Pilot plant design for the recycling of lead

scrap from Lead Acid Batteries

Hassan Naeem & Faizan Ali Nasir
ME-03
Project Supervisor: Dr Muhammad Shahid

Dept. of Materials Engineering, SCME
Lead Properties

Density 11.34 g/cm
3

Atomic weight 207

Atomic number 82

Melting point 327
o
C

Boiling point 1770
o
C

Specific Heat 130 (J/Kg-K)

Soft and Ductile

Lead Acid Battery Composition




Metallic lead in the form of grids =
31.6%

Lead sulphate (PbSO
4)
/oxides
(PbO) = 40%

Plastic = 6.5%

Separators = 1.9%

Acid (H
2
SO
4
) = 20%
[1] Reference: Al Raaziq Industries
Why recycle? Aims and Objectives

Recycling energy is 1/3
rd
of the energy needed to produce lead
from the ores
Unsafe practices of smelters
To conserve mineral resources (ores)
Only two operating lead recycling industries in Pakistan based
in Lahore and Karachi
Lead demand of the local industry unmet
Reducing import costs- 3.47 Million USD during Jul-Oct
2010[1]

[1]Reference: Export/Import Report Jul-Oct 2009-10 EDB

Uses of Lead




80%
6%
14%
Battery
Manufacture
Building
Industry
Other
Reference: Lead Action 21, International Lead
Association
Recycling Methods
Hydrometallurgy:Recycling in hydrometallurgy consists of
dissolving the metal from the scrap into a solution through acid or
base leaching

Pyrometallurgy: A process for the extraction of Lead by smelting the
Lead scrap in a rotary furnace at temperatures of around 1200
o
C.


Reference: An overview on the current processes for the recycling of batteries (July
2004), Sao Paulo, Brazil.


Hydrometallurgy

Advantages
A low temperature technique thus reduction of energy consumption
Reduction of slag
Higher yield of lead
Elimination of gaseous emissions and dust i.e. environment friendly

Reference for advantages: D. Andrews et al.r Journal of Power Sources 88
(2000) 124129 & lead.stcitaly.com

Limitations
Capital Intensive
Transformers and rectifiers are needed
Time consuming as compared to pyrometallurgy

Reference for limitations: D. Andrews et al.r Journal of Power Sources 88
(2000) 124129


Pyrometallurgy
Advantages:-
Most widely used process
No waste treatment required
Greater yield

Disadvantages:-
High energy consumption
Requires complex pollution control setup

Reference: D. Andrews et al.r Journal of Power Sources 88 (2000) 124129
& lead.stcitaly.com






Our method: Hydro-Pyro Metallurgy
Reasons for selection of this process:-

Less operating costs due to reduced furnace temperatures
compared to pyrometallurgy

Low emissions of lead

Minimized sulphur emissions to atmosphere i.e. improved
environmental control

Profitable by-products of the process

No need for a complex pollution control equipment hence
saving the cost

Hydro-Pyro Metallurgy: The Process
Battery Breaking

Separation of components which are electrolyte, plastic, separators,
lead grids and battery paste

Desulphurization of battery paste with 50% sodium hydroxide
solution, the best promising approach for hydrometallurgy until
now. [1]

PbSO
4(s)
+ 2NaOH
(aq)
Na
2
SO
4(aq)
+ PbO(s) + H
2
O

Smelting of lead components in furnace

Refining of Lead in the kettle furnace

[1] Reference: Journal of Power sources 53 (1995) 303-306


Battery Breaking and Separation
of the components
Desulphurization of the Lead
Paste
Smelting of Lead Paste and Lead
grids in a rotary furnace
Kettle Refining
Lead Ingots
Electroly-
te
Lead
Paste
Lead
Grids
Plastic
Filtration
Coke
Flux
PbO/Pb obtained from crushing grids
Flux
Smelting
Smelting is the process of extraction of the metal from its ore
or a compound

PbO is exposed to reduction at temperatures approximately
800
0
C in a furnace (rotary furnace in case of industry)

A mixture of reducing agent and flux is used which are
charcoal, soda ash (Na
2
CO
3
), iron chips and limestone

The ratio of feed material : Iron : Soda ash : coal is
approximately 10 : 2 : 1 : 0.5 [5]


[5] Reference: Fundamentals of the recycling of lead acid batteries Dr Heino Vest
2002, Infogate GTZ
Smelting
The reactions are as follows [3]:-
2PbO + C Pb + CO
2

PbO
2
+ C Pb + CO
2

If still a few amount of PbSO
4
remains in the paste it
is converted to Lead by Iron (Fe)
PbSO
4
+ 2C PbS +2 CO
2

PbS + Fe Pb + FeS

[3]Reference: Fundamentals of the recycling of lead acid batteries Dr Heino
Vest 2002, Infogate GTZ


Kettle Refining
Crude Lead produced from the rotary furnace is
again melted in the Kettle furnace in order to further
purify the Lead at temperatures of 450
o
C

To remove the Antimony(Sb) a slight amount of
Sodium Nitrate is added to the melt that forms dross
or slag [1]

The molten Lead then can be casted into ingots and
is ready to be supplied to the industry

[1] Reference: Fundamentals of the recycling of lead acid batteries Dr Heino Vest
2002, Infogate GTZ
FYP
Literature
Review
Outlining Main
Methods
Comparison
of Methods
Devising feasible
method
Design Work
Pilot Plant
Layout
Lab
Experiments
Individual
Component
design
Yield &
Efficiency
Calculations
Design Revisions
Final Results
Revisions
Conclusion of
thesis
Future Work
Timeline Work
March
Week 1 Desulphurization Reactions
Week 2 Filtration and overall yield of PbO
Week 3
Reactor Designing
Week 4
April
Week 1 Furnace Reduction Reactions
Week 2 Yield and Characterization
Week 3
Furnace Designing
Week 4
May
Week 1
Lead Refining Reactions and
Melting
Week 2
Characterization and Yield - Thesis
Work
Week 3
Kettle Furnace Designing
Week 4
Literature Review
Lead/Acid Battery Recycling and the new Isasmelt Process. Journal of Power
sources 42 (1993) 299-313
A low temperature technique for recycling lead/acid battery scrap without wastes
and with improved environmental control
The YMG-ISA Lead Smelting Process, 2005
Infogate GTZ: Fundamentals of Lead Recycling 2002
Opportunities for cost reduction and improved environmental impact in the
lead/acid battery industries, Journal of Power Sources 67 (1997) 243-249
Recycling of Lead/Acid Batteries in a small plant, Journal of Power Sources 57
(1995) 81-83
Environmentally sound technologies for Lead/acid Battery Recycling, Journal of
Power Sources 88 (2000) 124-129
Implementing Efficient Lead Recycling, Journal of Power Sources 78 (1999) 267-
269
Comparative Analysis of two desulphurization methods of battery paste, Journal of
Achievements in Materials and Manufacturing Engineering Volume 55 Issue 2
December 2012
An overview on the current processes for Lead Batteries Recycling, Journal of
Power Sources 135 (2004) 311-319
Preparation of basic Lead Oxide from spent Lead battery paste via chemical
conversion, Hydrometallurgy 117-118 (2012) 24-31
Stc.leaditaly.com

Acknowledgements
Dr. Muhammad Shahid
Special thanks to Mr. Hasham Ahmed of Al-
Raaziq Industries