VDI Verlag, 1996
ISBN 3-18-401386-3 • www.epa.gov (Us Environmental
Protection Agency (EPA)
• Vest, H., F. Jantsch;
Environmental Sound Battery • www.eea.dk European Environmental
Disposal and Recycling; Agency
Environmental Handbook;
German Ministry for Economic • www.gm.com Global Recycling
Cooperation and Development, Network
1999
• www.residua.com Information service
resource recovery
10

Fundamentals of The Recycling of Lead-Acid Batteries: Dr.-Ing. Heino Vest (2002)

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Fundamentals of the Recycling of Lead-Acid Batteries

Information & Knowledge Management

Fundamentals of the Technical Information

1. Battery scrap – raw material for lead containing components 58,8%

Fig. 1: Design of a starter battery

Therefore, recyclers have to be aware that components of an accumulators like lead,

Fig. 4: Hand sorting of coarse feed

Fig. 5: Rotary drum furnace for battery

Off-gas and flue dust from the operation is

2.3.3 Melting of grids, terminals and

The coarse fraction of the crushed battery

Fig. 7: Off-gas cleaning system of a lead

3. Environmental considerations - inadequate removal of gases and

References and further information: Internet addresses:

• www.wrf.org.uk (World Resource

• Nickel, W.; • www.ens-news.com (Environmental

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