Metalurgia Extractiva Del PB PDF

The Extractive
Metallurgy of Lead
By
Roderick J Sinclair
Consultant in extractive metallurgy and formerly with The Electrolytic
Zinc Company of Australasia and Pasminco Limited.
The Australasian Institute of Mining and Metallurgy

Spectrum Series Volume Number 15
2009
Published by:
THE AUSTRALASIAN INSTITUTE OF MINING AND METALLURGY

Level 3, 15 - 31 Pelham Street, Carlton Victoria 3053 Australia
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© The Australasian Institute of Mining and Metallurgy 2009
First Edition, June 2009
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in any form or by any means without permission in writing from the publishers.
The AusIMM is not responsible as a body for the facts and opinions advanced in any of
its publications.
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Preface
The history of lead is as old as the recorded history of mankind. Its use as a valuable material in
society has been equally long and varied. In more recent times awareness of lead’s toxicity has
restricted its widespread use and many older applications have been replaced by newer materials
or have been phased out. Today the use of lead is dominated by the automotive lead-acid battery,
and a key feature of this application is the ability to achieve a high level of recovery and recycle of
scrap batteries. This attribute now makes lead the most recycled metal in use and approaching
60 per cent of the world’s supply of lead is provided by recycled metal. Secondary processing and
smelting is consequently as important a part of the extractive metallurgical industry as primary
extraction from ores and concentrates.
The growing market share of batteries and the corresponding growing availability of secondary
lead has meant that the demand growth has largely been met by secondary lead and the production
of primary lead has been static or in decline for many decades. Coupled with increased regulation
and controls of the environmental and occupational health aspects of the industry, there has been
little incentive to change other than to meet higher regulatory standards. There has been a steady
decline in the number of operating primary smelters and technology change has been slow.
Nevertheless the industry plays a vital role in the supply of materials to society and there is a need
for awareness of processing options so that the most efficient and cost-effective methods of lead
extraction and refining can be applied.
There is a singular deficiency in the technical literature of a comprehensive text covering the
extractive metallurgy of lead. The purpose of this text is to hopefully fill that gap and to summarise
the main processes in use for lead extraction and refining, the reasons why they are used, and the
key features of their design and operation. It is primarily written for those in the industry, as an
introduction to the issues involved, and to provide a means of developing a broader perspective of
the extractive lead industry, and the ramifications of actions within any one sector of the lead
production chain. It is by no means an exhaustive exposé of all aspects of individual processing
steps in the extractive metallurgy of lead, but it is hoped that it has covered most key aspects and
can serve as a reference and guide to stimulate further enquiry as required.
This work follows the completion of a similar text on the extractive metallurgy of zinc, written
with the same purpose in mind. The two metals are so closely associated in terms of mineral
occurrence and extraction, that it seemed necessary to develop a complementary text on lead and
have companion reference volumes covering each metal. Some of the details in this text repeat to
some extent sections in the earlier zinc text, such as the coverage of slag fuming, but this has been
done to allow each to stand alone, with sufficient information for those only interested in lead.
As with the zinc text, the material is drawn from both the technical literature and from a long
term association with the industry and many experienced and competent technical experts over
many years.
Much appreciation is expressed to my colleagues for comments, in particular Jim Happ and
Denby Ward, and for the support and encouragement from Dr Rod Grant.
Roderick J Sinclair
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Part A – General Context . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Chapter 1 – Industry Perspective and Introduction . . . . . . . . . . . . . . . . . . . . . . . . . 3
Introduction, Properties and Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3
World Supply and Demand. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6
The Lead Smelting Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7
Primary Smelting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
Secondary Lead Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13
References and Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15
Chapter 2 – Historical Background. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Lead Production in Early Times . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .17
The Lead Blast Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21
Preparation of Blast Furnace Feed. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .23
Blast Furnace Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25
Lead Refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26
Silver Recovery. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26
Direct Smelting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27
Secondary Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28
Historical Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .29
Chapter 3 – Raw Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Lead Mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .31
Separation and Concentration Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Commercial Lead Concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .36
Commercial Terms for the Purchase of Standard Lead Concentrates . . . . . . . . 38
Commercial Terms for the Purchase of Bulk Concentrates . . . . . . . . . . . . . . . . . 40
Commercial Terms for the Sale of Lead Bullion . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Secondary Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .41
Part B – Primary Smelting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

Chapter 4 – Sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Process Chemistry and Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
The Sintering Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .46
xiii
The Structure of Sinter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .49
Process Operating Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .50
Updraught Sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .55
Sinter Machine Capacity and Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Gas Handling and Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .60
Sulfuric Acid Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .62
Chapter 5 – The Blast Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .65
Chemical Principles and Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Furnace Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .67
Slag Characteristics and Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Furnace Construction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .75
Furnace Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .80
Environmental Issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .85
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .86
Chapter 6 – The Imperial Smelting Furnace ( ISF) . . . . . . . . . . . . . . . . . . . . . . . . . 89
General Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .89
Process Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .89
Slag Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .92
Evolution of Furnace Design and Operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Coke Use and Furnace Capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .96
Chapter 7 – Direct Smelting Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .99
The Boliden Lead Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .105
The Kaldo Process (Top Blown Rotary Converter – TBRC) . . . . . . . . . . . . . . . 106
The Kivcet Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
The Queneau-Schuhmann-Lurgi (QSL) Process . . . . . . . . . . . . . . . . . . . . . . . . 116
Top Submerged Lance (TSL) – Slag Bath Processes . . . . . . . . . . . . . . . . . . . . 119
The Isasmelt Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .120
The Ausmelt Lead Process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .123
The Outokumpu Lead Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .125
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .126
Chapter 8 – Smelter By-Products and Treatment Processes. . . . . . . . . . . . . . . . 129
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .129
xiv
Slag Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .129
Zinc Recovery from Slags. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .130
The Conventional Slag Fuming Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Top Submerged Lance Slag Fuming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
High Intensity Fuming Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
Fume Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .144
Electric Arc Fuming Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .146
Treatment of Lead Smelter Mattes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .147
Sinter Plant and Smelter Dusts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .147
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .148
Chapter 9 – Electrochemical Reduction Processes . . . . . . . . . . . . . . . . . . . . . . . 151
Background. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .151
Processes Based on Molten Salt Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Processes Based on Aqueous Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .163
Part C – Secondary Smelting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165

Chapter 10 – Secondary Materials and Pretreatment . . . . . . . . . . . . . . . . . . . . . 167
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .167
Lead-Acid Battery Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .168
Battery Breaking and Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .170
Paste Desulfurisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .172
Processing of Secondary Residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .174
Chapter 11 – Secondary Smelting Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .175
Reverberatory Furnace. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .175
The Blast Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .178
The Electric Arc Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .180
Rotary Furnace Smelting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .181
Top Blown Rotary Converter (TBRC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
Top Lance Slag Bath Reactors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .188
Electrowinning Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .188
Refining of Secondary Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .193
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .194
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Part D – Refining of Lead Bullion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
Chapter 12 – Thermal Refining of Primary Lead Bullion. . . . . . . . . . . . . . . . . . . . 197
Methods and Equipment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .199
Copper Removal or Copper Drossing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
Softening for Arsenic, Antimony and Tin Removal . . . . . . . . . . . . . . . . . . . . . . . 205
Removal of Silver and Other Precious Metals . . . . . . . . . . . . . . . . . . . . . . . . . . 210
Separation of Thallium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .217
Separation of Zinc from Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .217
Separation of Bismuth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .219
Final Caustic Refining. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .220
Refining of Secondary Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .221
Summary of Common Impurities, Their Control and Recovery . . . . . . . . . . . . . 221
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .224
Chapter 13 – Electrolytic Refining of Lead. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
Process Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .227
Practical Operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .230
Current Modulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .236
Periodic Current Reversal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .237
Bipolar Electrode Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .238
Final Refining of Cathode Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .238
Anode Slimes Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .238
Other Electrolytic Refining Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .241
Chapter 14 – Alloying and Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
Handling Molten Lead and Alloying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .243
Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .243
Part E – Environmental and Economic Issues . . . . . . . . . . . . . . . . . . . . . . . . . . 247

Chapter 15 – Health and Environment Issues . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .249
Lead in the Environment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .249
The Toxicology of Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .249
Exposure Pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .251
Occupational Standards and Controls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
External Environmental Controls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .254
xvi
Product Controls and Life Cycle Management . . . . . . . . . . . . . . . . . . . . . . . . . . 256
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .257
Chapter 16 – Energy Consumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
Purpose and Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .259
Energy Consumption for the Sinter Plant–Blast Furnace. . . . . . . . . . . . . . . . . . 259
Thermal Refining of Lead Bullion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .261
Electrolytic Lead Refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .261
Direct Smelting Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .262
Electrochemical Lead Extraction Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Comparison of Extraction Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
Energy Consumption in Supply of Lead Concentrates. . . . . . . . . . . . . . . . . . . . 266
Energy Consumption for Secondary Lead Production . . . . . . . . . . . . . . . . . . . . 267
Chapter 17 – Costs and Economics of Lead Production . . . . . . . . . . . . . . . . . . . 269
Purpose and Basis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .269
Smelting by the Sinter Plant–Blast Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
Smelting by the Kivcet Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .274
Smelting by the Isasmelt Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .277
Comparison of Smelting Technologies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
Lead Refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .280
Metal Pricing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .284
By-Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .285
Overall Economics for Refined Lead Production . . . . . . . . . . . . . . . . . . . . . . . . 286
Economics of Secondary Lead Production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
Appendix 1 – Properties of Lead and Associated Compounds. . . . . . . . . . . . . . . 293
Lead Metal Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .293
Binary Lead Rich Eutectics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .294
Properties of Lead Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .294
Vapour Pressures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .295
Silver Metal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .295
Thermodynamic Properties of Compounds Involved in Lead Extraction . . . . . . 296
Heat Capacities at Constant Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
xvii
PART A
GENERAL CONTEXT
This part of the text covers the general structure of the lead smelting industry,
including its scope, its history and details of raw material supplies used for
the recovery of lead metal.
Chapter 1 Industry Perspective and Introduction

Chapter 2 Historical Background
Chapter 3 Raw Materials
CHAPTER 1
Industry Perspective and Introduction
INTRODUCTION, PROPERTIES AND USES
Lead is a metal of wide historical significance. It is now a very mature commodity and as such exhibits
declining intensity of use, with broad replacement in many of its traditional uses. Much of the
replacement results from acute awareness of the effects of lead on human health and the environment.
Lead was widely used in ancient times, dating back over 7000 years. It was often mined and
produced as a co-product of silver, which was highly prized for ornamentation and jewellery and later
for coinage. Lead served as a collector for silver and gold and often smelting was conducted primarily
for this purpose. Lead was separated from the precious metals by oxidation in the ‘cupellation process’.
The Phoenicians and later the Romans mined silver and lead in Spain. Lead was mined at Laurium
in ancient Greece and on the islands of Rhodes and Cyprus. The Romans also produced lead in Britain
and in ancient Gaul. In the Middle Ages, silver and lead mining and production flourished at
Rammelsburg, in the Hartz region of Germany, and in the Erzgebirge, and in Upper Silesia. Large
deposits were later found and developed in the New World – in the USA, Mexico and Canada, as well
as in Australia and these deposits represent major supplies of lead today.
In Roman times, lead was used for making water piping, for lining water tanks and baths, as a
roofing material and as a seal for weatherproofing buildings. It was used in soldered lead sheets by the
Assyrians in the Hanging Gardens of Babylon. The Latin word ‘plumbum’ for lead has been
synonymous with the working of lead metal for handling water, hence the trade of ‘plumbing’. Lead’s
low melting point and softness enabled it to be used to seal bronze and iron connectors into building
stone, and this can still be seen in many ancient buildings and ruins today.
It was used for the construction of large windows from smaller fragments of glass at a time before
large-sheet glass production was possible. Stained glass windows still remain as a prominent example
of this art.
Because of its high density and ease of moulding, lead was used as a projectile in warfare, initially
for slingshots and catapults, but following the invention of gunpowder and firearms, was primarily
used for the manufacture of ammunition. The production of lead shot using a high tower to form small
spherical shapes was a significant industry up until the 19th century.
Also due to the ease of moulding, as well as the hardness of its alloy with antimony, lead was used
by Gutenberg in the first printing process for the fabrication of moveable type, and is still the basis of
large-scale printing type setting where this is still used. However, the new technologies of offset and
electronic printing are rapidly replacing this use.
Lead’s oxides as red and white lead were used as paint pigments dating from ancient Egyptian
times until the mid 20th century. They provide good pigment coverage and relatively stable colour,
but have been phased out of use in recent times for health and environmental reasons.
The unique electrochemical properties of lead in combination with its oxides and sulfates
provided a means of constructing high capacity and high powered electrical storage batteries. This
low cost application has developed into the major use for lead today, principally for starting, lighting
and ignition (SLI) power supply in the automotive industry. Traction batteries for fork-lift trucks,
buses and other heavy vehicles are commonly lead-acid. Large installations of lead-acid batteries are
used for standby and uninterruptible power supplies, and for electrical energy storage from renewable
The Extractive Metallurgy of Lead Spectrum Series Volume 15 3

CHAPTER 1 – Industry Perspective and Introduction
energy sources. Because lead in this application remains concentrated and is not dispersed, it can be
readily recovered, making lead the most recycled metal, at around 60 per cent of total world supply.
This has given rise to a major part of the lead smelting industry being structured around secondary
sources of feed.
The use of lead-acid batteries for portable power sources such as power tools has not been high
due to lead’s high density, and alternatives such as nickel-cadmium, nickel-metal-hydride and
lithium-based batteries have predominated, with much higher energy-to-weight ratios. In this regard,
the future trends in electric vehicles are not yet clear, but lead-acid batteries have the advantage of
relatively low cost, with high power delivery.
As a pure metal, lead is soft and malleable with low mechanical strength. This is an advantage in
some applications such as weatherproofing, but one consequence is that under stress the metal will
easily deform to relieve that stress, or ‘creep’, and this can take place over long periods of time.
Indeed, lead can creep under its own weight, and to avoid this effect the safe tensile stress is
1.7 MN/m2 and in compression, 2.75 MN/m2. Lead can be alloyed to improve its strength properties,
and antimony was commonly used as a hardener. Pure lead is in fact rarely used.
The corrosion resistance of lead is due to the formation of dense coherent surface films such as
oxide, carbonate or sulfate. This, coupled with its ability to be alloyed and rolled into sheet, has
enabled lead to be used as a construction material in the chemical industry, particularly in sulfuric,
phosphoric or chromic acid environments. For these applications it was often used as a protective
coating on steel, applied by melting and wiping, or ‘burning’, the lead onto the steel surface.
The high density of lead, and the fact that its oxides will dissolve in glass without causing
colouration, have enabled its use to increase refractive index and form decorative ‘crystal’ glass
products. High quality crystal can contain up to 70 per cent lead and was first introduced in the
17th century.
Many lead compounds have unique properties with corresponding useful applications. The
organo-metallic compound tetraethyl lead has been important as an additive to automotive fuel to
control pre-ignition in the internal combustion engine. It is effective in very small amounts, and the
petrol-driven internal combustion engine and, indeed, the automobile itself, owed much of their early
development to this use. Tetraethyl lead represented a large use of lead in the mid 20th century, but
health and environmental concerns have seen this largely eliminated in the early 21st century.
Lead compounds are also used for a range of plastic stabilisers to overcome the degradation of the
plastic by heat and UV radiation. This is particularly applied to polyvinyl chloride (PVC), where it is
used for construction applications such as house siding, window frames and rainwater products.
Degradation causes decomposition and loss of HCl from the polymer structure, in turn causing
discolouration and brittleness. A number of base metal salts, particularly lead, zinc, tin and cadmium,
are effective in HCl bonding and preventing free HCl formation. The lead salts are usually tri-basic
lead sulfate, phosphate or stearate. There are some legislative requirements that products of this
nature must be recycled because of their lead content.
Other significant uses of lead are for the sheathing of electrical and communication cables, and for
protection against high energy radiation. Its high coefficient of absorption of X-rays and gamma rays
at 0.48 cm-1, combined with the ability to dissolve lead oxides in glass, provided for the construction
of cathode ray tubes for television and computer monitor applications. This has been an important use
for lead, although there is a significant trend to replacement by more compact alternative display
technologies, such as LCD and plasma screens. Apart from addition to glass, radiation shielding in
many forms in the nuclear industry relies on the use of lead.
4 Spectrum Series Volume 15 The Extractive Metallurgy of Lead

A generalised list of the major uses of lead may be given as follows:

• batteries:
• automotive SLI, and
• energy storage,
• sheet for the building industry,
• sheathing of power and telecommunication cables,
• plastic stabiliser chemicals,
• radiation shielding:
• cathode ray tubes, and
• general applications,
• ammunition,
• corrosion protection:
• chemical lead applications,
• glass additive for production of crystal,
• glazes for ceramics,
• colouring pigments for plastics,
• paints:
• both pigment and preservative uses,
• weights,
• sound insulation barriers, and
• automotive fuel additives.
Many old uses of lead such as for ammunition remain, but many have been phased out with the
availability of new materials, and because of the recognition of the health hazards associated with
some of those old uses. Health concerns have also seen lead removed from paints and petrol. Lead
poisoning and its effect on mental health has been known about for many years, and regulations
covering permissible maximum lead levels in the blood of those working with lead have been
introduced and progressively tightened. Children are more susceptible to lead poisoning, and the
effect on childhood mental development has been a significant issue in the formulation of
environmental controls. The ancient practices of using lead in cosmetics and sweetening wine by
storing it in lead containers or adding lead acetate have long been eliminated. These practices have
even been given as a cause for the downfall of the Roman Empire, for the madness of King George III
of England and his subsequent loss of the American colonies. Lead shot in cartridges for hunting
waterfowl has largely been replaced with iron shot because of concerns about the poisoning of birds
from shot ingestion collected with feed from the bottom of waterways. With these health and
environmental pressures, the pattern of lead use has shifted markedly, as illustrated in Table 1.1 which
shows lead end uses for 1960 and for 2005.
Due to environmental and health concerns, the clear general trend is to replace lead in the
dispersive uses and to concentrate its application to uses where it can be recycled. This trend will
necessarily see an increase in the proportion of lead supply derived from secondary processing, and
minimal growth or a decline in the future demand for primary lead.

TABLE 1.1
End uses for lead in 1960 and 2005 (source: Lead Development Association).
End use 1960 2005

Batteries 28% 75%
Pigments and chemicals 10% 8%
Rolled extrusions 16% 6%
Alloys and ammunition 15% 5%
Cable sheathing 18% 2%
Miscellaneous (including tetraethyl lead) 13% 4%
WORLD SUPPLY AND DEMAND

World consumption of lead totalled close to 7 800 000 t in 2005, of which about 3 400 000 t was
derived from mine and primary smelter production. The balance came from secondary production
from recycled scrap products – predominantly batteries.
Total world lead consumption and mine production since 1970 are illustrated in Figure 1.1 and
2005 production figures are given in Table 1.2.
8000
7000
6000
5000
Lead ’000 (t)
4000
3000
2000
1000 Consumption Mine Production
0
1970 1975 1980 1985 1990 1995 2000 2005
Year
FIG 1.1 - Global lead consumption and mine production.
TABLE 1.2
Lead metal and lead mine production for 2005 (source: International Lead Zinc Study Group).
Region Metal (t) Mine (t)

Europe 1 702 000 256 000
Africa 130 000 130 000
America 2 043 000 1 013 000
Asia 3 486 000 1 322 000
Oceania 276 000 715 000
World total 7 636 000 3 436 000

Figure 1.1 shows a slight decline in mine production, although it has been relatively steady over
the past two decades. Mined lead will correspond closely with primary metal production at around
3 300 000 t/a. The gap between mine production and total consumption closely matched the
production of lead from secondary sources, which was 4 200 000 t/a in 2005 and growing significantly.
This increase in secondary lead production matches the increasing proportion of lead being used for
lead-acid batteries.
Primary lead is produced largely from the smelting of lead sulfide (galena). This is often mined in
conjunction with zinc sulfides where both metals are sought. However, the growth in demand for zinc
has outstripped the growth in demand for primary lead and there has been a relative decline in the
mined lead to zinc ratio, to match smelter requirements. The ratio of lead to zinc mined was 0.7 in
1960, declining to 0.5 in 1983 and to 0.32 in 2005.
THE LEAD SMELTING INDUSTRY

The lead smelting industry is divided broadly into primary and secondary smelters, producing a crude
lead bullion, and refineries, removing impurities from the crude bullion to achieve the market grade of
refined lead as set by the London Metal Exchange (LME) or the customer. Refineries may be directly
associated with the smelting operations or may be separate independent operations, taking crude
bullion from the smelters. There are, for instance, large independent refining operations in Japan and
in the UK. Japan, for example, has a surplus of stand-alone refining capacity and has traditionally
purchased bullion. This can be an efficient approach where a primary smelter is located at a mine site
and the refinery is located close to final refined lead markets. Refining of primary bullion is more
complex than for secondary bullion, and most independent refineries have the capability for handling
primary bullion. Secondary refining can be relatively simple with few impurities to remove, and is
usually part of the secondary smelter.
A broad schematic of the structure of the industry is shown in Figure 1.2.
Primary lead production is based on the smelting of lead sulfide concentrates. There is a large
disparity between regional mining and smelting operations and a significant world trade in lead
concentrates. Table 1.3 shows the major lead mining countries and Table 1.4 the major smelting
capacities in 2004.
Primary smelters are often associated with major mining operations, but are usually centrally
located in major industrial centres. Because of the environmental issues associated with lead smelting
sites in the past, it will be very difficult in the future to obtain licences for the construction of new
TABLE 1.3
Major lead mining countries in 2004 (source: Lead Development Association).
Country Mined lead production (tonnes of contained lead)

Australia 654 000
China 618 000
USA 464 000
Peru 308 000
Canada 200 000
Mexico 152 000
Others 804 000
Total 3 200 000

TABLE 1.4
Major lead smelting production in 2004.
Country Total smelter production Production from mined Secondary lead production
(t/a) lead (t/a) (t/a)
China 1 533 000 1 350 000† 183 000
†
USA 1 338 000 290 000 1 048 000

Australia 390 000 365 000 25 000
Japan 375 000 175 000 200 000
Canada 370 000 250 000 120 000
Germany 350 000 75 000 275 000
Kazakhstan 330 000 300 000 30 000
Italy 283 000 130 000 153 000
UK 176 000 0 176 000
Others 1 685 000 135 000 1 540 000
Total 6 820 000 3 070 000 3 750 000
† Estimated.
Mining Scrap
Collection
Ore
Breaking
Mineral
and
Processing
Separation
Zinc and Copper
Concentrates
Tailings Plastics Waste
Lead Concentrate
Residues
Primary Lead Secondary
Smelting Smelting
Slag
Slag Fuming
Sulfuric Acid
Lead Bullion Waste Zinc

Slag Oxide
Lead Bullion
Lead
Refining
Copper Matte Silver and Gold
Antimonial Lead
Refined Lead
FIG 1.2 - Lead extraction industry schematic.

primary lead smelting sites. As a result there have been very few new greenfield primary smelters
constructed in the past 20 to 30 years. This is reinforced by the fact that primary smelting of lead has
been static over that period, so there has been no need for additional capacity. This approach is likely
to continue, and existing primary smelters will tend to be upgraded or replaced with improved
technology at existing sites.
Secondary lead smelting tends to be localised around major population centres and the supply of
waste batteries, due to the relatively high cost associated with the transport of used batteries. The
secondary smelting technologies used are also suited to relatively small-scale operations in
comparison with primary smelters, which can benefit significantly from the economies of scale.
The balance of lead metal flows for the total lead industry is illustrated in Figure 1.3, with the
horizontal width of the bars representing the annual tonnage of metal produced and used. This
illustrates the relatively high level of production by secondary lead recycling in comparison with new
lead from mine production. New lead essentially reports to a growing inventory of lead-acid batteries
and other metal uses, and to losses from the system as dispersive uses. The inventory effect reflects
both the growing demand for batteries and the life of the battery before it is scrapped and recycled.
Lead Residues from

Zinc / Copper Smelting
Mine Production
Scrap Batteries
Secondary Smelting Primary Smelting Recycle

Residues
Lead Metal Produced
Other
Batteries Metal
Uses
RecycleRecycle
Scrap
Batteries Inventory
Growth
Losses Losses
Recycle Metal Scrap
FIG 1.3 - Lead metal cycle.
PRIMARY SMELTING
Primary lead smelting is largely based on the treatment of lead sulfide (galena) concentrates. A
number of processes are used but the traditional sinter plant–blast furnace technology (as illustrated in
Figure 1.4) has predominated.
The sinter plant eliminates sulfur and produces an agglomerated material with lead feed and fluxes
present as oxides, which is subsequently reduced to lead metal in the blast furnace using metallurgical
coke. Crude lead bullion is refined either by the thermal process, which individually separates
impurities, or by the electrorefining process, to give a refined lead with less than 0.01 per cent total
impurities.

Lead concentrates
Recycles Fluxes – silica, lime, ironstone
Gas Sulfuric Acid

Sinter Plant
Cleaning Production
Dusts
Sulfuric acid
Gas
Blast Furnace
Cleaning
Dusts
Slag to waste or fumer
Lead bullion to refinery
FIG 1.4 - Sinter plant–blast furnace flow sheet.
More recent process developments have been applied to direct smelting in which sulfur
elimination and oxide reduction take place in the one unit, enabling the heat of sulfide oxidation to be
utilised, and thus improving the overall thermal efficiency of the process. Direct smelting processes
avoid the use of metallurgical coke as a relatively high cost fuel and reductant. The incentive to
change from the sinter plant–blast furnace technology has also been driven by environmental issues,
since these operations are difficult to contain, and can contribute significant emissions of lead
particulates to the atmosphere.
The major primary lead smelting processes in use are:
• the sinter plant–blast furnace combination (see Chapters 4 and 5),
• the Imperial Smelting Process (also a sinter plant with closed top blast furnace for co-production
of zinc) (see Chapter 6), and
• direct smelting processes (see Chapter 7):
• the Kivcet process,
• the QSL process,
• the ISASMELT and Ausmelt processes,
• the Boliden process, and
• the Kaldo TBRC process.
As indicated in Table 1.4, production of lead from primary sources is of the order of 3 100 000 t/a.
However, the capacity of primary smelters is significantly in excess of this figure, since most primary
smelters also accept varying proportions of secondary materials as part of their feed. These additional
feeds are commonly in the form of lead residues, containing oxide lead as well as sulfates. These
residues may arise from scrap processing or from other metal extraction such as zinc and copper,

which give rise to fumes and leach residue containing high levels of lead. In the latter case, the lead
produced from such materials is still primary lead, but is not accounted for in the statistics for mine
lead production. These materials can represent around ten per cent of total lead output from the sinter
plant, and lead bullion production from the blast furnace can be significantly greater due to direct
feeds to the furnace, particularly if those materials contain metallic lead. It is therefore difficult to
arrive at a figure which truly represents primary lead production capacity; however, it will be of the
order of 4 000 000 t/a (2005). The number of primary smelters listed in 2004 totals 53, and Table 1.5
shows the distribution of the world’s primary lead smelters by the process used.
TABLE 1.5
Distribution of primary smelter capacity by process type in 2004.
Process type Capacity (t/a) Percentage of total Number of smelters

Sinter plant–blast furnace 2 470 000 70% 34
Imperial Smelting Furnace 280 000 8% 8
Kivcet 360 000 10% 3
QSL 270 000 8% 3
Other processes 160 000 4% 5
Total 3 540 000 100% 53
The sinter plant–blast furnace technology represented over 90 per cent of total primary lead capacity
in 1980, so there has been a significant replacement of that technology. There has been virtually no
additional primary capacity in that period, hence there has been a net closure of blast furnaces and the
remaining plants are relatively old. It is likely that there will need to be progressive closures of
sintering–blast furnace operations and replacement by direct smelting technologies in the future.
The capacity distribution of primary smelting capacity is shown in Figure 1.5. The vertical axis
represents cumulative capacity of plants above a given plant size, as given by the horizontal axis.
Figure 1.5 indicates that almost half of the primary production capacity (or 1 750 000 t), is
attributed to plants above 100 000 t/a, and 80 per cent of the primary production capacity (or
2 800 000 t) is attributed to plants above 50 000 t/a capacity, of which there are only 25 presently
operating, as detailed in Table 1.6. Of those 25, three use the Kivcet process, three use the QSL
4000
Cumulative Capacity Above ’000 (t/a)
3500
3000
2500
2000
1500
1000
500
0
0 50 100 150 200 250
Smelter Capacity ’000 (t/a)
FIG 1.5 - Distribution of world primary lead smelter capacity.

process, one uses Kaldo and two Ausmelt technology. The remaining 16 use sinter plant–blast
furnace. The average primary smelter capacity is 67 000 t/a of lead bullion, whereas the median
capacity is 50 000 t/a.
TABLE 1.6
Major primary lead smelters in 2004 (capacity over 50 000 t/a).
Region, country and company name Location Process Annual capacity (t)
Europe
Belgium
Umicore Hoboken S-BF 125 000
France
Metaleurop Noyelles Godault S-BF 110 000
Germany
Berzelius Stolberg Binsfeldhammer QSL 100 000
Metaleurop Weser Blei Nordenham Ausmelt 90 000
Italy Porto Vesme Kivcet 100 000
Eniresorse
Kazakhstan
Kazpolymetal Ust Kamenogorsk Kivcet 140 000
Chimkent S-BF 160 000
Serbia
Trepca Kosovska Mitrovica S-BF 125 000
Sweden
Boliden Mineral AB Ronnskar Kaldo 55 000
Americas
USA
Doe Run Herculaneum S-BF 205 000
Doe Run Glover S-BF 95 000
Canada
Teck-Cominco Trail, BC Kivcet 120 000
Brunswick M&S Co Belledune S-BF 108 000
Mexico
Met Mex Penoles Torreon S-BF 180 000
Peru
Centromin La Oroya S-BF 93 000
Asia and Oceania
China
Zhouzhou Smelter Zhouzhou S-BF 100 000
Baiyin Northwest Smelter Baiyin (Gansu) QSL 52 000
Fankou Mine Fankou (Guandong) S-BF 60 000
Shenyang Smelter Shenyang (Liaoning) S-BF 70 000
India
Hindustan Zinc Chanderiya (Rajasthan) Ausmelt 50 000
Japan
Toho Zinc Co Chigirishima S-BF 90 000
South Korea
Korea Zinc Co Onsan QSL 120 000
North Korea
Korea Metals and Chemicals Mumpyong S-BF 90 000
Australia
Nyrstar Port Pirie S-BF 220 000
Xstrata Zinc Mount Isa S-BF 150 000

Refining is a significant and separate part of primary lead smelting, and two different approaches are
used involving pyrometallurgical separation processes or electrorefining. Pyrometallurgical methods
involve the oxidation of selected impurities from molten lead bullion for collection as a slag or dross, or
the precipitation of impurities to form a dross or crust by the addition of reagents and/or by changes in
temperature. A number of steps are usually applied for removal of copper, arsenic and antimony, silver
and precious metals, zinc, then bismuth, and finally, residual minor impurities and drossing reagents by
treatment with caustic soda. Operations are usually conducted in externally heated crucibles or ‘kettles’,
holding between 100 and 300 t of molten lead.
A significant part of the refining operation involves the recovery of by-products, particularly the
precious metals silver and gold.
Electrorefining involves the transfer of lead from an impure anode sheet, through an electrolyte to
a high purity lead cathode. Crude bullion, after copper, arsenic and antimony removal, is cast into
anodes, which are placed in tank cells. The electrolyte commonly used in the Betts Process is a
solution of lead fluorosilicate and free fluorosilicic acid. Lead is deposited on lead starter sheets,
which are removed from the cells and melted to high purity refined lead. Impurities are contained in
the anode slimes and are collected and processed by pyrometallurgical methods for recovery of
precious metals, bismuth and copper.
SECONDARY LEAD PRODUCTION

Secondary lead is primarily sourced from scrap lead-acid batteries but also processed scrap metallics
such as sheet and pipe. Secondary operations are characterised by relatively small plants in comparison
with primary smelters, and are sized to handle scrap availability within a local area. This is determined
by the economics of scrap battery collection and transport to the secondary operation, and it follows that
the largest secondary plants are located in the high vehicle density areas of the USA.
The first step in secondary lead processing is the breaking and separation of scrap batteries. In this
step, batteries are shredded or disintegrated, then the battery components are separated by physical
methods into metallic components, pastes containing lead oxides and sulfate, plastics from battery
cases and plate separators, and waste battery acid, which is usually neutralised with lime to form
gypsum. Polypropylene recovered from cases is a valuable material and can be recycled for reuse.
The metallic components may be simply melted to recover lead, largely contaminated with antimony,
but the battery pastes are treated in a smelting process in which they are reduced, using a carbon-based
fuel, to lead bullion and a waste slag. Processes used for secondary smelting include the following:
• blast furnace,
• reverberatory furnace,
• short rotary furnace,
• rotary kiln,
• submerged lance slag bath reactor (eg Isasmelt or Ausmelt Processes),
• electric furnaces, and
• leaching and electrowinning processes.
Some refining of secondary bullion is required for the removal of antimony, arsenic, copper and
tin. This is usually done in kettles using standard pyrometallurgical refining techniques, but is far less
extensive than for primary lead.

Secondary lead is recovered either as ‘soft lead’ or as ‘hard’ or antimonial lead. The metallic
components of automobile batteries such as plate grids and posts may be made from antimonial lead
alloys containing up to ten per cent antimony, but usually less than three per cent. This provides the
source of antimony in secondary lead, but it can be controlled to some extent by separately processing
metallics and non-metallic scrap. There is a trend to the use of calcium lead alloys in place of
antimony for sealed batteries, which significantly reduces the quantity of antimonial lead produced by
secondary smelters.
4000
Cumulative Capacity Above ’000 (t/a)
3500
3000
2500
2000
1500
1000
500
0
0 20 40 60 80 100 120 140
Capacity ’000 (t/a)
FIG 1.6 - Distribution of world secondary lead smelter capacity.
100
Primary
90
Secondary
80
70
Number of Plants
60
50
40
30
20
10
0
0 to 20 to 40 to 60 to 80 to 100 to 120 to 140 to 160 to 180 to 200 to
20 40 60 80 100 120 140 160 180 200 220
Capacity Range ’000 (t/a)
FIG 1.7 - World lead smelters – size distribution.

There are around 150 secondary smelters worldwide with a median capacity of 15 000 t/a of lead,
although there are many small plants and the first quartile size is 6000 t/a. Figure 1.6 shows the
distribution of world secondary capacity as the cumulative capacity above a given plant size, and
compares with Figure 1.5 covering primary smelters. Clearly secondary smelters are much smaller
than primary smelters.
The number of primary and secondary smelters within a given size range is illustrated in
Figure 1.7, which shows the significant difference in numbers and in plant capacities. The scale of
these plants also has an impact on the technologies used for secondary smelting in comparison with
primary smelting, and the most common approach is the use of the short rotary furnace.
REFERENCES AND FURTHER READING

Henstock, M E, 1996. The Recycling of Non-Ferrous Metals, 342 p (International Council on Metals and the
Environment: Ottawa).
International Lead Association website, <http://www.ila-lead.org>.
International Lead Association Europe website, <http://www.ila-europe.org>.
Lead Development Association International website, <http://www.ldaint.org>.
Siegmund, A H J, 2000. Primary lead production – A survey of existing smelters and refineries, in Proceedings
Lead-Zinc 2000, pp 55-116 (The Minerals, Metals and Materials Society: Warrendale).

CHAPTER 2
Historical Background
As already discussed, lead has been used by humans for over 7000 years. Lead oxides were used as
pigments in ancient Egypt and also as glazes for pottery, and objects made of the metal have been
found dating from 3800 BC. The Chinese used lead coinage dating back to 2000 BC. Lead sheet was
reportedly used in the construction of the Hanging Gardens of Babylon, and it is known that lead was
used at that time for embedding bronze and iron connection brackets into stone blocks used in
construction. It was extensively used by the Romans in building construction, for water pipes, for
coinage and in warfare. The Romans were also familiar with lead-tin alloys for use as solder.
Mining of lead ores is recorded at Mount Laurion in Greece in the fifth century BC. It was mined
by the Phoenicians in Spain and later by the Romans in the Rio Tinto region, as well as in Derbyshire
in Great Britain and widely throughout Europe, but particularly in Silesia, Bohemia and the Hartz
Mountain area of Germany.
The history of lead is also inextricably linked with the mining and recovery of silver, which was
produced for its value as a currency of trade, as well as a precious metal for the manufacture of
jewellery and artefacts. Because of lead’s association with silver and its potential use for degrading
silver coinage, lead mining and smelting operations were often closely controlled by the application
of strict laws.
LEAD PRODUCTION IN EARLY TIMES
Lead can be reduced from its oxide at relatively low temperatures compared with other metals, and
the use of a wood fire is sufficient to produce lead metal. Early lead smelting methods used a stack
of wood and ore piled in a hollow or ‘bole’ on the side of a hill crest to utilise strong winds to
intensify the fire. In Britain these smelting sites were known as ‘bolehill’ or ‘bloomery’ sites, and
were common for metal smelting in general. A small retaining wall could be built around the base to
retain a bed of coals and provide a reducing zone. Channels allowed molten lead to run out from the
furnace.
The next development was the application of hand, or foot, operated bellows to provide an air blast
to the hearth, which enabled the smelting site to be more conveniently located near ore supplies. The
furnace was constructed as a short, square shaft with a bottom opening for the bellows and to allow
metal and slag to run out. The shaft was packed with charcoal and ore. An example of this type of
furnace is the Catalan Forge, introduced in Spain about 700 AD.
These furnaces were primarily used for iron production and evolved into the blast furnace in time.
The furnaces in use for general smelting applications in the 1500s, including lead and silver, have
been described by Agricola, in the first detailed descriptions of smelting practices up to that time.
(Agricola, 1950). The furnace was typically a rectangular shaft 370 mm wide by 460 mm deep and
1500 mm high, equipped with a single tuyere through the rear wall close to the hearth, and operated by
bellows. It was constructed of stone for the rear and side walls, with brick for the front wall. The
hearth was made of rammed clay mixed with powdered charcoal. A number of furnaces were
constructed against a large stone wall, behind which were located a series of bellows – one for each
furnace – operated by a shaft linked to a water wheel. Figure 2.1 gives an illustration taken from De Re
Metallica (Agricola, 1950).

CHAPTER 2 – Historical Background
FIG 2.1 - Medieval smelting furnaces (from Agricola, 1950).
The medieval furnaces operated on charcoal, but wood was also used when smelting lead ores,
which was the simplest of the various smelting operations for which the furnaces were employed. For
the smelting of silver and gold ores, lead was also added to the furnace and to the forehearth, as a
solvent for the precious metals. Production of slags and matte were also common with precious metal
smelting and there was considerable recycling and reworking of these materials.
The furnace generally operated only for a few days and was then cleared of accretions and the
walls were replastered with ‘lute’, a paste of clay and fine charcoal. The skill of the furnace operator
was most important in regulating the air blast from the bellows and in the placement of the ore charge
towards the front of the shaft so as to avoid the formation of a sintered mass or ‘sow’. Natural fluxing
materials such as fluorspar were often also added to the charge depending on the nature of the ore.
In the 16th century, lead smelting tended to develop towards the use of a shallower hearth akin to
the blacksmith’s forge, with rear fixed tuyeres blown by bellows that were driven by water power, and
a mix of selected lump lead ore or concentrate and charcoal was piled on the hearth and hand rabbled.
Crushing and simple gravity or hand-sorting of ores was becoming more common at this time.
Hearths of this type were the Scotch hearth, as shown in Figure 2.2, and the Moffat ore hearth. Early
hearth dimensions were 0.6 to 0.9 m2, with a central depression of around 100 mm deep to retain lead.

To Chimney
Charge Door
Charge and Fuel Bed
Tuyere
Lead Pot
Lead Pool in
Hearth
Air Blast
FIG 2.2 - Schematic of the Scotch hearth furnace.
The hearth was started with a charcoal fire, onto which lead ore was added with more fuel. The
charge was worked by hand-stirring with iron tools. Lump material was removed onto the front
working stone, was broken to allow oxidation and then pushed back onto the heap. The basin in the
hearth filled with molten lead, which then overflowed into a cast iron collection pot located at the
front of the hearth. Lime was added at around one to 1.5 per cent of the ore charge to cover the molten
lead and enhance the formation of a crumbly slag, which allowed good blast penetration and sulfur
removal. The temperature was kept as low as practical to maintain this slag regime and to minimise
lead fuming. A lumpy slag was removed periodically and generally reported around 20 per cent lead.
The high lead slag was stockpiled and, with improved smelting techniques, many of these old hearth
slags were reworked to recover additional lead.
The hearth furnace required lump material of high lead grade to avoid excessive dusting and
fuming, and to minimise slag formation and loss of lead in that slag. It was consequently favoured by
early lead smelting operations in the Mississippi Valley with clean high-grade galena ore. At these
sites a water-jacketed version was developed, constructed of water-cooled cast iron panels in a
U-configuration on the long axis, and termed the ‘American Water Backed Hearth’. A later
development favoured by the Missouri lead producers was the Newman Hearth, a mechanically
rabbled version of this technique. An eight foot (2400 mm) long by 20 inch (203 mm) wide hearth
containing an eight inch deep bed could produce three tons of lead in eight hours from high-grade
concentrates. The mechanical version relieved the smelterman of the laborious task of constantly
hand-rabbling the charge to break up accretions and ‘sows’, with exposure to heat and fumes.

The copious fume emissions from these furnaces and the need to process finer ores eventually
favoured the use of the reverberatory style hearth furnace, which did not require the use of bellows
and is illustrated in cross-section in Figure 2.3. These furnaces probably evolved from the open oven
style hearth furnaces used at Carni in Austria, and the Saxon furnaces, which resembled baking ovens.
Filling port
Firebox
Flue
Hearth
Tap hole
FIG 2.3 - Reverberatory lead furnace.
For the standard reverberatory furnace, a batch of galena was added to the furnace hearth and was
roasted with hand-rabbling for about two hours, in which time part of the lead sulfide was directly
oxidised to lead sulfate. The resulting mixture of lead sulfate and unreacted lead sulfide was
thoroughly mixed and the temperature of the furnace was increased. This allowed the ‘roast reaction’,
as given in Equation 2.1, to take place, with copious emission of sulfur dioxide:
PbSO4 + 2PbS = 3Pb + 2SO2 (2.1)
Any silica in the concentrate tended to react with lead oxide (PbO) to form lead silicate, and in the
final stage of the process lime was added to the furnace charge and mixed in with the slag and
unreacted ore, for the purpose of decomposing the lead silicate in accordance with Equation 2.2:
2PbSiO3 + 2CaO + C = 2CaSiO3 + CO2 + 2Pb (2.2)
Following this step, molten lead bullion was tapped from the base of the furnace hearth as a crude
impure or ‘hard’ lead.
In some operations, particularly for those processing lump feed, the roast-reduction cycle was
repeated a number of times, with the temperature raised for each cycle. In this situation silver tended
to concentrate in the first run lead bullion, and could be four times the silver content of the final lead
run. This was a useful approach to handling high silver ores, so as to reduce the effort required in
silver recovery by the Pattinson Process or by cupellation.
The earliest reverberatory hearths were introduced around 1720 in Silesia and England. Early
types were the Corinthian furnace, the English or Flintshire furnace and the Silesian furnace. Silesian
furnaces used in Germany were up to 25 foot (7600 mm) long by 8 foot (2400 mm) wide, with five
working doors in each side. Labour requirements were 15 to 20 man hours per tonne of lead produced,
with coal consumption close to 0.8 tonnes per tonne of lead produced.

In later practice during the 1800s two hearth furnaces were commonly used: one for calcining with
gases going to a chamber-type sulfuric acid plant, and the second or ‘flowing’ furnace operating at a
higher temperature, in which calcined material and coke were melted with the addition of lime and
fluorspar to produce a fluid slag. Often pig iron or scrap iron was also added as a reductant. As well as
lead bullion and a low lead slag, matte (or ‘regulus’) was also produced and could contain significant
amounts of lead. The matte was reworked by calcining and returned to the reduction furnace, thus
producing a second matte enriched in copper. Matte could be recycled a number of times.
The above smelting operation still resulted in a significant amount of lead being volatilised,
forming a fume in the exit gases from the furnace, probably rich in toxic elements such as arsenic, as
well as sulfur dioxide. This caused the destruction of vegetation around the smelting operation, and
the poisoning of farm animals and cattle feeding nearby. To reduce this effect, long horizontal flues
up to 1.5 km in length were constructed from the furnace to the final vent stack, allowing the bulk of
the fume to settle out onto the walls and base of the flue. Collected fume contained of the order of
33 per cent lead and was recycled. Collection methods were improved by the addition of drop-out or
condensing chambers immediately following the smelting furnace, which were introduced in England
around 1780.
The crude bullion from the smelting furnace was allowed to oxidise in shallow open pans and the
dross skimmed from the top removed arsenic and antimony, ‘softening’ the resulting lead metal.
The use of iron metal additions to reduce galena or lead oxide was first noted in India in the
14th century. In this method, iron was combined with lead sulfide to form metallic lead and an iron
matte as in Equation 2.3, thus limiting the formation and emission of SO 2 (Dube, 2006):
PbS + Fe = FeS + Pb (2.3)
Lead ore, charcoal and iron were placed in crucibles within a furnace and later removed to separate
and recover the lead. In the late 18th century in Europe, iron reduction was applied with the addition
of high-grade lump ore, charcoal and iron to a small shaft furnace. Iron use was around 12 to
15 per cent of the ore charge. This practice first appeared in Claustal in the Upper Hartz region and
later at Tarnowitz in Silesia and Przibram in Bohemia.
The use of iron for lead reduction also occurred in Japan, but using an open pan hearth filled with
burning charcoal into which lead ore and pig iron were charged. Iron use was two to three times higher
than reported in European practice.
THE LEAD BLAST FURNACE

The hearth furnace processes described above were only efficient for the smelting of lump high-grade
ores with low levels of associated ‘earthy materials’ such as silica and iron minerals, as well as zinc.
To handle lower grade materials it was preferable to use a higher temperature process and produce a
molten slag containing the gangue minerals, and hence the blast furnace was applied.
The blast furnace for the production of iron had evolved from the early charcoal, fuelled hearth
and shaft furnaces blown by water-powered bellows. Coke was first used by Abraham Derby at
Coalbrook Dale, in England in 1713, and with the invention of the steam engine and its use for
operating blowing engines, together with the development of the hot blast by Neilson in Glasgow in
1830, the iron blast furnace was well established by the mid 19th century. Furnaces were originally
constructed from massive sandstone blocks bound with iron straps. Later, thin steel shell construction
was used lined with refractory brick.

Early shaft furnaces for lead were used in Freiberg and in the Harz region in Germany. These
evolved from the earlier hearths, using a rectangular cross-section with one tuyere at the back of the
furnace facing a tapping access at the front. This developed into a horseshoe shape with a number of
tuyeres and finally into a circular shaft. The Castilian furnace from Spain was an example of the early
circular shaft furnaces for lead. It was constructed of sandstone blocks and is shown in Figure 2.4.
Flue
Charging Ports
Sandstone Block Shaft
Tuyeres (5)
Lead Pot
Slag Car
Rammed Hearth
FIG 2.4 - Castilian blast furnace.
Later furnaces, such as the Lower Harz furnace, the Claustal furnace and the Przibram furnace
(small versions of an iron blast furnace), were of brick construction. In 1863 the Pilz furnace in
Germany introduced water-cooled cast iron plates at the base of the furnace in the tuyere zone. This
was followed in 1891 by the American Water Jacketed furnace, at Great Falls in Montana, and the
Globe smelter furnace at Denver, Colorado. Water jackets contributed significant benefits by
enabling rapid repairs and much longer operating campaigns, due to the reduction in accretion
formation in critical narrow areas of the furnace. With the adoption of water jackets, furnace design
tended to move from circular to rectangular cross-section for construction simplicity, also allowing
significant increases in productivity from each furnace. The Rochette furnace used at the Atenau
smelter near Claustal in the Upper Hartz region introduced the concept of a long rectangular hearth,
with rows of tuyeres on each of the long sides and tap holes at each end. The main driver for this
change was the realisation that blast penetration from the tuyeres was a limiting factor; the only way to
get higher production was therefore to retain optimum width for this purpose and to make the furnace
longer. Around the end of the 19th century large furnaces were 36 inches wide (914 mm) × 108 inches
long (2740 mm) at the tuyere level (2.5 m 2 hearth area), and around 16 ft high (4870 mm).

With the use of higher blast pressures at the Port Pirie smelter, blast penetration at the base of the
furnace was increased to an optimum width of around 1200 mm. Capacity was further increased by
extending the length of the furnace, but this reached limits at around 7.5 m, set by the ability to tap slag
from one end. By tapping slag at both ends or from the centre, the length could be extended to around
11 m, giving a hearth area of around 13 m 2, which is similar to the typical lead blast furnace today.
Although the width at the base of the furnace was limited to achieve blast penetration, narrow
shafts permitted shaft accretions to readily bridge across and block the furnace. This was corrected by
expanding the width of the furnace above the tuyeres using a short sloping section or ‘bosh’, with
either a tapered or straight upper shaft. In the early 1900s the upper limit to the furnace width was
around 2000 mm. In 1935 Port Pirie further extended the width at the tuyeres to 1524 mm and added a
‘chair jacket’ and a second upper row of tuyeres with a width of 3048 mm. Further, in 1940 the
formation of accretions was minimised by extending the water jackets to the full height of the furnace.
This design evolved to the largest lead blast furnace currently in operation. The Port Pirie blast
furnace is shown in Figure 5.6 (Chapter 5).
The use of oxygen enrichment of blast air has also enabled the capacity of the blast furnace to be
further increased, and is applied in most operations.
Details of blast furnace performance and operation are covered in Chapter 5.
In 1960 the first standard commercial scale Imperial Smelting Furnace (ISF) was constructed at
Swansea in the UK, as an adaptation of the lead blast furnace, to simultaneously produce zinc and
lead. The furnace operated with a hot top to retain zinc in the vapour phase. The top was sealed and
gases passed through a lead splash condenser to strip zinc from the gas phase into a lead-zinc bullion
which could be cooled for separation of crude zinc and lead metals. The ratio of zinc to lead
production from these units is generally more than 2:1, and lead production from the standard unit is
close to 40 000 t/a. Thirteen plants were constructed around the world but due to unfavourable
economics a number of these have now closed. Details are given in Chapter 6.
PREPARATION OF BLAST FURNACE FEED

Originally, lump sulfide ores were fed to the blast furnace, but this tended to produce large quantities
of matte, requiring appropriate levels of iron flux to form the matte. Silica fluxing was also important
to displace lead from sulfates and to form a slag. Limits on the input of sulfur due to excessive matte
formation were generally around 15 per cent in the feed material. Speiss (an iron-arsenic-antimony
intermetallic) was often also present as a separate phase.
For lower grade ores with higher sulfur contents, and for ores with high arsenic content, it was
necessary to eliminate these elements by roasting prior to feeding to the blast furnace. Early roasting
was done in open heaps over fuel beds with a tunnel beneath to supply combustion air. This was
applied at Broken Hill, Australia for the sintering of lead slimes, which were formed into bricks and
dried, and then stacked in an open heap over a fuel bed and burned for ten to 15 days. The resulting
material was sintered and quite suitable as blast furnace feed.
Open compartmented pads or stalls were also used, often venting to a central collection flue for
combustion gases. However, roasting at low temperatures produced fine calcines, which were not a
practical feed for the blast furnace, and higher temperature roasting to melt or sinter the material was
necessary, so that lump material could be produced. To effectively achieve this, roasting furnaces
were developed in the form of reverberatory hearths, and were introduced around 1790. Typical
roasting furnaces were up to 5 m wide and 20 m long, with a fire at one end and exhaust flue at the
other end. A series of doors along the side of the furnace allowed access for hand-raking and

movement of material along the length of the furnace from the cold feed end. Lead concentrate and
ironstone, lime and silica fluxes were fed at the cold end. The hot end of the hearth, near the fire,
contained a depression or sump called the ‘fuse box’ where the calcine melted and from where it was
manually scrapped out into slag pots. The slag was cooled and solidified, and then broken into lump
material suitable for blast furnace feed. A typical roaster of the size indicated would process 5 t/d of
lead feed using three men per shift and consuming 3 t/d of coal.
At the Pontgibaud smelter in France, a reverberatory hearth was used for batch calcining, followed
by elevation in furnace temperature to cause surface melting and sintering of the calcine into an
agglomerated mass, rather than complete melting of the charge. This was withdrawn from the
furnace, cooled and broken into lump for blast furnace feed.
In order to improve the intensity and efficiency of the roasting process, the Huntington-Heberlein
process was introduced in the 1890s. Partly roasted material from the hearth roaster was moistened
and placed in a pot fitted with a lower grate (or converter), with a layer of hot material on the grate, and
was subjected to an air blast. The construction of the roasting pot or converter is shown in Figure 2.5.
Hood
Trunnions
Grate
Air Blast
FIG 2.5 - Sintering pot (or converter).
These converters could be considered the forerunners of today’s updraft sintering machines.
However, they had serious deficiencies: they were batch operations, they generated much fume, and
the work of manually handling and breaking the sintered material from the pots was laborious and
unhealthy.
This approach significantly improved the productivity of both the roasting operation and the blast
furnace, and lead smelters in the early 1900s had large numbers of converters producing blast furnace
feed.

Alternative processes at the time were the Bradford-Carmichael process, in which lead ore was
mixed with dehydrated gypsum (plaster) as a binder, was formed into lumps and then processed in the
converter, the Savelsberg Process, which fired ore and limestone over a fuel bed in a converter to
produce a sintered material as blast furnace feed.
A circular rotating furnace using a downward blast through a bed of ore and limestone, covered
with a surface layer of wood chips as a starting fuel, was developed by the Cerro de Pasco Corporation
in Peru to provide a suitable sintered blast furnace feed.
The major advance to overcome the disadvantages of the pot roasting methods came with
Dwight-Lloyd sintering machine. Originally this consisted of a series of boxes with an open grate
base, running on rails over a suction box. The boxes or ‘pallets’ were firstly pushed through a small
reverberatory furnace to ignite the top surface of the charge in each pallet box, and then continued
over the suction box until combustion was completed. The pallets were inverted to empty the contents
and were returned to the beginning of the process. The principle was extended to the development of
the standard downdraft sinter machine around 1910 and later to the updraft machine in 1955. Details
of current sintering processes are covered in Chapter 4.
BLAST FURNACE PRODUCTS

Early blast furnace operations processing lead ores or concentrates from hand-sorting or gravity
separation methods had to contend with much higher levels of impurity metals than later operations
processing flotation concentrates. In particular, blast furnace feed contained high levels of sulfur,
iron, arsenic, copper and zinc. As well as bullion and slag, the blast furnace produced significant
quantities of matte and speiss, and the presence of zinc created significant problems with furnace
accretions and high slag viscosities.
As well as containing iron at around 40 to 45 per cent, matte contained about 12 per cent lead, most
of the copper from blast furnace feed, about half the zinc and a substantial proportion of the silver.
Matte was initially roasted in open heaps or stalls to remove sulfur and was then recycled to the blast
furnace, but later reverberatory roasting furnaces were used. A shaft kiln was used at the Harz smelter
in Germany.
The recycle of roasted matte to the blast furnace resulted in the progressive enrichment of the
copper content of matte, until it reached a grade where it could be processed to blister copper in a
converter. Table 2.1 shows the composition of matte produced after five recycling stages from a
smelting operation around the 1890s (Hoffman, 1899).
TABLE 2.1
Progressive matte enrichment.
Matte production cycle 1 2 3 4 5

Lead content (%) 13.5 8.3 10.0 9.0 9.0
Iron content (%) 48 44 31 20 12
Copper content (%) 5.7 12.8 27.8 42.9 50.9
Sulfur content (%) 25 20 21 18 21
Zinc proved to be a particularly troublesome problem and many techniques were developed to
remove zinc from blast furnace feed. Mineral separation techniques using gravity had limited
effectiveness for some ores, and in particular cases it was necessary to leach zinc from roasted ores

either using water after low temperature sulfation roasting, using dilute sulfuric acid to extract zinc
sulfate, or water and SO2 to remove zinc as a sulfite. The development of practical froth flotation from
around 1913 substantially improved the separation of zinc and lead sulfides and presented cleaner
lead concentrates to the lead smelters. This also increased the fineness of concentrates and
necessitated the introduction of sintering methods for blast furnace feed preparation.
Speiss was the other significant blast furnace product from earlier smelting operations. It
contained significant amounts of entrained particulate lead as well as silver and gold. Speiss was often
roasted in heaps or a calcining furnace and recycled to the blast furnace. At the Trail smelter in Canada
it was treated in a bottom blown converter with the addition of molten lead. The lead captured most of
the silver and gold and no doubt significant amounts of arsenic were volatilised into the gas stream.
LEAD REFINING
Simple cooling of the lead bullion from the smelting furnace initially allowed the separation of a black
dross containing most of the dissolved zinc, iron, tin and oxygen in hot furnace bullion. This dross
could be skimmed off and worked up if the tin content was high enough. With further cooling, much
of the copper and sulfur content came out of solution forming copper-rich crusts. The process was
termed ‘copper drossing’.
In early lead-refining practices, further purification firstly involved the oxidation of bullion in
shallow open pans. The dross formed contained antimony and arsenic and was skimmed off until the
lead was ‘softened’. Oxidation softening in a reverberatory furnace was practised in the mid 1800s
and was developed into a continuous operation in the early 1900s. The alternative Harris Process, for
removal of arsenic, antimony and tin by the addition of caustic soda and sodium nitrate, was
introduced in 1920.
Separation of low levels of silver was not practised until the development of the Pattinson Process
in 1829 as detailed in the next section. The Parkes Process for silver and gold removal by zinc addition
was introduced in 1872.
Remaining copper and other impurities were originally removed by the addition of zinc, and the
removal of zinc was by chlorine to form a zinc chloride dross or by drossing with caustic soda.
Vacuum dezincing of lead was developed as a practical technique in 1946.
‘Fine’ copper removal by sulfur drossing was developed in 1923.
Bismuth became a significant issue as the uses of lead became more demanding and was the prime
reason for development of the Betts Electrolytic refining process in 1902. The alternative Kroll-
Betterton process involving the use of calcium and magnesium metal additions was introduced in 1936.
Details of thermal refining practices are covered in Chapter 12 and electrolytic refining in
Chapter 13.
SILVER RECOVERY
From early times silver was an important source of wealth, but particularly so during the Middle Ages
in Europe. Many early lead smelting operations were for the prime purpose of recovering silver, and
lead could be regarded as a collector for silver and as a by-product. Extensive mining of silver with
co-product copper and lead occurred throughout central Europe, notably in Austria, Saxony and the
Harz district of northern Germany. Most silver ores are sulfides and contain argentite or silver glance
(Ag2S), although there are also many complex mixed sulfides with antimony, arsenic, copper and
lead. In general these minerals occur with lead sulfide or galena and with copper sulfide ores.

Up to the Middle Ages silver rich ores were smelted with charcoal in hearth or shaft furnaces as
previously described, usually with the addition of lead and the use of a lead pool in the forehearth to
collect a lead-silver alloy. Silver was then separated from the lead by cupellation.
The cupellation process involved blowing air over a crucible or pan containing molten alloy on a bed
of bone ashes, so as to oxidise the lead to molten litharge. The bone ashes absorb the molten litharge, but
surface tension effects cause rejection of the residual silver, which remains as a pool of metal on the
surface. This procedure was probably known as far back as 2500 BC, and is mentioned in a number of
places in the Old Testament. It is also well accounted for in descriptions of the Mount Laurion Mines in
Attica, Greece, which provided much of the wealth of the city state of Athens around 500 BC. Mount
Laurion ores contained 40 to 90 ounces (or 1.2 to 2.8 kg) of silver per tonne of lead. The litharge
produced by cupellation was known as ‘spuma argenti’ and could be re-smelted back to lead metal.
Although normal lead bullion usually contained varying but relatively small amounts of silver, it was
not until the development of a process for the desilverising of lead by Pattinson in 1829 that silver could
be produced from ores containing relatively small quantities, such as the ores from Great Britain.
The separation of silver by the Pattinson process used fractional crystallisation, in which molten
lead was cooled and partly solidified in a pan while being briskly stirred. The solid lead crystals were
relatively pure, leaving silver in the remaining liquid. A row of about nine pans were used, each
heated by a fire from below. Crude bullion from the smelter was fed to the middle pan, from which
solid crystals were transferred to the first pan on one side and the remaining liquid to the first pan on
the other side. This process was repeated from one pan to the next up and down the line to give a
purified lead with low silver content at one end and a residual liquid of around 9 kg of silver per tonne
at the other end. The silver rich lead was subjected to cupellation to recover a silver bullion. Today,
precious metals are separated from lead bullion using the Parkes Process, following the removal of
copper, arsenic and antimony. In this process, zinc is added and the lead bullion is cooled to
precipitate a zinc-silver alloy, which is removed and separately treated.
DIRECT SMELTING
Up until the 1980s, the sinter plant–blast furnace technology was almost exclusively used for the
production of primary lead. The early exception was the Boliden electric furnace process from the
1950s, and the Boliden Kaldo or top-blown rotary converter in the 1970s. Major effort was
concentrated in the l970s and 1980s on alternative smelting processes to achieve sulfide oxidation
directly to lead bullion without full oxidation, to lead oxide, followed by reduction of the lead oxide to
metal. The aim was not only to reduce overall energy consumption and the use of coke as a costly
reducing agent, but also to address growing attention to occupational health and environmental issues
associated with the older technologies. This could be achieved by full enclosure of processes and
reduction in the volume of gases produced by more intensive smelting using high levels of oxygen
enrichment. As a result, the Kivcet flash smelting process, the QSL process and the Sirosmelt
top-submerged lance slag bath process (as Isasmelt and Ausmelt processes) were all developed at this
time and are detailed in Chapter 7.
With direct smelting from sulfide to lead metal, involving partial oxidation in a single stage, it is
not possible to achieve good lead recovery with high sulfur elimination and low lead levels in slag.
Hence, most processes involve a two-stage sequence of oxidation, followed by reduction of the lead
oxide so formed to lead metal. Conducting these steps within the same piece of equipment can enable
the excess heat generated by oxidation to be used in the reduction stage, and hence greatly improve the
thermal efficiency of the smelting operation.

Copper smelting in the Balkans

Neolithic Age Lead metal produced in Egypt
Silver recovered by cupellation
Egyptian Kingdoms
Bronze Age
Hellenistic Period Bolehill lead smelters

0 Ore concentration by water washing
Iron Age Roman Empire
Catalan Forge for lead smelting
Medieval World Iron blast furnace

Stamp mills for ore crushing
Renaissance Hearth smelters for lead
Europe
1713 Use of coke for iron smelting
Industrial 1720 Reverberatory hearth smelter for lead

Revolution 1778 Fume collection from smelter gases
1790 Roasting of lead ores in a hearth furnace
1829 Pattinson silver removal process

Industrial Age 1863 Water jacketed blast furnace
1872 Parkes process for silver removal
1895 Sintering pots in use
1900 AD 1902 Betts electrolytic lead refining
1910 Dwight Lloyd sintering machine
World War I
1920 Harris process for arsenic /antimony removal
1923 Copper removal by sulfur addition
1935 Full water jacketed blast furnace
World War 2 1936 Kroll Bretterton process for bismuth removal

1946 Vacuum dezincing process
1953 Boliden electric furnace lead process
1955 Updraft sintering machine
1976 Kaldo lead smelting process
1978 Kivcet process development
1980 Isasmelt lead process
1984 QSL process
Electronic Age 1990s Electrowinning processes
FIG 2.6 - Key technology milestones.
SECONDARY LEAD
Until the widespread use of the lead-acid battery, metallic lead scrap was originally simply melted for
reuse by smelters or by consumers and foundries. Although the battery was invented by Gaston Plante
in 1859, it was not until the automobile became ubiquitous that specialised secondary smelters came

to prominence. When the quantity of available batteries was relatively small they could be added to a
primary blast furnace. However, as the quantity grew, this created problems with the sulfate load and
the introduction of chloride from the plastic materials contained in the batteries.
Initially the older reverberatory furnaces were used for processing battery scrap, with slag
treatment in a small blast furnace. This practice has persisted in North America, but in Europe the
reverberatory furnace evolved from the stationary form to the short rotary furnace. This provided
much improved mixing and operational efficiency, and separate equipment for slag treatment was not
required. The use of soda slags in the short rotary furnace also captured sulfur from the battery paste,
and provided an efficient simple operation. However, problems with the disposal of soda slags
resulted in the development of pre-treatment techniques to remove sulfur prior to smelting, and this
has been coupled with the separation of battery components and the recovery of polypropylene as a
valuable by-product. Presently there is a range of process configurations used for the recovery of
secondary lead. These are detailed in Chapters 10 and 11.
The secondary lead industry now represents almost 70 per cent of total lead supply and hence
exceeds the scale of the primary smelting industry.
HISTORICAL SUMMARY
A timeline summary of important milestones in the development of lead smelting technology is
shown in Figure 2.6. Major changes in smelting technology have been few over the past 250 years and
may be limited to:
• the reverberatory hearth process;
• the blast furnace and application of water jackets;
• the Dwight-Lloyd sintering machine;
• direct smelting technologies – Kivcet, QSL and Top submerged lance processes; and
• direct leach – electrowin processes – yet to be commercialised.
In relation to lead refining major innovations have mainly occurred in the 70-year period from the
late 1800s to the early 1900s, largely due to the quality demands for lead as the industrial age developed.

Agricola, G, 1950. De Re Metallica (1556), translation by H C and L H Hoover (Dover Publications Inc: New York).
Collins, H F, 1910. The Metallurgy of Lead (Charles Griffin and Co: London).
Dube, R K, 2006. The extraction of lead from its ores by the iron-reduction process: A historical perspective,
Journal of Metals, October, pp 18-23.
Eissler, M, 1891. Metallurgy of Argentiferous Lead: A Practical Treatise on the Smelting of Silver – Lead Ores
(Crosby-Lockwood and Son: London).
Hoffman, H O, 1899. The Metallurgy of Lead (The Scientific Publishing Company: New York). Also revised
edition, 1918 (McGraw Hill: New York).
Percy, J, 1870. The Metallurgy of Lead (John Murray: London).

CHAPTER 3
Raw Materials
Lead sulfide or galena is the main source mineral for lead. It was earlier mined as massive rich veins
and was smelted directly. Today it is usually extracted as a co-product with zinc mineralisation and is
separated and concentrated using flotation.
LEAD MINERALOGY
The common lead minerals are given in Table 3.1.
TABLE 3.1
Common lead minerals.
Mineral Formula Lead content (%)
Galena PbS 86.6%
Anglesite PbSO4 68.3%
Cerussite PbCO3 77.5%
Leadhillite PbSO4.2PbCO3.Pb(OH)2 76.8%
Jamesonite Pb4FeSb6S14 50.8%
Pyromorphite 3Pb3P2O8.PbCl2 76.4%
Bournonite 3(Pb,Cu2)S.Sb2S3 24.7%
Mimetite (PbCl)Pb4(AsO4)3 69.7%
As the predominant source of lead, galena deposits were commonly formed by hydrochemical
processes through the cooling of mineral-rich solutions associated with magmatic eruptions or
intrusions, and occur in beds or veins. Galena can occur as a replacement or metasomatic deposit in
limestone associated with dolomitisation, and is typified by the Mississippi zinc–lead deposits.
Associated minerals are frequently zinc sulfide or sphalerite, chalcopyrite, pyrite and minor mixed
sulfide minerals often containing silver. Weathering and oxidation of the primary sulfides leads to the
formation of deposits of anglesite and cerussite, which were the early source minerals in Britain.
Most lead ores also contain silver, antimony, arsenic and bismuth. Silver is an economically
important constituent of lead concentrates and is often necessary to allow the smelting operation to be
profitable. Silver may be present as argentite (Ag2S) but is probably more commonly present in
association with antimony, copper and arsenic minerals such as pyrargyrite (Ag3SbS3), proustite
(Ag3AsS3), freieslebenite ((Pb,Ag)8Sb5S12), polybasite ((Ag,Cu)16(Sb,As)2S11), and tetrahedrite
((Cu,Fe)12Sb4S13) in which silver can partly replace copper. Small amounts of many of these minerals
can be present in solid solution in galena. The presence of gold is also common and can be of value as
it is recovered with the silver.
Bismuth is an unwanted element in refined lead and is difficult to remove in the refining process.
Hence, its presence in lead concentrates attracts a significant cost penalty. In general there is a
complex series of sulfide minerals of the form MS:(As,Sb,Bi)2S3 in which M may be Pb, Fe, Cu, Ag or
Tl. There is a wide range of ratios between the two components and mix or replacement of the various
elements. This gives rise to the common presence of these elements to varying degrees in lead
concentrates.

CHAPTER 3 – Raw Materials
SEPARATION AND CONCENTRATION METHODS

Early lead smelting used directly mined massive sulfide vein ores rich in galena, as well as surface
deposits of carbonates (cerussite). Any concentration may originally have been by hand-sorting of
lump ore. However, because of their high density, it was relatively simple to separate and concentrate
coarse-grained lead ores by gravity concentration methods. Relative densities of commonly occurring
minerals are shown in Table 3.2.
TABLE 3.2
Density of common minerals.
Mineral Specific gravity Hardness (Mohs’ Scale)
Galena (PbS) 7.4 - 7.6 2.5 - 3.0
Anglesite (PbSO4) 6.1 - 6.4 2.8 - 3.0
Cerussite (PbCO3) 6.5 - 6.6 3.0 - 3.5
Sphalerite (ZnS) 3.9 - 4.1 3.5 - 4.0
Smithsonite (ZnCO3) 4.3 - 4.5 5.0
Willemite (Zn2SiO4) 3.9 - 4.2 5.5
Pyrite (FeS2) 5.0 6.0 - 6.5
Pyrrhotite (FeS) 4.6 3.5 - 4.6
Siderite (FeCO3) 3.9 3.5 - 4.0
Haematite (Fe2O3) 4.9 - 5.3 5.5 - 6.5
As shown in Table 3.2, there are significant differences between the specific gravity of common
lead minerals and associated minerals. These differences enabled gravity classification methods such
as elutriation classifiers, spirals, shaking tables, jigs and vanners to be used to produce a concentrate,
and gravity concentration was the sole method used prior to the development of flotation in the early
1900s. One issue was the relative softness of the lead minerals, which results in the formation of
slimes in crushing and grinding circuits. After size classification using equipment such as the Dorr
rake classifier, the fines were filtered to form a lead-rich concentrate of around 50 - 60 per cent lead.
The classifier sands were then subjected to gravity separation on shaking tables or similar devices to
reject gangue minerals and yield a concentrate of 60 - 70 per cent lead content. To use these methods
it was necessary to limit the degree of size reduction and to separate the minerals at the earliest
opportunity, and hence it was a successful approach only for relatively coarse-grained ores.
The development of flotation separation methods was originally for the purpose of separating zinc
minerals from mixed lead–zinc ores and initially from gravity separation tailings. Once this great
breakthrough was achieved, attention was turned to the separation and concentration of lead minerals
and thereafter flotation became the primary method of concentrating sulfide ores.
In the past, lead ores were mined for the production of lead and silver. Today this is uncommon and
most lead concentrates are produced in conjunction with zinc concentrates from lead–zinc ores. As
discussed in Chapter 1, the ratio of lead to zinc mined has fallen significantly to around 0.3 in 2005. It is
therefore common for ores to contain around five per cent lead or less. Generally the aim is to produce a
marketable lead concentrate around 60 per cent lead or greater, although concentrates of 50 per cent lead
are produced and treated. There is reasonable flexibility in the ability of smelting processes to handle a
wide range of concentrate grades (50 - 75 per cent lead) and the principal effect of lower grade is the
reduction in capacity of the initial or sulfur elimination stages of the smelting process.

Separation and concentration involves two main steps:

1. size reduction of the ore so that the individual mineral grains are liberated and separated from
one another, and
2. selective physiochemical separation of the individual mineral grains by froth flotation to form
separate metal concentrates.
Size reduction for mineral grain liberation involves crushing and grinding to an 80 per cent
passing size of less than 50 µm and for particularly complex fine grained ores to less than 10 µm. Fine
grinding is a high cost in both equipment and energy and there have been developments to improve
the efficiency of this operation, such as tower and stirred mills. Fine grinding is a particular problem
for lead sulfide recovery because of the softness of galena and its tendency to fragment into ultra fine
particles or ‘slimes’, which are difficult to capture and recover during flotation. Because of this
problem it is preferable to float lead minerals before extensive fine grinding. Fine grinding can then be
applied to the tailings of galena flotation and is primarily targeted at improving zinc recovery and
concentrate grade.
Primary crushing may reduce ‘as mined ore’ to less than 200 mm and then, in the conventional
approach, it is further reduced in secondary and tertiary crushers followed by rod and ball mill
grinding to the required particle size. Final sizing classification is usually achieved by operating the
ball mill in closed circuit with hydrocyclones.
If the ore is suitable, autogenous grinding may be used, in which large lump ore is added directly
to a large tumbling mill. This replaces conventional secondary and tertiary crushing, rod and possibly
ball mills, saving on the cost of steel grinding media, which can be consumed at a rate of the order of
1 - 2 kg/t of ore. The low density of lump ore in comparison with steel balls requires a much larger
diameter mill to achieve the same grinding forces. Full autogenous grinding is often difficult to
achieve if the ore tends to fracture and break down readily on a macro scale; however, in this case
some steel balls can be added to give semi-autogenous operation and greatly extend the application of
this approach, to the point where this has largely replaced the conventional multi-stage size reduction.
For fine grinding, additional ball mill capacity is necessary. For very fine grinding tower or stirred
mills have been developed to significantly reduce energy costs. In this type of equipment, grinding of
the mineral pulp occurs within an agitated bed of coarse gravel. The bed may be agitated by
circulation using a screw or by slow-moving paddle mixers. These mills have significantly lower
specific energy consumption, which is critical for size reductions to 10 µm or less. To avoid ‘sliming’,
fine grinding can be applied partway through the separation process rather than on total ore feed and
after separation of galena and a large part of the gangue minerals. This minimises ‘sliming’ and
reduces the quantity of material subjected to fine grinding, and hence minimises overall grinding
costs.
Physical separation of minerals generally relies on the use of froth flotation. Flotation is based on
the following principles:
• sulfide minerals may be conditioned by the addition of surface active chemicals to cause them to
become water repellent (hydrophobic),
• the collisions between mineral particles with hydrophobic surfaces and bubbles of air within the
mineral pulp will result in the attachment of the mineral particles to the air bubbles,
• mineral particles which remain wetted (hydrophilic) will not attach to the air bubbles, and
• reagents are used to produce a froth of reasonable stability to allow its collection and separation
from the surface of the mineral pulp.

Flotation equipment consists of a series of agitated tanks through which the mineral pulp flows
and into which air is dispersed as a stream of fine bubbles. A froth is formed on the surface, containing
the hydrophobic mineral particles, and is skimmed off into a trough where it collapses and flows into a
collection tank.
It is a relatively simple matter to bulk float all sulfide minerals by the addition of surface active
chemicals known as collectors. This type of material is usually an organic molecule containing a
sulfur-bearing group at the polarised end which can bond with the sulfide mineral, forming an
attached organic and hydrophilic surface layer. The most common collectors are:
Dithiophosphates such as:
• sodium diethyl dithiophosphate Na+(PS2(OC2H5)2)-
Xanthates such as:
• sodium isopropyl xanthate Na+(CS2-O-C3H7)-
Differential flotation can be achieved when only specific minerals are floated. This is done by the
use of additives to the pulp to depress or promote the collection of particular mineral surfaces. The
particular response of minerals contained in an ore will differ widely, and hence there is a considerable
variation in flotation practices from one plant to another. The general approach, however, is to first float
copper and depress the other base metal sulfides, then float lead and finally zinc. The aim is generally to
depress pyrite, but this can be difficult and it is often the major diluent in lead and zinc concentrates.
The pH of the pulp is an important depressant, showing selectivity for individual minerals and
depression in the following order as pH is raised:
• sphalerite (ZnS),
• pyrrhotite (FeS),
• galena (PbS),
• pyrite (FeS2),
• chalcopyrite (CuFeS2),
• sphalerite activated with copper sulfate, and
• tetrahedrite ((CuFe)12Sb4S13) for silver mineralisation.
Other depressants that have been used are zinc sulfate for sphalerite and cyanide for sphalerite and
pyrite, although CMCs (carboxy methyl cellulose – dextrose or starch derivatives) tend to be more
commonly used at the present time.
Following depression of most of the sulfide mineralisation, copper can be initially floated, followed
by the flotation of lead after pH adjustment. Copper sulfate is generally then added to promote the
flotation of sphalerite. In simplistic terms, copper ions react with the zinc sulfide surface to form a
copper sulfide layer which will readily respond to the collector. The action of cyanide as a depressant is
partly due to its ability to form a complex with copper ions in solution and prevent any such activation.
The kinetics of the flotation process are an important factor and some of the relative reaction rates
may be quite different, allowing some opportunity for differentiation by this means, and placing
emphasis on the importance of process residence times. Other factors of importance in control of the
process are the pulp density, pulp temperature, aeration rates and bubble size.
A sample copper/lead/zinc separation flow sheet is shown in Figure 3.1.

Ore Input
Primary Grind
Copper
Rougher
Float concentrate Float tails
Copper Copper
Cleaner Scavenger
Concentrate
Tailing Tail
Copper concentrate
Lead Rougher
Concentrate Tailing
Lead
Lead Cleaner
Scavenger
Tailing Concentrate
Re-grind Tailing
Lead concentrate
Zinc Rougher
Concentrate Tailing
Zinc
Zinc Cleaner
Scavenger
Tailing Concentrate
Re-grind Final
Zinc concentrate Tailing
FIG 3.1 - Typical flotation flow sheet for copper/lead/zinc ore.
There are many different flow sheets used for the handling of particular ores; however, a typical
flow sheet usually involves an initial flotation stage or ‘rougher circuit’, the crude concentrate from
which is refloated in a ‘cleaner circuit’ for upgrading. The tailings from the ‘rougher circuit’ are also
refloated in a ‘scavenger circuit’ to recover any residual mineral values. A multiplicity of such stages
and the recycling of intermediate streams can lead to a highly complex flow sheet with a high level of
internal recycle and difficult control problems.
The basic aim is to optimise the grade of the concentrate produced and the recovery of valuable
metals into their respective concentrates. This may be expressed as a grade-recovery curve for a
particular ore, as illustrated in Figure 3.2. The position of the curve is to some extent a function of the
flow sheet used, but is critically dependent on the grind size. Finer grinding will improve minerals
liberation, but the recovery of very fine particles or slimes can be reduced, due in large part to their
inability to collide with and attach to air bubbles. Specialised flotation cells to generate fine bubbles
can improve this situation and significantly improve lead recovery from the ore in such situations.

Recovery
%
Decreasing
Grind Size
0 Ore Pure Mineral

Grade Grade
Concentrate Grade % Zn
FIG 3.2 - Concentrate grade–recovery relationship.
Conditioning of the pulp with reagents prior to flotation is also of great importance, particularly
when processing very finely ground material. This involves the degree of agitation and residence time
used, as well as the concentration of added reagents in the pulp.
The particular position on the grade-recovery curve for flotation plant operation is dictated by
competitive pressures for sale of the concentrate and overall economics of the mining operation,
including transportation issues. It is a complex balance, and many variables, together with the total
mineral value recovered from the ore, must be considered in order to select the optimum set of operating
conditions. This involves consideration of all primary and by-product concentrates produced.
In some instances it is impractical to grind fine enough to achieve satisfactory separation, or
excessive sliming causes loss of recovery. For these types of ores, production of a bulk or middling
concentrate containing high levels of two or more valuable metals at relatively high recovery may be
the only feasible method for metal concentration. This can be a suitable feed to an Imperial Smelting
Furnace. In such circumstances it is possible to produce part of the zinc and lead content of the ore as
high-grade concentrates, and part as a bulk or middling concentrate to maximise recovery. The
economics of the mining operation are largely determined by the head grade of the ore and the metal
recovery achieved into commercially acceptable concentrates.
COMMERCIAL LEAD CONCENTRATES

Lead sulfide concentrates produced by the above described separation processes have individual
characteristics which need to be carefully assessed by the smelter, although they are largely treated as a
commodity, with compositions falling within common and accepted ranges and limits. In general, lead
concentrates vary over a much wider range of compositions than zinc concentrates. This is partly due to
the greater tolerance of the standard smelting processes to accept gangue minerals which form smelter
slags, but it also due to the wider variation of lead recovery as a function of concentrate grade and the
wider range of optimum grades for a particular mining operation than applies for zinc concentrates.
Of key importance is the lead to sulfur ratio of the concentrate, since low levels (corresponding
with low lead grades) will markedly restrict the lead throughput of the sulfur elimination stage of the
smelting process (see Chapter 4, Table 4.2).

Also of major importance is the content of precious metals, particularly silver, which contributes
significant value, and the presence of the critical impurity elements arsenic, antimony and bismuth,
which attract cost penalties. Smelters often have a limited capacity to remove penalty elements within
the lead bullion refining operation, and hence need to balance the intake of impurities so as to remain
within various capacity limitations. This can often require careful blending of a range of feed
concentrates to obtain the optimum feed mix.
The average composition range for traded lead concentrates is given in Table 3.3, which also
shows the maximum limits commonly preferred for critical impurity elements.
TABLE 3.3
Commercial lead concentrate specifications.
Element Normal range Preferred maximum limits

Lead 55 - 75%
Zinc 3 - 15% 10%
Iron 2 - 12%
Sulfur 14 - 25%
Silica 2 - 10%
Calcium 0.05 - 1.5%
Aluminium 0.2%
Arsenic 0.02 - 0.5% 0.2%
Antimony 0.01 - 0.3% 0.2%
Silver 100 - 2000 g/t
Gold 0 - 5 g/t
Copper 0.005 - 1.0%
Cadmium 0.005 - 0.20%
Nickel 5 - 50 g/t
Cobalt 0 - 20 g/t
Mercury 5 - 50 g/t 10 g/t
Selenium 0 - 30 g/t
Tin 2 - 50 g/t
Bismuth 5 - 1000 g/t 10 g/t
Fluorine 5 - 500 g/t 100 g/t
Chlorine 10 - 1000 g/t 500 g/t
To form slags in the smelting process, fluxes need to be added; these generally consist of CaO (as
limestone), SiO2 (as sand or ground quartz), and in some situations Fe2O3 (as ironstone). Certain
dilution of concentrates by flux additions is necessary, particularly for sinter plant–blast furnace
operations, since typical sinter composition is in the range of 45 - 50 per cent lead with defined ratios
of FeO:SiO2:CaO. Generally the amounts of CaO and SiO2 in concentrate are below requirements for
fluxing, hence the presence of these components in the concentrate is not of concern to the smelter
unless they are in excessive amounts. Other gangue impurities such as MgO, Al2O3, Mn, Na and K
will also report to the slag with minimal impact, and hence their presence in minor amounts is not of
significance.

There are limits to the amount of zinc contained in the lead concentrate, as determined by the
capacity of the slag to hold the zinc in solution. The limits of zinc in slag are around 18 per cent, and
for a common slag to lead bullion ratio of 1:1 might suggest an upper limit of zinc in a 60 per cent lead
concentrate of ten per cent. Higher levels may be accepted if blended down in smelter feed with
concentrates containing lower levels of zinc. The presence of some zinc is beneficial in sinter–blast
furnace operations due to its effect on the microstructure and quality of sinter, and at low levels
economic recovery of zinc from slag by fuming will not be possible (see Chapter 8).
A range of impurity elements need to be separated in the lead refining process. If the concentrate is
relatively clean with few impurities, it may be possible to produce a primary bullion with minimal
impurity separation procedures to produce an acceptable refined lead. If impurities are in excess of the
minimal levels, then cost penalties can be applied to cover the additional operations and associated
costs of removing those impurities. In particular, this applies to arsenic, antimony and bismuth.
Alternatively, the material may be unacceptable or will only be accepted in limited amounts as part of
a feed blend, depending on the capabilities of the particular smelter and associated refinery.
For feed to the Imperial Smelting Process, there can be penalties on silica, as well as arsenic,
bismuth and antimony.
COMMERCIAL TERMS FOR THE PURCHASE OF STANDARD LEAD

CONCENTRATES
The structure of the terms formula on which the price of lead concentrates is determined is essentially
based on payment for 95 per cent of the lead content of the concentrate (subject to a minimum
deduction of three percentage points) at the prevailing market price for refined lead, such as the
London Metal Exchange (LME) settlement price, less a treatment charge, which is a fixed amount per
tonne of concentrate. Examples of lead payments at different concentrate grades are given in
Table 3.4. At lower grades the price formulation to some degree reflects that the losses in metal from
the smelter are governed by the quantity of slag produced.
TABLE 3.4
Lead concentrate metal payments.
Concentrate lead content (%) Lead in concentrate paid for (%) Lead content paid for (%)
75 71.25 95
65 61.75 95
60 57 95
55 52 94.5
50 47 94
45 42 93.3
In addition to lead payments, silver and gold are also paid for above minimum levels. Silver
payments are commonly made for 90 - 95 per cent of the silver content above 50 g/t, and gold for
85 per cent of the gold content above 1.0 - 1.5 g/t.
The treatment charge is negotiable and can escalate with the lead price, but is typically of the order
of US$250 per tonne of concentrates at an LME lead price of US$1000 per tonne. The escalation is
typically 15 per cent of the increase in the lead price, but is a negotiable item. In times of surplus

concentrate supply the negotiated treatment charge will tend to be high, favouring the purchaser,
whereas in times of concentrate shortage the treatment charge will tend to be low, favouring the seller.
The treatment charge normally covers the production of refined lead and so includes charges for both
the smelting and bullion refining operations. Refining can be separately charged and the treatment
charge for refining is around US$150 per tonne of bullion, which represents about US$80 per tonne of
concentrates or around one-third of the total treatment charge.
In addition to the basic lead treatment charge, charges are levied for the refining of silver and gold
and for the removal of key penalty elements. Silver refining charges are typically US$12 per kg of
silver paid for and gold refining at US$200 per kg of gold paid for in the concentrate.
Penalties for arsenic, antimony and bismuth are:
• arsenic US$4 per 0.1 per cent of contained arsenic above 0.2 or 0.3 per cent,
• antimony US$3 per 0.1 per cent of contained antimony above 0.2 or 0.3 per cent, and
• bismuth US$1 per 0.01 per cent of contained bismuth above 0.05 per cent.
For a typical lead concentrate, the following gives a calculation of standard commercial terms:
• concentrate grade: 60 per cent lead (Pb)
1000 g/t silver (Ag)
3 g/t gold (Au)
0.5 per cent arsenic (As)
0.3 per cent antimony (Sb)
0.06 per cent bismuth (Bi)
• metal prices: lead US$1100 per tonne
silver US$10 per troy ounce
gold US$600 per troy ounce
• metal payments: lead 60 per cent × 95 per cent × US$1100 = US$627 per tonne
silver (1000 - 50) × 90 per cent = 855 g/t = 27.49 troy oz/t
= 27.49 × US$10 = US$274.9 per tonne
gold (3 - 1) × 85 per cent = 1.7 g/t = 0.0546 troy oz/t
= 0.0546 × US$600 = US$32.8 per tonne
Total metal payments = US$934.7 per tonne of concentrates
• treatment charges: lead TC = US$265 per tonne
silver refining = 0.855 kg × US$12 = US$10.26/t
gold refining = 0.0017 kg × US$200 = US$0.34/t
Total charges = US$275.6 per tonne of concentrates
• penalties: arsenic = (0. 5 - 0.3)/0.1 × US$4 = US$8/t
antimony = (0.3 - 0.3) = 0
bismuth = (0.06 - 0.05)/0.01 × US$1 = US$1/t
Total penalties = US$9 per tonne of concentrates
Total value of concentrate = (934.7 - 275.6 - 9.0) = US$650.1 per tonne

The smelter primarily makes a return from the treatment charge, plus any free metals derived from
recoveries achieved for lead and precious metals above the recoveries implied in the terms. For instance
it may be possible to achieve 98 per cent lead recovery, giving three per cent free metal. Silver and gold
recoveries may also significantly exceed the terms values, depending on process efficiencies.
Smelter revenues are also boosted by an ability to recover and sell by-products such as sulfuric
acid and copper, as well as some minor elements such as antimony in the form of antimonial lead
alloys, mercury and cadmium. In some instances zinc can be recovered from smelter slags by fuming.
Pricing of concentrates for delivery on a particular date is based on average daily LME metal
prices over a defined period (‘The Quotational Period’) and usually is set as the month following the
month of delivery. This is intended to provide a close match with the timing of consumption of the
concentrate and delivery of product metal. Otherwise there can be serious discrepancies and
variations in pricing of the metal contained in the concentrates used, and the pricing of the metal
recovered and sold from those concentrates.
COMMERCIAL TERMS FOR THE PURCHASE OF BULK CONCENTRATES

The Imperial Smelting Process produces both zinc and lead, and can blend standard zinc concentrates
with lead concentrates or, preferably, can use mixed bulk concentrates. Since the terms for low grade
and mixed bulk concentrates are more favourable to the smelter due to the greater percentage of ‘free
metal’, it is in the interests of an ISF smelter to source as much of its raw material as possible as bulk
concentrates. The metal output of the plant will be reduced as more lower grade materials are
processed due to the increased formation of slag, the associated losses of zinc in that slag, and the fuel
utilisation to heat and melt the slag. Hence there is a balance between lower cost raw materials and
lower zinc production, which leads to an optimum grade of mixed feed. The best option is possibly the
total use of bulk feed of relatively high grade in terms of total zinc plus lead content.
The terms for mixed bulk concentrates represent a mix between standard zinc and lead concentrate
terms and the following is a typical example:
• zinc payment for the balance of the zinc content after deduction of 7.5 units at the LME zinc price
for SHG zinc metal,
• lead payment for the balance of the lead content after deduction of three units at the LME lead price,
• silver payment for 90 per cent of the balance after deduction of 90 g per tonne of concentrate, and
• gold payment for 60 per cent of the balance after deduction of 2 g per tonne of concentrate.
Penalties and refining charges are similar to lead concentrate terms and often there can be
additional penalties, such as for silica above a minimum level. This critically depends on the mix of
feed stocks normally received by the smelter.
The treatment charge is commonly US$10 to US$15 above the ruling treatment charge for
standard zinc concentrates, at around US$220 per tonne, and with the price escalator three per cent
lower than standard zinc concentrates at around nine per cent.
COMMERCIAL TERMS FOR THE SALE OF LEAD BULLION

The production of refined lead is commonly broken into two discrete stages:
• the smelting stage, with sulfide concentrate feed producing a crude lead bullion; and
• the refining stage, in which a range of impurities are removed from the bullion to produce refined
lead.

These two stages may be within the one smelting site or may be two separate businesses, with
crude lead bullion being the traded intermediary. Traded lead bullion is commonly derived from the
treatment of primary concentrates, but can also be lead bullion produced from secondary sources.
Secondary bullion generally contains much fewer impurities. As an example, ISF smelters do not
usually include lead refining operations and consequently sell their crude lead bullion to a refinery.
The commercial terms for the sale of lead bullion are typically as follows:
• lead payment 98 per cent of the lead content at the prevailing LME price for lead
• silver payment 98 per cent of the silver content with a minimum deduction of 50 g/t at the
specified silver price
• gold payment 95 per cent of the gold content with a minimum deduction of 1 g/t at the
specified gold price
• copper payment 80 per cent of the copper content with a minimum deduction of two
per cent at the LME price for copper
• lead refining charge US$150 per tonne of bullion treated
• silver refining charge US$12 per kg of silver paid for
• gold refining charge US$200 per kg of gold paid for
• bismuth penalty US$15 per 0.1 per cent contained bismuth
Penalties will depend on the refinery and the process used. For instance, for the electrolytic
refineries the cost structures for impurity removal and treatment are quite different to the
pyrometallurgical refineries, where the costs of removal of bismuth, for instance, are quite high.
SECONDARY MATERIALS
Metallic scrap is one significant source and can be purchased by the smelter or refinery at prices
reflecting a nominal discount to the prevailing LME price for refined lead. However, the bulk of
secondary lead is derived from the processing of recycled scrap lead-acid batteries. The trade is very
localised with no general standard terms and the cost to the secondary smelter often simply reflects the
cost of collection of scrap batteries.
The other source of secondary lead can be low-grade residues such as oxides or sulfate leach
residues, often sourced from electrolytic zinc plants as secondary leach residue and containing
between 20 and 40 per cent lead. Often these residues contain substantial amounts of silver, which can
economically justify treatment. Similar residues can be sourced from copper smelting operations, as
well as miscellaneous dusts and fumes containing high levels of lead and precious metals. Many of
these metallurgical fumes, such as copper converter dusts, can contain up to 30 per cent lead but also
usually contain high levels of minor impurities such as bismuth, arsenic, antimony, cadmium,
selenium and tin, which add significantly to the bullion refining load.
Terms are similarly structured to sulfide concentrates, with the exception that treatment charges
will be negotiable given the individual smelter’s capacity and ability to take additional secondary
materials. Treatment charges are generally lower per tonne of material treated, but up to 50 per cent
higher when expressed as per tonne of contained lead. There may also be additional penalties where
high levels of particular impurities are present.


Henley, K J, Radke, F and Tilyard, P A, 1998. Determining the deportment of minor trace elements in base metal
concentrates with examples from Broken Hill, in Proceedings The Mining Cycle – AusIMM Annual
Conference, pp 381-388 (The Australasian Institute of Mining and Metallurgy: Melbourne).
Sutherland, K L and Wark, I W, 1955. Principles of Flotation (The Australasian Institute of Mining and Metallurgy:
Melbourne).
Wilson, P C and Chanroux, C, 1993. Lead, in Cost Estimation Handbook for the Australian Mining Industry,
pp 346-348 (The Australasian Institute of Mining and Metallurgy: Melbourne).

PART B
PRIMARY SMELTING
This part of the text covers smelting processes used for the extraction of crude
lead bullion from ores and mineral concentrates.
Chapter 4 Sintering
Chapter 5 The Blast Furnace
Chapter 6 The Imperial Smelting Furnace (ISF)
Chapter 7 Direct Smelting Processes
Chapter 8 Smelter By-Products and Treatment Processes
Chapter 9 Electrochemical Reduction Processes
CHAPTER 4
Sintering
The purposes of sintering are:
• to roast lead sulfide concentrates so as to remove sulfur, and
• to achieve sufficient temperature to cause partial melting in order to form a porous cake of sufficient
cohesion and strength to be suitable as feed to the blast furnace.
PROCESS CHEMISTRY AND THERMODYNAMICS

The primary roasting reaction required is shown in Equation 4.1:
PbS + 1.5O2 = PbO + SO2 (4.1)
Other side reactions that can occur are shown in Equations 4.2 to 4.6:
PbS + 2O2 = PbSO4 (4.2)
2PbS + 3.5O2 = PbO.PbSO4 + SO2 (4.3)
PbS + O2 = Pb + SO2 (4.4)
PbS + PbSO4 = Pb + 2SO2 (4.5)
PbS + 2PbO = 3Pb + SO 2 (4.6)
Relevant thermodynamic data for the above reactions are given in Table 4.1.
TABLE 4.1
Thermodynamic data for principal reactions.
Reaction Heat of reaction at Heat of reaction at Gibbs Free Energy Gibbs Free Energy
number 25 C 1000 C change at 25 C change at 1000 C
(kJ/g mole PbS) (kJ/g mole PbS) (kJ/g mole PbS) (kJ/g mole PbS)
4.1 -419.4 -390.8 -392.3 -318.6
4.2 -822.5 -831.6 -716.6 -369.1
4.3 -628.8 -613.4 -573.2 -358.9
4.4 -198.7 -183.7 -203.4 -220.8
4.5 +212.5 +232.0 +154.9 -72.6
4.6 +255.4 +245.3 +182.4 -41.0
Most reactions are highly exothermic and, with a highly negative Gibbs Free Energy change, have
the potential to readily proceed. The ‘roast-reduction reactions’ given as Equations 4.5 and 4.6 are
endothermic and have a negative Gibbs Free Energy change only at high temperature.
Reaction equilibria for these reactions are controlled by the partial pressures of oxygen and sulfur
dioxide, and can be simply explained by reference to the phase diagram for the Pb-S-O system as

CHAPTER 4 – Sintering
shown in Figure 4.1. This shows the equilibrium boundaries between various phases at two different
temperatures of 1000 and 1200°C, in terms of the log10 of the equilibrium partial pressures (in
atmospheres) of sulfur dioxide and oxygen. Since the system is at atmospheric pressure, the log
(partial pressure) cannot exceed zero. To maximise PbO formation and ensure that sulfates are
avoided, the temperature must be high and the SO2 levels low, particularly if excess oxygen is present.
This is achieved in the sinter bed by sweeping generated SO2 away from the reaction zone with a high
gas flow. If oxygen levels are low, (moving to the left of the diagram in Figure 4.1), there is an
opportunity to form metallic lead. This effect is more probable at higher temperatures.
PbSO4
PbS PbO.PbSO 4
PbO.PbSO 4
-5
Log(SO 2 partial
pressure - atm)
Pb PbO
-10
1000 oC 1200 oC
-15
-15 -10 -5 0
Log(O 2 partial pressure - atm)
FIG 4.1 - Phase diagram PbO-S-O system.
Figure 4.1 assumes solid state conditions for the non-gaseous components. In reality some phases
will be molten at these temperatures and will have mutual solubility, which will alter the activities
from unity. In particular the solubility of sulfur both in lead metal and PbO will mean that elimination
of sulfur is not as complete as implied by Figure 4.1.
THE SINTERING PROCESS

Sintering was first developed as a batch pot roasting technique using a crucible fitted with a grid base
through which air could be blown. Coal was first ignited on the base then sulfide materials were
progressively added and burned until the crucible was full. It was then emptied and the process
repeated. The Huntington-Heberlein Pot was a widely used form of the batch sintering method. This
approach was soon mechanised with the development of the Dwight Lloyd sintering machine based
on the principles of the chain grate stoker used for coal-fired boilers, as shown in Figure 4.2. It
consisted of an endless looped chain of steel pallets, each made from a frame fitted with steel bars to
form a grate. Material to be sintered was placed on the grate which then moved under a gas or oil fired

Feed
Ignition Stove
Feed Hopper
Gas
Air Sinter Bed
Moving Grate
Product Sinter
To Crusher
Suction Boxes
Gas Containing SO2
Fan
FIG 4.2 - Schematic of a Dwight Lloyd downdraught sintering machine.
ignition stove to heat and ignite the top layer. Air was drawn through the charge using a series of
suction windboxes located beneath the pallet chain and sealed by side plates attached to each pallet.
As the grate slowly moved forward, the combustion zone moved downward through the material until
combustion was completed. At the end of the machine, air passing through the sintered material
served to cool the sinter before it was discharged. The pallets moved over guides at the discharge end
of the machine and returned beneath the windboxes to the feed end.
The time required for sintering a bed of up to 400 mm deep is usually of the order of 30 minutes,
which represents the speed of one pallet traverse from the position of ignition to the discharge end or
‘tip end’ of the machine.
The process may be considered in terms of a number of zones moving through the charge bed as
illustrated in Figure 4.3.
Air
Ignition Stove
Wet Charge Charge Drying Charge Heating Reaction Air Heating

Zone Gas Cooling to Ignition Zone Sinter Cooling
Zone Zone Zone
FIG 4.3 - Separate zones in the sinter charge bed – downdraught conditions.

In the top zone, sinter already formed is cooled by incoming air and the air is heated. Hot air then
passes through the reaction zone where combustion of the fuel occurs with some degree of melting. In
the third zone hot combustion gases heat the unburned charge up to ignition temperature and the gases
are progressively cooled and pass to the fourth zone where drying of the material takes place and
gases are further cooled and humidified.
As the reaction front moves through the sinter bed the temperature at any one point will rise to a
maximum level and then decline as the bed is cooled by incoming air. The temperature profile of a
point within the bed as a function of time (or position along the machine) is illustrated in Figure 4.4.
The ‘peak bed temperature’ is the key parameter to follow and control.
1400
1200
Temperature (degrees Celsius)
1000
800
600
400
200
0
0 5 10 15 20 25 30
Time (minutes)
FIG 4.4 - Typical sinter bed temperature profile.
Gas permeability of the bed during the sintering process is a critical issue for maintaining
productivity and sinter quality. Permeability can be reduced by the effect of moisture evaporation
from the charge and recondensation in the colder downstream layers of the bed. More importantly,
with dry feeds permeability can be reduced by entrainment of fine particles on drying causing
blockage of the bed by collection and concentration of these fines in the downstream layers,
aggravated by the collection of excess moisture. To avoid this some form of binding of fine
concentrate particles to the return sinter is needed and often the addition of a small amount of CaO will
serve this purpose. In addition, excessive melting and formation of liquid phases can also cause a
reduction in bed permeability. However, a sinter feed mix which generates excessive amounts of low
melting point phases is not likely to be of acceptable quality, and needs to be avoided in any event.
Sinter quality is of key importance for efficient operation of the blast furnace, but is difficult to
define and measure in quantitative terms, as the ultimate measure is essentially optimum performance of
the blast furnace. Sinter must be strong enough to withstand handling without significant degradation
and breakage. It should be reasonably porous to allow gas-solid reduction reactions to take place to the
maximum extent, and it should have a suitably high melting temperature or softening range in order to

maintain its structure and integrity for the maximum possible time during the reduction process.
Strength and a high softening temperature are most important and can be compromised by a structure
which is too open and porous, even though this is also desirable for access of reduction gases.
Clearly the reaction temperature and peak bed temperature as discussed above are important and
key parameters for the formation of sinter with the required composition and properties.
The uniformity of attainment of this condition throughout the sinter bed is critical. In order that
this uniformity is achieved there must be constant conditions for the combustion reactions. This in
turn requires close attention to the sulfur or fuel content of the charge, and hence, uniformity in the
blending of charge components. Sizing and packing uniformity of the bed is also important to allow
for even airflow and oxygen access. A number of operating parameters need to be closely controlled
to achieve this, as discussed below.
THE STRUCTURE OF SINTER

In order to perform in a blast furnace, sinter must retain its physical structure for as long as possible
before melting and forming slag. Lead oxide reduction rates are highest from gas-solid reactions and
lowest from the liquid slag. If the sinter softens and becomes a sticky mass it can restrict access of
reduction gases to PbO surfaces and can, in extreme cases, plug the furnace and restrict the flow of
both the charge and gas. The key parameter is therefore the melting temperature or the softening
temperature range of the sinter. This is very much a function of the mineralogical composition and
structure of the sinter. The structure may simplistically be considered as a matrix of crystalline phases
cemented together by a glassy phase usually composed of lead silicate glass (CaO-PbO-SiO2). The
crystalline phases are primarily the high melting point zinc containing minerals melilite (a complex
mixture of calcium and aluminium silicates containing zinc, iron and magnesium) of which
hardystonite is one particular form, and ferrites such as franklinite (ZnFe2O4), which contains the bulk
of the trivalent iron and can also contain magnesium and aluminium as a replacement for zinc. This
structure develops only at high temperature and it is important that peak bed temperature is above
1200°C for this to occur.
Poorly performing sinters exhibit excessive lead silicate phases without the tight matrix of
intergrown crystal phases to provide structural support. This allows the sinter to soften and slump as
the temperature is raised.
The relative amount and melting temperature of the glassy phase or phases are also critical in
terms of determining the softening of the sinter structure. For instance, lead silicates have low melting
points in the range of 600 to 800°C depending on composition. Melting points can be raised by the
addition of CaO to increase the CaO:SiO2 ratio. The addition of CaO usually raises the temperature at
which softening commences as well as reducing the temperature range between initial softening and
the molten state. This effect is due to the decrease in the volume fraction of lead silicate phases with a
wide softening range.
For a typical sinter containing 46 per cent Pb, five per cent Zn, 11 per cent Fe, nine per cent CaO,
and 11 per cent SiO2, the glassy matrix will represent close to 40 per cent of the volume of the sinter,
the melilite phase is of the order of 30 per cent and the ferrites of the order of 20 per cent.
The microstructure of sinter can be quite complex where low-grade feed concentrates are
processed and there is a significant level of gangue minerals present. However, consideration of the
details generally points to the need for high peak bed temperatures during sintering to promote
crystallisation, and to the need for correct fluxing in order to achieve the appropriate matrix

composition as well as the ultimate process slag composition. In evaluating the needs for achieving a
given slag composition with respect to SiO2 in particular, the contribution from the ash derived from
coke used in the blast furnace must be taken into account.
The residual level of sulfur in sinter is also important in achieving the most suitable sinter structure
as well as meeting maximum limits for the blast furnace, and should generally be less than two per
cent. Common levels are around 1.7 per cent but can be as low as 0.7 per cent.
PROCESS OPERATING PARAMETERS
Sinter charge
The basic composition of sinter is determined by the target composition of blast furnace slag and a
lead content generally in the range of 45 to 50 per cent. Limits on the lead content of sinter at around
50 per cent are imposed to provide for sufficient slag fall within the blast furnace and to restrict the
formation of metallic lead within the sintering process. Good quality sinter usually contains some
metallic lead, but excessive amounts can result in drainage to the base of the sinter bed where it can
freeze and cause blockages of the airflow. It can also drain into the grate and windboxes, again
causing blockages as well as corrosion of the grate by PbO. This problem is more severe with
downdraft rather than updraft machines.
The sinter plant feed consists primarily of lead sulfide concentrates diluted with recycle sinter, flue
dusts, reverts and fluxing materials. Fluxes consist of silica sand, lime or limestone, and haematite if
additional iron units are required. The flux additions are determined by the target composition of blast
furnace slag with preset ratios of various components such as CaO:SiO2, FeO:SiO2 and Fe:Zn ratios
(details are given in Chapter 6 – Slag Composition). This determines the target composition of sinter and
hence determines the feed additions required to the sinter plant. In addition it is common practice to also
process secondary materials such as lead-rich leach residues arising from electrolytic zinc operations,
reclaimed battery pastes and miscellaneous recycle fumes and metallurgical residues rich in lead and
precious metals. Lead is predominantly present as lead sulfate in these materials, and they also
commonly contain zinc and iron. Lead concentrates contain a range of impurity elements, primarily zinc
and copper but also arsenic and antimony as well as variable amounts of silver and gold.
The composition of blast furnace coke with respect to its lime, silica and alumina contents also
needs to be taken into account when calculating the required sinter composition and corresponding
flux additives to give the required blast furnace slag composition.
Most sinter plants involve significant spillage from conveyors, from chute and equipment
blockages and from equipment maintenance activities. The quantity of spillage is highly variable, but
can be in the range of one to four per cent of sinter production. Spillage is collected into a storage bin
from where it is returned at a controlled rate to the sinter plant charge, together with dusts and fumes
collected from gas cleaning and from ventilation systems.
Fuel content of the sinter charge

In practice, for the sintering of lead sulfide concentrates, a sulfide sulfur content of the charge of
around six to seven per cent is required to achieve the necessary peak bed temperature. Since lead
concentrates normally range from 15 per cent to 25 per cent sulfide sulfur they must either be diluted
or partially roasted before sintering. Some dilution with return material occurs, but dilution with
recycled sinter is the preferred approach because of the high degree of control over the sinter feed mix

particle sizing that can be achieved. Depending on concentrate grade, fluxing needs and other inert
recycle materials added to the sinter charge, the ratio of recycle sinter to net product sinter will be
between 1:1 and 3:1.
The benefit of using crushed recycled sinter (termed ‘return sinter’) is to provide a relatively
coarse inert particle, which acts to form an open permeable structure allowing good airflow and
controlled energy release (from combustion) per unit volume, so as to prevent excessive fusion and
collapse of the bed. Another key benefit of return sinter is that fine concentrates in the charge will coat
onto the coarse sinter particles, improving bed permeability and thus providing maximum oxygen
access for rapid combustion.
Reduced levels of return sinter will cause a decrease in bed permeability, reducing possible gas
flow and hence, sinter machine capacity. On the other hand gas permeability is enhanced by increased
levels of return sinter, but fuel value of the charge is reduced and peak bed temperature is lowered.
This leads to poorer quality sinter with increased fines, which report to ‘returns’ and reduce sinter bed
permeability, thus reducing gas flow and machine capacity. The product sinter in this case is also
weak and readily breaks up in the shaft of the blast furnace, reducing permeability and blast furnace
throughput. Hence, there is an optimum level of recycle sinter and of fuel to maximise sinter machine
capacity. This normally corresponds to a sulfide sulfur content of sinter feed of six to seven per cent
and a minimum recycle ratio of 1:1 (recycle: net sinter production), or 50 per cent of total sinter
production.
If the minimum return sinter setting, or a heavy load of residues results in inadequate fuelling, then
a fuel supplement in the form of coke fines can also be used. One kilogram of carbon is roughly
equivalent to 2.2 kg of sulfide sulfur. Coke can be used in the case of a heavy charge of residues
containing sulfates, which have highly endothermic decomposition reactions; it also assists by
reducing the sulfates. However, it needs to be noted that coke tends to burn preferentially to lead
sulfide and if fine, can burn too rapidly. It generally broadens the temperature profile and must be
carefully sized to raise the peak temperature. Coke also promotes the formation of metallic lead within
the product sinter and its use has been attributed to an increase in lead volatility, and therefore an
increase in the production of fume in sinter gases. However, a partially prereduced sinter can bring
benefits in the blast furnace smelting stage by raising the sinter softening temperature.
Charge mixing and moisture control

Because of the high degree of compositional uniformity required, controlled proportioning and
mixing of all feed components is critical. This includes weigh feeding and controlled blending of a
number of concentrate feeds as well as fluxing materials, recycle fumes and residues, and return
sinter. For this purpose the plant usually includes a feed blending and proportioning facility made up
of a series of storage silos for each component, each fitted with weigh feeders and discharging onto a
common collection conveyor which feeds the primary mixer.
Another method used for blending of feed materials is the use of ‘bedding’ or the building of a
heap made up of layers of component materials on the floor of a storage building. The material is then
reclaimed by fully excavating the face of the heap, thus producing a blend in the same proportions as
the heap was constructed. This method is inflexible in that the blend cannot be varied once the heap
has been constructed, unless trimming additions of mix components can be made after reclamation.
Many lead sinter plants incorporate secondary materials such as lead residues containing lead sulfate
in their charge. The decomposition of sulfate is endothermic and can significantly affect peak bed
temperature and the quality of the sinter produced. Consequently, there are limits to the amount of

residues and secondary materials added to the charge. Some compensation can be achieved by the
addition of coke fines to the charge, but this can burn too quickly and must be carefully sized to provide
the desired effect. As a general rule the total quantity of secondary materials should not exceed 25 per
cent of the charge, but will depend on the total fuel value of the concentrates used as determined by the
relative amounts of minerals such as galena and pyrite present in the concentrates.
In order to have sufficient uniform flow of air through the sinter bed there needs to be a uniformly
sized porous bed, with a reasonably coarse average particle size. Since concentrates are usually quite
fine, the sizing of the charge will largely be determined by the sizing of the return sinter representing
the bulk of the charge, and the degree of agglomeration achieved in feed preparation. The ideal
situation is to have uniformly sized and relatively coarse particles of return sinter coated with a layer
of fine concentrates, thus forming an open structure with the concentrates exposed to the airflow to the
maximum extent. To meet this condition, return sinter is crushed using a combination of ribbed and
flat crushing rolls to a particle size of less than 5 mm. Moisture is added to the charge to assist in
binding the concentrate particles to the surface of the sinter. The total charge is mixed in a pug mill
and tumbled in a drum or table mixer to achieve the coating action and some degree of pelletisation
and conditioning. Disc pelletisers have been used in place of a drum, but generally the residence time
is too short for efficient final mixing and product uniformity, especially in terms of size distribution
and penetration of moisture evenly throughout the charge. Some water is added in the form of filter
cake from returned dusts and fumes collected from gas cleaning and ventilation systems.
The level of moisture is quite critical for the mixing and preparation operation, and is usually
between six and seven per cent. Too much moisture will physically reduce porosity and permeability
of the bed, whereas too little will not give the degree of uniformity of coating of the sinter particles and
hence, uniformity of the particle sizing of the bed. Inadequate moisture addition will also cause a
reduction in bed permeability. This is due to the lack of attachment of fines to the coarser particles and
their tendency to move and block gas passage through the bed. Excessive moisture can also give rise
to condensation in colder regions of the bed, resulting in blockage and reduced airflows. This effect
can result from the addition of residues containing chemically bound water such as water of hydration
or hydroxides and will place limits on the acceptable proportion of these materials in the charge mix.
Measurement of the moisture content of sinter feed with feedback to direct water additions at
various mixing points is thus an essential part of good sinter machine control. Various devices are
used for online moisture measurement, including infrared devices and electrical conductivity probes.
The latter are most common and can simply be two trailing electrodes in contact with the feed material
on a conveyor belt. These devices are not highly reliable and need careful and regular calibration since
they are affected by the presence of soluble salts, which can change the electrical conductivity of the
free interstitial water in the sinter bed.
Machine feeding
Even laying of the charge across the width of the sinter machine grate is critical in avoiding variable
permeability and uneven airflow through the bed. A reciprocating conveyor or swing chute are
commonly used to evenly fill an open hopper located above the grate. The gap between the grate and
the base of the hopper sets the depth of the bed and can be adjusted using a sliding plate. Bed depths
range from 200 to 500 mm.
The width of the gap (or bed depth) in relation to the width of the hopper (or throat width) can also
influence the packing density of the bed and needs to be carefully evaluated. It generally should be
greater than 1:1. Variations in the depth of material held in the hopper can also impact to some degree

on the packing density and it is preferable to maintain the hopper at a constant level. This can be done
by varying the machine speed for a given feed rate or by varying the feed rate to the hopper for a set
machine speed. The latter control is probably preferable but is more complex since feedback control
to all components of the feed preparation chain will be necessary. However, since this represents a
fine balancing control it is more usual to set a feed rate and vary machine speed as a balancing control.
Gas distribution
In general the combustion of most of the sulfur tends to take place towards the feed end of the sinter
machine, and the concentration of SO2 in gas is much lower towards the ‘tip end’ of the machine. A
typical gas concentration profile is shown in Figure 4.5 for a machine with ten windboxes. Average
SO2 levels as shown are about half the maximum and need to be above five per cent for sulfuric acid
production by the standard contact plant technology.
10
9
SO2 concentration (%)
8
7
6
Point
5
Average
4
3
2
1
0
0 2 4 6 8 10
Windbox No.
FIG 4.5 - Typical sinter gas composition profile.
Total airflow through the sinter machine far exceeds the requirements for sulfur combustion, in
part due to cooling requirements at the ‘tip end’ of the machine and leakage around the grate pallets.
High air leakage will be accentuated by deeper beds and hence, windbox pressure. This will dilute
SO2 levels in sinter plant gas and create difficulties with an associated sulfuric acid plant. If windbox
pressure is reduced to reduce leakage, then airflow will be lower and the machine speed will need to
be reduced, thus affecting machine capacity. Consequently, there are compromises between the
operating variables of bed depth, machine speed, windbox pressure and gas composition to give
optimum productivity.
Since there is considerable excess oxygen in the gas stream it is common practice to recirculate gas
from the tip end of the machine back into the front end in order to reduce the volume of sinter gas and
raise the average SO2 concentration from 4.5 per cent to around six or seven per cent so that it is
suitable for sulfuric acid production. Otherwise it has been the practice to collect only part of the gas
from the feed end for acid production and discharge the tail end gas to atmosphere. However, that
practice is less acceptable today, and tip end gas recirculation is now an important requirement for
environmental control.

Ventilation and hygiene

The handling of high lead oxide materials is hazardous and strict controls of lead particulates in air in
the workplace is required. Consequently, in addition to combustion gases, there is a large volume of
ventilation air for the purpose of collecting dust generated at many points within the sinter train. This
covers conveyors and transfer points, and particularly the sinter size reduction, screening and
handling equipment. Ventilation air is usually filtered in a bag house before discharge to atmosphere.
Temperatures are generally not high at around 100 to 150°C and polyester bags are commonly used,
fitted with reverse pulse cleaning mechanisms. Bag filter areas required for these duties are of the
order of 30 m2 per 1000 m3/h of air filtered.
Collected dusts are commonly pulped in water for ease of handling, and are filtered and the filter
cake combined with dusts collected from sinter plant combustion gases and blast furnace fumes for
return to the sinter feed mixing facility. The total load of collected dusts can be up to 2.5 per cent of
total sinter production, and the volume of ventilation gases for the sintering operation can be of the
order of 1500 Nm 3/h/m2 of sinter plant grate area.
Sinter handling
Sinter breaks away and falls from the tip end of the machine in large slabs, which fall through breaker
bars and a set of spiked rolls to break the sinter into lumps, which are separated using a 25 mm screen.
Oversize represents product sinter suitable for feed to the blast furnace. Undersize is cooled through a
drum or cooler conveyor and is then crushed using two sets of rolls in series. The final rolls are
normally set at around 5 to 6 mm. The resulting crushed sinter constitutes return material and is sent
via a surge bin to the feed mixing facility. Control of the gap in the final roll’s crusher is quite critical
to the sizing of the return sinter and to the performance of the process and the production of quality
sinter. These rolls tend to wear unevenly and give rise to a variable gap width and hence, a wider size
distribution of crushed sinter than is desirable. Hence, regular maintenance and re-machining of the
rolls’ surfaces is necessary.
Coarse product sinter from the primary screen is sent directly to surge bins from where it is
proportioned and mixed with lump coke to provide feed to the blast furnace. Provision is made to
crush and return product sinter to make up the required recycle ratio if necessary. Under steady state
operation of the sinter machine, control of the amount of product sinter returned is normally through
the level of material in the returns sinter surge bin, which is drawn off at a steady rate to satisfy feed
blend requirements.
Severe imbalances and instability of the process can result from the production of poor quality
sinter. Friable sinter of low strength gives excessive fines, which can exceed the requirements for
recycle. In such a situation recycle sizing can be reduced, sending more fine material to product,
which can have a detrimental effect on blast furnace operation. Finer sizing of the returns sinter can
also affect sinter machine performance by restricting the permeability of the sinter bed, and can
possibly perpetuate the problem. This situation can particularly arise on machine start-up and it is
often preferable to discard poor quality material to stockpile for later slow reclamation as returns. The
problem can also arise with departure from critical controls such as moisture content of the feed,
sizing and feed blending controls, and can lead to process instability and difficulty in restoring
product sinter quality. A disturbance will recycle with the returns cycle time, which can be measured
in hours. It may dampen with time (requiring many hours), but in extreme cases can increase out of
control, necessitating rejection from circuit to restore stable operation. In this regard the sintering
process is inherently unstable and is a particularly difficult process with a high degree of intolerance
to departure from stable operating conditions.

Sinter tends to degrade and disintegrate with time and hence stockpiling for any length of time can
significantly reduce its quality with adverse effect on the blast furnace. This property of sinter varies
greatly from one operation to another depending on the nature of the concentrates and other feed
materials used. A high calcium content can aggravate this problem.
UPDRAUGHT SINTERING
The initial development of sintering was based on the principles described above, wherein air passes
down through the sinter bed to windboxes located beneath the sinter machine grate and under suction
– so termed ‘downdraught sintering’.
The downdraught action tends to compress the bed against the grate and reduce permeability as
well as tending to lodge particles in the grate openings, causing blockages. It was also found that
where significant levels of metallic lead are present in the sinter it tends to more readily drain down
onto the grate where it can freeze, causing blockages, but more particularly causes severe corrosion of
the grate bars. ‘Lead fall’ into the windboxes themselves could also be a major operational burden. In
many cases sinter gases were also too low in SO2 content for sulfuric acid production and were
discharged to atmosphere.
In the downdraught operation any molten oxide phases formed tended to flow downwards into
unreacted material and could dissolve some of the sulfides. Hence, it was difficult to reduce sulfur to
low levels in product sinter and often grinding and re-roasting was necessary (Willis, 1980).
These problems can be overcome to a large extent by blowing air upwards from pressurised
windboxes and collecting sinter gas from a hood covering the machine. The first updraft sinter
machine was developed at the Port Pirie smelter in the early 1950s (Burrow, Ridley and Adams,
1956). This concept significantly improved the productivity and efficiency of the sintering operation
and is now the most commonly used design. A typical schematic of an updraft sinter machine is given
in Figure 4.6.
Ignition of the charge is still by downdraught on a shallow layer of around 30 mm laid on the grate
ahead of the ignition stove. After ignition of that layer the full charge depth of 300 to 400 mm is placed
on top of the ignited layer and airflow is reversed to updraught for the remainder of the machine. The
combustion zone moves upwards through the charge and breaks through the upper surface at around
80 per cent of the machine length.
Feeding the machine is then in two parts – one position for the ignition layer and one for the main
layer. In some machines entirely separate feed systems are used; in others the feed is split to the
ignition hopper and the main hopper using an intermittent diversion chute or conveyor. The
disadvantage of the latter system is that the level in the hoppers varies and as indicated above can vary
the packing density of the sinter charge. It also makes smooth control of the machine more difficult if
controls are linked to the level of material in the main feed hopper.
Machine speed is generally in the range of 1.0 to 1.5 m/min, and machines are generally wider at
around 3 m to minimise the edge effects which result in air bypassing the bed.
Initially updraught sinters performed poorly in the blast furnace due to relatively low softening
temperatures, which was raised by restricting the combined lead content (as PbO) to less than
35 per cent (Grant and Cunningham, 1971). This was achieved by the addition of coke fines to
reduce some of the combined lead to metallic lead. Such a practice was not considered for
downdraught sintering because of the significant problems with ‘lead fall’ into the windboxes
which already existed.

Gas Cleaning To Acid

Raw Material Hoppers Plant
Dust
Separation
ESP
Scrubber
Conditioning
Return Dust Collection
Sinter Drum
and Treatment
Mixer
Splitter
Main Feed
Ignition
Hopper
Hopper
and Stove Hood
Air Air
Ignition Gas to
Spiked Rolls
Gas Cleaning
Tip-end Gas
Recycle Screen
Crushing Rolls
Cooler
Crushing Rolls
Product
Return Sinter Sinter
FIG 4.6 - Flow sheet of an updraught sintering machine.
SINTER MACHINE CAPACITY AND PERFORMANCE

In general the sintering process involves a large number of variables and the formation of a material with
a complex microstructure. It is a difficult process to control and is inherently unstable when subject to
significant disturbances. Good performance thus tends to rely on a skilled and experienced workforce.
The generation of poor quality sinter can have significant impact on the performance of the reduction
processes which follow, particularly the blast furnace, and can greatly restrict its throughput.
Sinter machine capacity is normally expressed in terms of the sulfur burning capacity and is in the
range of 1 - 2 t/m2/d of grate area, with a typical figure of 1.8 t/m2/d. For a typical lead concentrate
containing 60 per cent Pb and 20 per cent S producing a sinter containing 45 per cent Pb and 1.7 per
cent S, this would correspond with a theoretical net sinter production of around 13.5 t/m2/d of grate
area or 6.1 t of Pb throughput per m 2 per day.

Sulfur burning capacities are relatively uniform amongst different plants, but sinter or lead
throughput varies significantly depending on the grade of the concentrate and the grade of the sinter
produced. This is illustrated in Table 4.2 and shows considerable variation in machine capacity.
Clearly capacity in terms of sinter output is significantly higher for primary lead smelters treating
high-grade lead concentrates with relatively low sulfur contents in comparison with ISF plants.
TABLE 4.2
Commercial sinter machine capacities.
Plant (see Table 1.6) Grate area Sulfur burning rate Sinter rate Lead capacity
(m2) 2
(t/m /d)
2
(t/m /d)
2
(t/m /d)
Primary lead smelters
Belledune (Canada) 99 1.7 9.7 3.6
Chigirishima (Japan) 33 1.8 16.0 6.9
East Helena (USA) 83.3 1.2 10.1 2.6
Glover (USA) 70.8 1.1 13.2 5.2
Herculeneum (USA) 90 1.5 16.0 7.8
Hoboken (Belgium) 56 1.6 17.6 6.2
Mount Isa (Australia) 93 2.3 11.4 5.5
Port Pirie (Australia) 83.6 1.9 15.5 7.8
Torreon (Mexico) 160 1.3 9.4 3.1
ISF smelters
Chanderiya (India) 120 1.6 6.5
Cockle Creek (Australia) 95 1.8 6.8
Hachinohe (Japan) 90 1.78 7.4
Harima (Japan) 70 1.63 7.8
Porto Vesme (Italy) 70 2.2 8.6
Sinter machines vary largely in size, ranging from small machines of 12 m2 grate area up to 110 m2
with a grate width of up to 3 m. Details of a number of commercial machines are given in Table 4.3.
Comparison between the operating performances of different sinter machines needs to recognise
that the sinter plant is coupled with a blast furnace and the blast furnace could be the primary
restriction, thus limiting the output of the sinter plant. It would appear to be a common feature that
smelters processing high-grade lead concentrates are usually limited by blast furnace capacity rather
than the sinter plant. The opposite is also the case, and smelters treating low-grade lead concentrates,
or a high level of secondary materials are often restricted by sinter plant capacity. ISF smelters
demonstrate that sinter production capacity per unit grate area is much lower than for primary lead
smelters due to the much higher sulfur content of concentrates at around 32 per cent, compared with
around 18 to 20 per cent for lead concentrates. Otherwise sulfur burning capacity, as the rate
determining parameter, is much the same.
The effect of lead concentrate grade on sinter machine capacity is most significant and may be
illustrated in Table 4.4 for a basic sulfur burning capacity of 1.8 t/m2/d, a target sinter feed of
6.5 per cent S and a target sinter composition of 45 per cent Pb and 1.7 per cent residual S. In all cases
the net sinter gas production at five per cent SO2 will be 1050 Nm3/m2 of sinter grate area. Because of
the varying Pb:S ratio the volume of sinter gas per unit of lead will also increase markedly as the
concentrate lead grade is reduced.

58
TABLE 4.3
Data for commercial lead sinter plants.
Plant Belledune Binsfeld- Chigirishima East Glover Herculeneum Hoboken Mount Isa Nordenham Port Pirie Torreon
hammer Helena
Lead production (t/a) 108 000 92 000 90 000 70 000 120 000 225 000 125 000 156 000 102 300 215 000 180 000
Concentrates
(t/a) 275 000 141 000 235 000 160 000 320 000 315 000 335 000 474 200
% Pb 45 to 72 62 to 75 76.5 72 40 51 65 43.5
%S 10 to 35 18 13 to 30 13.5 16.1 23 23.1 18 19.8
% Fe 2 to 25 5.5 to 30 1.2 3.3 10 11.6 6.6 10.5
Hearth length (m) × width (m) 3.0 × 33 1.5 × 25 2 × 15.2 2.44 × 29 3 × 30 2 × 28 3.05 × 30.5 3.05 × 27
2
Hearth area (m ) 99 37.5 33 83.3 70.8 90 56 93 36 83.6 160
Spectrum Series Volume 15
Bed depth (mm) 355 267 254 440 300

Speed (m/min) 1.1 to 1.4 1.0 to 1.1 0.75 to 1.15 0.65 to 2.5 1.2 1.3
Returns ratio 3 1 1.25 3.2 1.5
2
Sulfur capacity (tS/m /d) 1.6 to 1.8 1.7 1.81 1.21 1.11 1.54 1.64 2.29 1.7 1.94 1.29
2
Lead throughput (tPb/m /d) 3.6 7.5 6.9 2.6 5.2 7.8 6.2 5.5 8.1 7.8 3.1
2
Net sinter (t/m /d) 9.7 18.6 16.0 10.1 13.2 16.0 17.6 11.4 19.3 15.5 9.4
Sinter
% Pb 43.5 42 41.9 28 to 36 45.1 30 to 40 44.1 43 48 41.5
%S 1.6 2 1.8 1.3 to 1.9 1.3 1.7 2 to 2.5 1.7 1.6 to 2.1 1.7
% Fe 17.5 17 11.9 10 to 18 15.5 6 to 12 10.2 10 11.5 11.3
Gas
The Extractive Metallurgy of Lead
3
(Nm /h) 120 000 91 000 21 000 59 000 230 000 15 800 80 000 45 000 75 000 91 700
% SO2 4.2 5 to 6.5 7 3.3 4 5.5 2.8 4 to 5.0 5.5 5
TABLE 4.4
Effect of lead concentrate grade on sinter plant capacity.
Lead concentrate grade (% Pb) 50 60 65 70 75

Sulfur content (%) 23 20 18 16.5 15
Pb:S ratio 2.17 3.00 3.61 4.24 5.00
Sinter recycle ratio 3.10 2.11 1.67 1.28 1.07
Sinter production (t/m2/d) 9.4 13.5 16.6 20.8 24.5
Lead throughput (t/m2/d) 4.26 6.10 7.52 9.43 11.07
Sinter gas volume (Nm3/t Pb) 5910 4140 3350 2670 2270
Sulfur recovery to gas (%) 92.0 88.7 86.5 83.6 81.2
Theoretical capacities in terms of sinter production given in Table 4.4 are illustrated in Figure 4.7
together with actual plant data. The fact that actual sinter output can be higher than theoretical is due to
the addition of oxidised lead materials, such as residues, to the sinter feed as diluent. Where capacity
falls well short of theoretical, it is often due to the restrictive capacity of the blast furnace, which as
indicated above is more common with the processing of higher grade concentrates. There are also
variations in the sulfur burning rate of 1.8 t/m2/d due to characteristics of the sinter bed, such as porosity
and reaction characteristics of the particular concentrates, which will cause significant variations.
30
25
Sinter production (t/m2/d)
20
Plant data
15
Calculated
10
0
30.00% 40.00% 50.00% 60.00% 70.00% 80.00%
% Pb in concentrates
FIG 4.7 - Calculated and actual sinter plant capacities’ dependence on lead concentrate grade.
The use of oxygen enrichment of sinter plant air feed has been evaluated as a means of increasing
machine capacity in terms of the sulfur elimination rate. It is debatable whether there is any benefit,
since excessive bed temperatures must be avoided, requiring a reduction in the fuel content of sinter
feed and hence, lead sulfide feed. However, even if there were some benefit, oxygen is used in
considerable excess and inefficiently for sulfur combustion. On this basis alone enrichment is
generally not economically justified.

One means of increasing the lead throughput of a sinter machine is to use an oxidised lead feed
material as a sinter returns replacement. For this purpose the material needs to be correctly sized and
some form of agglomeration may be necessary, but it must be sufficiently strong to retain its form and
size. Clinkered Waelz oxide is a suitable material for this purpose and is used in ISF sinter plants. The
use of lead-rich slag produced by slag bath oxidation of lead concentrates, such as the Isasmelt
process, has been proposed as a method of adding high lead inert material to sinter feed and increasing
lead throughput.
In general terms sinter machine installations are complex with many moving parts. The operating
environment is hot and dusty and consequently can result in relatively high maintenance costs. There
is a complex array of parameters to be balanced and an inherent tendency towards instability with a
high reliance for optimum performance on the use of experienced operators. The high level of solids
recycle, and hence, the total material handling loads per unit of output, significantly adds to the costs
of the process. For these reasons the sinter plant–blast furnace combination is no longer cost
competitive in comparison with direct smelting processes for new greenfields installations.
GAS HANDLING AND CLEANING

The net gas output from the sinter machine is at a temperature of 200 to 500°C and contains a
significant load of dusts, fumes and volatile materials, including compounds of lead, cadmium,
mercury, chlorine and fluorine. The SO2 content can be variable from 2.5 per cent to 6.5 per cent,
depending on measures taken to raise its concentration such as tip end gas recirculation. Gas may also
be separated from the front end and tip end, giving relatively high SO2 concentrations from the front
end and low concentrations from the tip end.
For the production of sulfuric acid by the contact process gas strength should be above five per
cent and preferably closer to seven per cent. This is clearly difficult from lead sinter plants with a
single gas pass and either only front gas is used or tip end gas recirculation is applied. Where only
front end gas is used for sulfuric acid production, overall sulfur recovery to acid is of the order of
60 per cent; the remainder is discharged to atmosphere.
Gas that is not processed in an acid plant needs to be cooled to below 200°C using an open
humidification tower before being cleaned using bag filters to remove dusts and fumes before
discharge to atmosphere. In this process it is important to ensure that the gas temperature is not
lowered below its dewpoint as this can lead to serious corrosion problems. Although total or partial
discharge of sinter gas was commonly practiced in the past it is becoming less acceptable.
For acid production sinter gas is usually cleaned by drop out of dust in an open chamber or flue
followed by hot electrostatic precipitators of the plate and wire type with two or three fields in series.
This is followed by wet gas scrubbing and wet electrostatic precipitators to remove mist from the
scrubbing operation. A mercury removal scrubber may be included, if mercury levels in the clean gas
are high enough to give product acid above 1 ppm mercury. Mercury removal is not always necessary
as it is with zinc concentrate roasting.
Total collected dusts generally amount to between one and two per cent of the input sinter charge
and contain relatively high levels of lead, zinc, arsenic, antimony and cadmium, and sometimes other
volatile elements such as selenium and mercury. Collected dusts are usually directly recycled to the
sinter plant feed as a filter cake, but can be separately treated by leaching prior to recirculation in order
to remove highly volatile impurities such as cadmium and prevent high circulating loads developing.
Many devices are used for wet gas scrubbing such as spray towers, packed towers, plate scrubbers
such as the Peabody scrubber or Venturi scrubber. Scrubbing liquor is circulated through the scrubbing
system and becomes acidic due to the absorption of SO3 contained in sinter plant gas. Often the

scrubbing system consists of two stages, with the first as a quench or humidifying stage to reduce gas
temperature from 300°C to less than 100°C, followed by a second scrubbing–cooling stage, which
lowers the temperature to less than 38°C. The final temperature is important since the gas will be
saturated with water vapour and the temperature determines the amount of water going forward to acid
production, which must be less than that required to combine with the SO3 formed. Hence, there is a
direct relationship between the SO2 content of the gas and the maximum temperature of that gas leaving
the scrubbing system, as shown in Table 4.5.
TABLE 4.5
Temperature of wet gas as a function of SO2 content.
SO2 content of sinter gas (%) Maximum temperature of wet gas to acid production (°C)
8 40.1
7 38.1
6 35.2
5 32.2
4 28.6
The ‘weak acid’ scrubbing liquor containing sulfuric acid as well as chlorides and fluorides can be
very corrosive and appropriate materials of construction must be used. One particular area of high
corrosion potential is the boundary region where hot gas first meets scrubbing liquor. This is usually a
troublesome and high maintenance area for the containment equipment. In general these problems
appear to be less severe in the case of lead sintering than for zinc sintering or roasting operations.
The weak acid scrubbing liquor is bled from the system to maintain either a preset maximum
acidity or a maximum fluorine concentration. Otherwise the bleed will merely be set by the water
balance control. This solution also contains lead, zinc and cadmium dissolved from sinter dusts as
well as mercury and selenium. Mercury and selenium react to form mercuric selenide, which
precipitates and can foul heat transfer surfaces. The presence of selenium can be beneficial in
increasing the capture of mercury by the gas scrubbing system.
In some instances the scrubbing system includes a final stage of sacrificial silica packing to ensure
full capture of fluorine and to protect the acid conversion catalyst.
Following scrubbing and cooling, suspended droplets of scrubbing solution or mist are removed
in wet electrostatic precipitators. The cleaned gas may still contain unacceptable levels of mercury
vapour, which must be removed before transfer of gas to the acid conversion plant. There are a
number of mercury removal techniques but the most commonly used is the Boliden–Norzink mercury
removal process, which uses mercuric chloride solution to scrub the gas and absorb mercury
according to Equation 4.7 (Dyvik, 1985):
Hgo + HgCl2 = 2 HgCl (4.7)
Mercurous chloride or calomel is insoluble and precipitates from solution. It can be separated in a
thickener and removed from the system. Part of the calomel is treated with chlorine to regenerate the
mercuric chloride scrubbing solution. The system is capable of achieving less than 0.5 ppm mercury
in product acid or lower if reduced gas temperatures are used. It is important for efficient operation
that the gas coming forward from the electrostatic precipitators is free from suspended mist and is
classed as ‘optically clear’, otherwise contamination of the mercury scrubbing circuit will quickly
destroy mercury removal efficiency.

Following mercury removal the gas is suitable as feed to a conventional wet gas sulfuric acid
plant, of which there are many designs and configurations. This clean gas should be capable of
production of high-quality sulfuric acid.
The ‘weak acid’ or scrubbing solution bleed represents a disposal issue and is usually sent to an
effluent treatment facility where the acid is neutralised with lime to form gypsum and the dissolved
metals are precipitated. The filter cake can be returned to the sinter plant feed where the CaO content
will be useful as a flux addition. The filtrate solution containing chlorides can be discarded, provided
it meets relevant environmental standards.
After cleaning by scrubbing, the gas may be passed to a standard contact sulfuric plant.
SULFURIC ACID PRODUCTION

Sulfur dioxide in cleaned sinter gas is oxidised to sulfur trioxide at temperatures of around 400 to
500°C over a vanadium pentoxide catalyst. Resulting SO3 is absorbed in strong sulfuric acid and
reacts with contained water to form H2SO4.
The first stage of the acid plant involves drying the gas and any added air in a packed tower (drying
tower), where it is contacted with 93 to 96 per cent sulfuric acid at a temperature of around 65°C. Acid
is circulated between the drying and absorption towers to maintain the acid strength in the drying
tower and feed water into the absorption tower circuit. This provides most of the water required for the
formation of sulfuric acid by reaction with SO3. Hence, there are limits on the moisture content of
input gas as detailed in Table 4.5.
Dry cold gas usually then passes through the gas blower, is heated to 420°C and passes to the first
catalyst pass. The oxidation of SO2 to SO3 is exothermic and gas exiting the first pass may be of the
order of 600°C. Heat is extracted by heat exchange with incoming cold gas before transfer to the
second catalyst pass. There are many different arrangements of heat exchange between incoming cold
gas and the various gas streams to and from the catalyst beds, dependent on the particular plant design.
At least three, but more commonly four catalyst beds are used, and it is generally aimed to operate at
temperatures between 420 and 450°C.
Following the third catalyst pass, gas is treated in the interpass absorption tower to absorb SO3.
Exit gas from the interpass tower is reheated by heat exchange and passes to the fourth catalyst bed for
conversion of residual SO2, and then to the final absorption tower. With this double absorption
system, SO2 conversion can exceed 99.5 per cent.
A flow sheet of a typical sulfuric acid installation is given in Figure 4.8.
Single absorption is also used but achieves lower conversion at 98.0 to 98.5 per cent, and
emissions of SO2 in tail gas are much higher (five times). Unless tail gas scrubbing is applied, single
absorption plants will generally not meet normal environmental emission standards.
Controlled water additions are made to the final absorption circuit to control product and
circulating acid strength at 98.0 to 98.5 per cent H2SO4. Insufficient addition will result in oleum
formation with high corrosion potential, as well as the potential for fume generation.
Acid circulating over the absorption and drying towers must be cooled by heat exchange with
cooling water and represents a significant thermal load of low-grade heat. Plate exchangers are most
commonly used for this duty but shell and tube exchangers are also common. It is important to closely
control the temperature of circulating acid for optimum performance of the towers and to prevent the
generation of fine mist or SO3 fume, which can carry over into tail gas. Absorption tower acid is
generally controlled within the range of 80 to 90°C and high efficiency candle mist eliminators are
used to minimise carryover.

1st Pass
Heat Exchangers 1&2 Heat Exchangers 3&4
Blower Converter
Tail Gas
Air
Air
Clean
Gas Input
Cooler
Acid Pump Acid Pump

Tank Cooler Tank
Water
Additions
Product Acid
Stripping Interpass Final
Drying Tower
Tower Absorber Absorber
FIG 4.8 - Typical sulfuric acid plant flow sheet.
Product acid is drawn from the final absorption tower circuit and is cooled to 40°C before storage
in mild steel tanks.
Sulfuric acid produced from sinter gas is black in colour due to the presence of fine carbon. This is
derived from organic compounds such as flotation reagents present in lead concentrates, which distil
into the sinter gas on initial heating of the sinter charge. These compounds are captured in drying
tower acid and are decomposed by the strong acid to form finely divided carbon. Because of this the
acid has limited application – such as use for fertiliser production; otherwise it can be treated with
hydrogen peroxide to remove the coloration and form clean ‘white’ acid for more general application.


Burrow, W R, Ridley, K L and Adams, F C, 1956. Up-draught sintering at Port Pirie, The AusIMM Proceedings,
180:179-206.
Dyvik, F, 1985. Application of the Boliden Norzink mercury removal process to sulfuric acid production, in
Proceedings Extractive Metallurgy ’85 Symposium, p 189 (Institution of Mining and Metallurgy: London).
Grant, R M and Cunningham, B C, 1971. The relationship between sintering practice and lead blast furnace
performance at Port Pirie, paper A7 1-1 (The Minerals, Metals and Materials Society – American Institute
of Mining, Metallurgical and Petroleum Engineers: Warrendale).
Siegmund, A H J, 2000, Primary lead production – A survey of existing smelters and refineries, in Proceedings
Lead-Zinc 2000, pp 55-116 (The Minerals, Metals and Materials Society: Warrendale).
The AusIMM, 1958. Sintering Symposium (The Australasian Institute of Mining and Metallurgy: Melbourne).
Willis, M, 1980. The physical chemistry of lead extraction, in Proceedings Lead-Zinc-Tin ’80 Symposium,
pp 437-476 (The Minerals, Metals and Materials Society – American Institute of Mining, Metallurgical and
Petroleum Engineers: Warrendale).

CHAPTER 5
The Blast Furnace
INTRODUCTION
The blast furnace consists of a vertical shaft in which lead oxide contained in sinter is reduced to lead
metal by a counter-current flow of gas rich in carbon monoxide. Elevated temperatures are required and
the necessary heat and CO are generated by the combustion of coke with an air blast at the base of the
shaft. Coke is used to provide a non-fusible support for the charge and a free open structure to facilitate
uniform gas flow up through the shaft. Reduction of free PbO in the sinter by gaseous CO occurs from
the solid state in the upper shaft. The sinter melts in the lower part of the shaft and the bulk of the
contained lead, in the form of glassy silicates, is reduced to lead metal as it flows down over the hot coke
bed. Further reduction can take place in the slag pool contained in the hearth of the furnace.
The combustion zone at the base of the shaft is intense and is generated by an air blast through a set
of nozzles or tuyeres, impinging on the remaining coke charge. CO2 is generated and then reacts with
hot coke to form CO. Molten lead and slag collect in the furnace hearth with lead forming a lower
layer, which can be tapped either separately or with slag in a continuous tapper. With continuous
tapping a forehearth can then be used to separate slag and lead bullion.
The capacity of the blast furnace may be simply determined by the ability to burn carbon, which in
turn relates to the oxygen supply or blast rate. The latter is controlled by the permeability of the shaft
charge and hence depends critically on the nature and structure of the sinter and coke feed as well as
the presence of accretions, which can reduce the cross-sectional area of the shaft. Comparative
capacity can be defined by the carbon burning rate per unit of shaft cross-section. The carbon is
consumed to supply heat and CO, which in turn is consumed to reduce PbO, as well as Fe2O3, CuO,
ZnO and other minor metal oxides. Since most sinters have a reasonably consistent composition of
around 40 to 45 per cent Pb, it follows that the sinter treatment rate and bullion production rate per unit
of shaft cross-section also give meaningful comparative measures.
The ratio of CO:CO2 in the exit gas from the shaft is also an important parameter to be considered
in determining operational efficiency and is usually of the order of 0.4 for an open top furnace, but can
vary considerably. Under hot top conditions, which may represent excessive coke in the charge, the
ratio can increase to 1.0. The net heat generated in the furnace from a given quantity of coke is greatly
reduced as the CO:CO2 ratio increases. However, the distribution of that heat generation between the
lower and upper sections of the shaft is of considerable importance.
CHEMICAL PRINCIPLES AND THERMODYNAMICS

The basic reactions taking place in the furnace shaft are given in Equations 5.1 to 5.11:
C + O2 = CO2 (5.1)
C + CO2 = 2CO (5.2)
PbO + CO = Pbl + CO2 (5.3)
3Fe2O3 + CO = 2Fe3O4 + CO2 (5.4)

CHAPTER 5 – The Blast Furnace
Fe3O4 + CO = 3FeO + CO2 (5.5)
FeO + CO = Fe + CO2 (5.6)
ZnO + CO = Znv + CO2 (5.7)
Znv + PbO = Pb + ZnO (5.8)
Znv + PbS = ZnS + Pb (5.9)
PbSO4 + CO = PbO + SO2 + CO2 (5.10)
PbS + 2PbO = 3Pbl + SO2 (5.11)
The thermodynamic parameters for each reaction are given in Table 5.1.
TABLE 5.1
Thermodynamic factors for shaft reactions.
Reaction Heat of reaction at Heat of reaction at Free energy at 25°C Free energy at 1100°C
25°C (kJ/gmole) 1100°C (kJ/gmole) (kJ/gmole) (kJ/gmole)
5.1 -393.51 -392.48 -394.38 -403.21
5.2 172.43 169.54 119.83 -78.03
5.3 -58.57 -71.05 -68.39 -79.36
5.4 -50.75 -40.98 -62.53 -114.85
5.5 23.05 -17.55 24.05 -0.76
5.6 -12.60 -14.04 -12.75 -9.48
5.7 195.85 183.27 156.02 26.24
5.8 -254.42 -254.32 -224.41 -105.60
5.9 -232.65 -221.73 -193.74 -71.21
5.10 121.0 169.38 67.19 -143.18
5.11 255.93 246.84 182.37 -63.57
It is of note that except for ZnO, the principal reduction reactions of metal oxides with CO are
exothermic at operating temperature. However, the reaction of CO2 with coke regenerating CO for
reduction is highly endothermic, as well as the decomposition of lead sulfate (Equation 5.10) and the
‘roast reaction’ as given by Equation 5.11.
The equilibrium conditions for each reaction may be expressed in terms of the partial pressure
ratios of CO to CO2 and are illustrated in Figure 5.1. As a simplification this assumes solid–gas
reactions with unit activity of the solid oxide reactants. If in the molten phase, such as PbO dissolved
in slag, the activity will be much lower and the equilibrium ratios for CO:CO2 will be correspondingly
higher. For partial pressure ratios of one or above, covering the bulk of the reactions zones of the
shaft, Figure 5.1 indicates that PbO reduction should proceed readily, ZnO can be reduced to zinc
vapour above 800°C, and iron oxides will be reduced primarily to FeO. In Figure 5.1 the ZnO
reduction equilibrium is shown for a zinc vapour partial pressure of 0.01 atmospheres or one per cent
in the gas stream. Zinc partial pressure will vary widely; however, this serves only to illustrate that
zinc vapour will be present at partial pressures of this order.

2 PbO
C
Log(CO:CO2)
Fe2O3
0
Fe3O4
FeO
-2 ZnO
-4
-6
600 700 800 900 1000 1100 1200 1300
Temperature °C
FIG 5.1 - Equilibrium CO:CO2 ratios for reduction reactions (ZnO represents a Znv partial pressure of 0.01 atm).
FURNACE PERFORMANCE
The internal workings of the blast furnace are complex, with a range of reactions as above, often with
non-uniform gas flow due to charge variability and to accretion formation. The influence of volatile
components such as zinc metal and lead sulfide is significant and they can cause significant shifts in heat
generation from the base to higher levels in the shaft. Feed composition and furnace configuration can
have a major influence on performance and no two furnaces will operate in exactly the same way. This
makes operation more an art than a science, with high reliance on the experience of the operators. It is
also difficult to generalise on the performance characteristics and the following description must be
taken as one possible explanation of the mode of operation of the lead blast furnace.
There have been a number of attempts to model the lead blast furnace, notably Lumsden (1971),
Madelin, Sanchez and Rist (1990), as well as descriptions of the process chemistry by Willis (1980)
and Oldwright and Miller (1936).
Reaction zones
In simple terms, the furnace shaft may be divided into four zones.
Zone 1 – tuyere zone

The tuyere zone is from the hearth upwards to a point just above the tuyeres. This is the high
temperature zone in which carbon is oxidised by the air blast to CO 2 at temperatures above 1500°C.
Generally the lead blast furnace does not operate at high blast pressures compared with the iron
blast furnace or the ISF, and ‘raceways’ are not an important feature of the tuyere zone. Consequently
there can be differences in the oxygen content of gas across the furnace, with the chance of some gas
with relatively high oxygen levels being deflected by the charge and passing upwards in close
proximity to the wall. Towards the centre oxygen will be depleted and CO levels will tend to increase
and the temperature fall.

Liquid phases pass down through this zone over the hot coke bed and into the slag bath. Passage
of molten lead over the coke bed should counter any potential oxidation on passage through the
flame region.
Overall the gases leaving this zone have an oxygen potential (or CO:CO2 ratio) in thermodynamic
equilibrium with the slag and bullion formed and at the tapping temperature. There will be local
variations from tuyere to tuyere along the furnace and across its width, which may result in departure
from average equilibrium conditions. However, in general the outcome in terms of slag composition
and metal balance can be controlled by the carbon to air mass ratio.
The height of Zone 1 has been indicated by Madelin, Sanchez and Rist (1990) at 400 mm above the
tuyere level, but is likely to vary significantly and this should only be taken as an order of magnitude
guide.
Zone 2
In this zone, immediately above the tuyere level, reduction reactions predominate, particularly the
reaction of CO2 with coke to form CO at temperatures above 1000°C. Sinter commences to melt in
this zone and lead oxide in the form of glassy lead silicates is reduced by CO to metallic lead. Zinc
oxide is also reduced to form zinc metal vapour, which rises with the gas stream. Any lead sulfide
present can be volatilised and may react with zinc vapour in colder adjacent regions such as the
furnace walls or centre of the furnace, to form zinc sulfide and lead metal. This can give rise to the
formation of accretions.
The reaction of CO2 with coke to form CO is endothermic and will reduce the temperature in this
zone, but will be counteracted to some extent by the reduction of lead oxides, which is exothermic.
Zone 3
Above Zone 2 the charge is essentially in the solid state and below 900°C. Heat transfer from rising
gases to the descending charge occurs within this zone, and free PbO within the sinter is reduced to
lead metal by both CO and by zinc vapour in accordance with Equation 5.8. Reaction of zinc vapour
with CO2 to form ZnO occurs as the temperature falls below 800°C and generates heat. This tends to
form accretions on the colder furnace walls. However, zinc oxide formed in the upper part of the
furnace will descend with the charge and will again be reduced to zinc vapour at lower levels in the
shaft, thus forming a circulating load within the charge. This effect reduces temperatures in the lower
shaft by the endothermic reduction reaction and raises temperatures in the upper shaft by the
exothermic oxidation reaction. Although the furnace input of zinc can be low, the development of this
circulating load can mean that zinc still has a significant bearing on the performance of the furnace in
relation to the distribution of heat within the shaft.
Zone 4
The upper zone of the shaft essentially serves to transfer heat from the rising gas to the descending
charge with minimal reaction, and to remove any moisture contained in the coke. This zone can vary
widely from one furnace to another and exit gas temperature can vary upwards from around 200°C.
In general the gas flow is non-uniform. It is higher close to the furnace walls and lower in the
centre of the shaft. Gases close to the wall can still contain oxygen, particularly at lower blast rates and
consequently reduction is higher in the centre and temperatures are lower. This can lead to the

formation of a rigid core of material in the centre of the furnace. The effect can be more pronounced at
lower blast rates where more gas channels up the walls and gives rise to higher temperatures further
up the shaft, which in turn can cause melting and aggravate channelling.
Gas composition at the exit of the shaft is a key indicator of the overall mass balance of the blast
furnace and can be used as a controlling parameter. Normally this is a CO:CO2 ratio of close to 0.4:1.
The gas composition profile will show a low CO:CO2 ratio in Zone 1 at the tuyere level rising in
Zone 2 as CO2 reacts with hot coke and falling as CO is used for reduction in Zones 2 and 3. This basic
picture will be affected by the volatilisation of zinc and its reaction with CO2 as the temperature falls
to regenerate CO. Bearing in mind that a circulating load of zinc can build up between Zones 1 and 3,
this can have a significant effect on the gas composition profile and also on the zonal heat balance.
Bypassing of air up the walls of the furnace or through channels can result in the presence of some
oxygen in exit gas. This can be up to four per cent, suggesting utilisation of only 80 per cent of the
oxygen in blast air.
A schematic of a vertical cross-section through a typical blast furnace illustrating the above zones
and characteristics is shown in Figure 5.2.
Charge feed
Gas offtake
Furnace charge
Zone 4
Wall accretions
Zone 3
Zone 2 Central accretion

or ‘deadman’
Tuyeres
Zone 1
Blast air
Molten slag
Molten lead
Hearth
FIG 5.2 - Typical vertical cross-section of a lead blast furnace.
The above picture of the performance of the furnace is idealised and is complicated by
non-uniformity across the shaft section, giving rise to significant gas compositional changes from the
walls to the centre of the shaft with higher oxidation potential at the walls. Conditions at each tuyere

are also likely to vary in terms of access to coke and molten slag, as well as variations in gas flow.
Because of these multi-dimensional variations and the random occurrence of accretions, which
profoundly affect gas flow patterns in the shaft, it has been particularly difficult to adequately model
the operation of the blast furnace. Performance of a furnace is best with a new clean furnace and
charge, without accretions and when gas flow patterns are reasonably uniform. Performance
generally deteriorates from the start and the maintenance of a reasonable ongoing performance is the
art of an experienced operating crew.
Accretions
As illustrated in Figure 5.2 accretions are a key feature of the lead blast furnace and must be
adequately managed to maintain operation. Accretion formation is complex and as indicated above,
results from reactions of volatile components such as zinc and lead sulfide as well as fusion of the
charge and solidification in cooler regions of the furnace. Analysis has been reported by Oldwright
and Miller (1936), Ruddle (1957) and Polyvyannyi et al (1971).
Wall accretions can be of two types, those near the hearth comprising essentially of frozen slag
forming materials, and those higher up consisting of charge material bonded by condensed volatile
material or reaction products therefrom, such as zinc oxide lead sulfide and zinc sulfide. This latter
form of accretion can be sintered by an increase in temperature brought about by a rise in the level of
high temperature zone boundaries. Since these high temperature zones can rise and fall with furnace
variations, the accretions can exhibit a layered structure with varying degrees of sintering. Lead
present in wall accretions is largely as metal derived from the reaction of PbS with zinc. The sulfide
content of wall accretions tends to increase at lower levels of the furnace.
Hearth accretions are usually sulfide rich, extremely hard and refractory and can be a major cause
for shutdown for cleaning when they interfere with the flow of bullion or slag to the tapper.
The central accretion or ‘dead man’ or ‘sow’ is comprised of loosely bonded semiplastic fine
charge material formed as a result of attrition of larger material, displaced to the centre by the main
gas flow from the tuyeres, and bonded in much the same way as wall accretions. Since the ‘dead man’
is not removed and normally acquires a reasonably consistent shape and size, and further since it does
not normally impede the flow of lead bullion to the tapper, it is likely that the binding material has a
melting point below the temperature of the slag bath, and that the base of the column of the central
accretion is a reasonable open bed of coke.
Coke consumption reactions and heat balance
There must be careful balancing of operating parameters to achieve the necessary temperatures and
heat balance in various sections of the furnace shaft. Zone 1 supplies the heat and CO to drive the
furnace and must receive the required amount of coke to achieve the required temperature and to
generate reduction gases at the base of the shaft.
For a given sinter feed and blast rate, the operating parameters relating to fuel which affect furnace
performance are:
• coke supply rate,
• coke reactivity, and
• coke sizing.

Coke supply rate

If the coke rate is increased by increasing the relative proportion of coke in the furnace feed without
change to the blast air, the CO:CO2 ratio in smelter gas will rise, which means that less heat is
developed and the bottom temperature falls. In the extreme this has the potential to cause a freeze and
virtually stop the operation of the furnace and the phenomena is known as ‘over-coking’.
An overall mass balance of the furnace indicates that a five per cent change in the coke rate will
change the CO:CO2 ratio in exit gas from 0.4:1 to 0.58:1 or by almost 50 per cent. This provides a very
sensitive indicator of the furnace condition. If the furnace is ‘under-coked’ with the coke supply reduced
to give a low CO:CO2 ratio of say 0.2, then the slag temperature will rise and can theoretically exceed
1300°C. The oxidation conditions would increase and the loss of lead in slag would rise. Clearly, in
practice this situation could be rapidly controlled by reducing blast air, but this change will reduce lead
production. However, an increase in coke rate will also correct the situation without reducing lead
production, which tends to be counter-intuitive as a means of reducing bottom temperature.
Factors that affect the supply of coke to the oxidation zone will have a most significant impact on
the performance of the furnace, and are critical for adequate control of the furnace and for
achievement of optimum performance. It should also be noted that vapour phase reactions can shift
heat generation from the base to higher levels and reduce the amount of coke reaching lower levels of
the furnace. This will arise with high levels of zinc or sulfur in the furnace charge.
Coke reactivity
Since all the coke is consumed the overall heat generation and mass balance will not change due to
coke reactivity. A more reactive coke will promote reaction with CO2 to form CO in Zone 2. This
reaction is endothermic and will tend to lower the temperature at this point. The lower temperature
will promote the oxidation of zinc vapour by CO2, which is exothermic and will to some extent
compensate the effect of coke reactivity by heating the solids entering Zone 2. In the extreme this
could lead to partial melting of solids and then refreezing in the lower zone due to the formation of CO
(Oldwright and Miller 1936; Hopkins and Haney, 1954).
It is unlikely that coke reactivity will affect combustion rates and hence combustion efficiency in
Zone 1 where high temperatures are reached. Consequently, reactivity will only affect the relative
position of Zone 2 and is likely to have only minor impact on the performance of the furnace.
Coke size
The prime role of coke as a fuel and reductant as distinct from other fuels is to provide structure and
support for the charge, to allow uniform flow of gas and to separate lumps of sinter to prevent charge
fusion in the plastic temperature range. For this purpose the coke needs to be of similar size to the
sinter and is preferably of a uniform sizing to maintain the maximum voidage. With sinter at +50
-75 mm, coke should be similarly sized, although it is likely there will be some finer material present
from handling and attrition. For a given coke supply the size of the coke will affect reactivity in the
furnace. Coarser material will react less in the upper shaft and get through to the oxidation zone. In
some operations there is a practice of feeding both coarse and fine coke and to vary the proportions to
allow consumption of the fines in the upper zones, enhancing the retention of the size of the coarser
coke into the lower levels of the furnace. This provides an additional degree of control for
optimisation of the furnace, but it is generally best to minimise excessive amounts of both very coarse
and very fine coke to achieve a relatively narrow size distribution.

SLAG CHARACTERISTICS AND COMPOSITION

Lead blast furnace slags are basically represented by the CaO:FeO:SiO2 system, but with
significant additions of ZnO, Al2O3, Fe2O3 and MgO. The basic ternary phase diagram is given in
Figure 5.3, and shows that the commonly used slag region is within the low liquidus temperature
zone of the eutectic trough and roughly along the line joining Ca2SiO4 and Fe2SiO4 (Winterhager
and Kammel, 1961).
FIG 5.3 - Phase diagram CaO-FeO-SiO2 system.
Slag viscosity is a most important parameter for the performance of the furnace, with low
viscosity preferred to allow separation of slag and bullion, and to allow tapping of the furnace at a
practical rate. As well as lowering viscosity by raising temperature, slag viscosity at a given
temperature will increase with increases in the content of silica and alumina, and will decrease with
increases in the content of CaO, FeO and MgO, as well as PbO. Silica and alumina tend to form
polymers or network bonding in the melt, increasing viscosity, whereas those bonds can be broken
by the addition of CaO, FeO and MgO. However, changes in composition can also raise melting
points of the slag above practical levels, such as by MgO addition, and can also increase the
tendency to form solid phases in suspension, which can effectively raise viscosity. The latter effect
can be promoted by increases in alumina, and by the iron content, which can promote the formation
of solid magnetite (Fe3O4). Increasing the oxygen potential of the slag will tend to increase the
magnetite content, but this is offset by the increase in PbO content, which acts as a powerful fluxing
agent.

To work within a reasonable and practical melting temperature range, at or below 1200°C, it is
necessary to operate within a restricted region within the following boundaries of an idealised ternary
system:
• 30 to 40 per cent by weight SiO2
• 35 to 45 per cent by weight FeO
• 20 to 30 per cent by weight CaO
This will give average ratios as follows:
• FeO:SiO2 1.3
• CaO:SiO2 0.7
The presence of ZnO and Al2O3 will of course change the characteristics of the molten slag to
some extent, but it has been common practice and far less complex to initially consider the basic
ternary system as a means of defining the operating slag regime. Table 5.2 gives typical slag
compositions and composition ratios for most of the major lead blast furnace operations.
TABLE 5.2
Actual slag compositions and ratios.
Component Range Average

FeO 25 - 36% 30%
Fe3O4 2 - 5% 3%
SiO2 19 - 25% 22%
CaO 12 - 20% 16%
Al2O3 1 - 11% 6%
MgO 1 - 3% 2%
ZnO 8 - 22% 13%
PbO 1 - 4% 2.5%
CaO:SiO2 0.65 - 1.05 0.8
FeO:SiO2 1.14 - 1.76 1.43
Basicity index 0.9 - 1.3 1.05
Fluidity index 1.5 - 2.3 1.75
The basicity index = molar ratio of (CaO + MgO + FeO + ZnO + PbO) to (2SiO2 + 3Al2O3).
The fluidity index = mass ratio of (CaO + MgO + FeO) to (SiO2 + Al2O3).
The concept of ‘slag basicity’ is analogous to pH in aqueous systems and is useful in

characterising general behaviour of the slag as it affects the following:
• slag melting point and ‘shortness’ or softening – melting range;
• slag viscosity and therefore the ability to separate fine lead droplets;
• distribution of impurity elements between slag and molten lead in contact with the slag;
• electrical conductivity;
• oxygen and sulfur capacities; and

• interfacial tension between slag and molten lead, as affecting lead droplet size and a tendency of
the slag to foam.
Most simply, basicity can be expressed as the CaO:SiO2 ratio or by the more complete basicity
index as shown in Table 5.2. The fluidity index also shown in Table 5.2 is clearly a closely related
empirical guide, demonstrating that viscosity is influenced by basicity. A more basic slag will have a
higher fluidity or lower viscosity.
Of most importance is the effect of slag basicity on the activity of dissolved species such as PbO
and ZnO. The activity coefficient increases with increasing basicity and its effect can be illustrated by
Equations 5.12 and 5.13:
Pb + ½ O2 = PbOslag (5.12)
a PbO γ PbO . N PbO

K= 0. 5
= 0. 5
(5.13)
PO 2 PO 2
where:
K = the equilibrium constant for Equation 5.12
aPbO = the activity of PbO in the slag
PO2 = the partial pressure of oxygen
γPbO = the activity coefficient of PbO in the slag
NPbO = the mole fraction of PbO in the slag
From Equation 5.13, if the activity coefficient is increased by making the slag more basic, then for a
given fixed oxygen partial pressure, the mole fraction of PbO in the slag will fall. That is, the PbO
content of a slag in equilibrium with lead metal is reduced at a given oxygen potential by an increase in
basicity.
Basic slags have a similar effect on the ZnO activity coefficient and consequently will assist in the
fuming of zinc from the slag.
High CaO:SiO2 ratios tend to promote the formation of melilite structures in sinter, increasing its
strength and raising the softening temperature. Industry correlations suggest that at a lime:silica ratio
of 0.6 the softening temperature of typical slags is around 1025°C, whereas at a lime:silica ratio of 1.2
the softening temperature rises to 1110°C. Higher softening temperature means that the sinter
maintains its strength further down the blast furnace shaft, improving shaft permeability and
generally allowing for increased treatment rates. Slag fluidity is also increased to improve furnace
performance. Extra lime addition will increase the slag make and lead losses in slag, but this can be
compensated by the lower equilibrium concentration of lead in the more basic slag. To some extent
CaO can be replaced by ZnO in the slag and high zinc slags will generally correspond with lower lime
to silica ratios.
One downside to a high calcium slag regime is that the high CaO content of sinter is known to
cause its rapid degradation by absorption of water. This adversely affects the ability to hold stockpiles
of sinter for any length of time.
The Mount Isa lead smelter is a prime example of an operation with high lime to silica ratios at
around 1.2.
Basicity can theoretically be increased by raising the iron content, but high iron slags can have the
potential risk of forming magnetite (Fe3O4) in the lower oxidation zone of the shaft and in the slag bath.

This forms as a solid phase in suspension in the slag and considerably raises its viscosity, making
tapping difficult as well as the separation of slag and bullion. Simple tests are available for measuring
magnetite and can be applied to grab samples of slow cooled or granulated slag. This problem is not
generally encountered with the lead blast furnace, but can occur in the ISF.
In the case of high zinc inputs in concentrates and sinter, the quantity of slag will be dictated by the
limiting content of zinc in slag to around 17 per cent (or 22 per cent ZnO). Higher levels of zinc will
dramatically raise the slag viscosity and 17 per cent is generally regarded as a practical upper limit,
although for a typical operation no more than 15 per cent is preferred because of effects on accretion
formation and higher upper shaft temperatures. High zinc inputs in sinter plant feed will therefore
require additional fluxing to maintain these levels in blast furnace slag.
The lead content of slag is the sum of oxidised/dissolved lead and suspended droplets or prills, and
it is often difficult to distinguish between the two. Dissolved lead is affected by the oxygen potential
of the slag and entrained lead by slag viscosity. The total content of lead in typical blast furnace slag at
2.5 per cent is no longer acceptable for the dumping of slag as land fill, or for use as a construction
material, since it will fail the USEPA Toxicity Leach Procedure (TCLP), which is used as a
benchmark for the suitability of material for landfill. Some form of additional slag cleaning is
therefore required before dumping or utilisation. This may take the form of an electric furnace for
settling and further reduction, or a slag fuming furnace. The slag fuming furnace will primarily be
aimed at recovering zinc but is most efficient in also recovering most of the residual lead. Details of
these subsidiary operations are covered in Chapter 8.
FURNACE CONSTRUCTION
The lead blast furnace consists of a rectangular shaft with sidewalls made up from a series of water-
cooled hollow steel jackets. Refractory lining is unnecessary since an accretion layer forms on the
inner surface to protect the steel from attack.
The shaft narrows at the ‘bosh’ to the lower section containing the tuyeres. This allows for the
reducing volume of the charge as coke is consumed and the sinter melts. In older furnaces the top shaft
can be refractory brick within a steel shell, but the lower section around the tuyeres will be of water-
jacketed construction. Furnaces constructed in this way tend to burn out the joint between the upper
refractory and the lower water jackets and the full steel furnace was a significant improvement. It is
also easier to remove accretions from the steel surface compared to refractories and this is a key
advantage of a water jacketed furnace.
The tuyeres are fitted through the jackets and are constructed of copper, often fitted with stainless
steel tips to reduce corrosion and erosion. The cold air blast is sufficient to keep the tuyere bodies
cool. Jackets at the tuyere level can be refractory lined on initial installation, but this is gradually
replaced by accretions. The influence of the tuyeres can cause burn out of jackets, particularly with
oxygen enrichment of blast air, but this can be overcome by the projection of the tuyere further into
the furnace.
The lower section of the furnace sits on a hearth made up of several layers of refractory brick and a
castable refractory crucible, all held within a steel frame. The construction of the hearth and selection
of the bricks and refractories used is critical to avoid leakage of molten lead and expansion of the
brickwork, which can limit the operating life of the furnace before reconstruction. If properly
constructed this is not a problem and hearth life can be determined more by the build up of accretions,
which gradually restrict the flow of bullion to the tapping point.

The integrity of the jackets and any lining refractory is another key element in determining furnace
life, which is in the range of two to seven years, before extensive re-bricking and reconstruction is
required. An advantage of water-jacketed construction is that failed water jackets can be easily and
quickly replaced compared with difficult repairs for a refractory lined furnace shaft, although with
maintenance and good cooling water flow and the use of corrosion inhibitors in the cooling water,
jacket failure is not a common problem.
A schematic of a typical lead blast furnace is given in Figure 5.4, and shows an open topped
furnace with feeding by rail-mounted dump cars and fitted with a central gas offtake hood.
FIG 5.4 - Cross-section of a typical lead blast furnace.

The width of the furnace at the tuyeres or lower section is set by the penetration of the air blast and
is in the range of 1.2 to 2.0 m, but more commonly 1.5 to 1.8 m. The tuyeres are set at a height of
around 450 mm above the furnace tap hole. The upper shaft width can be expanded to 2 to 3 m and the
overall shaft height is around 5 to 6 m. Some experimentation with tuyere angle of inclination and
distance above the hearth may be needed for each furnace to achieve the desired crucible temperature
and lead content in slag.
The length of the furnace cross-section is variable depending on the required capacity, but is
limited by the distance slag is required to flow to the tapping hole. The limiting distance for slag flow
is of the order of 6 to 7 m, which dictates the length of a furnace with end tapping. A central tapping
hole will allow for increased length and in practice furnaces range from 5 to 10 m. Tuyere spacing is
also variable from 310 to 480 mm, but averages around 450 mm, giving ten to 20 tuyeres per side.
Blast air volume ranges between 1000 and 2000 Nm3/h per m2 of hearth area. Tuyeres have a jet
diameter ranging from 50 to 80 mm and carry 0.12 to 0.18 Nm3/s of air, indicating a superficial
velocity of 40 to 60 Nm/s. Blast pressure is in the range of 15 to 25 kPa, quite low compared with the
iron blast furnace, but necessary because of the continuous tapping systems used. Tuyeres are
constructed of copper and can have stainless steel inserts at the tip to limit corrosion and erosion. A
sight glass is fitted at the external end to allow the operator to view into the furnace. Airflow to
individual tuyeres can be controlled by dampers and they can be isolated to allow cleaning by
punching through with a bar from the sight glass port. Blast air is usually delivered by Rootes type
blowers and is normally not preheated, but can be enriched with oxygen.
Furnace cooling is by water circulating though the furnace wall jackets. The water is usually pumped
from a head tank to provide security supply, through the jackets and then through a heat exchanger,
removing heat to an evaporative water cooling system. It is important for the circulating water to be
treated and softened as internal corrosion or blockage of jackets can be a major cause of failure. The
temperature of water leaving each jacket is usually measured and recorded, since loss of cooling will
lead to jacket failure and leakage of water into the furnace. This is difficult to detect, but can cause
solidification of the charge adjacent to the leak and eventual blockage of the shaft and shutdown.
The furnace design at the Port Pirie smelter differs from the standard approach, having a second
row of tuyeres in the upper section and 990 mm above the lower row. There are fewer tuyeres in the
upper row and the airflow is less than for the lower tuyeres. This particular arrangement was designed
to allow for an increase in the upper shaft width to 3.0 m to overcome problems associated with
accretions bridging across the narrower shaft, particularly when operating with relatively high zinc
concentrations in slag, at 18 per cent (Green, 1977).
Details of the lower section and hearth construction of the Port Pirie furnace, and a plan showing
the centrally located tapping arrangement are given in Figure 5.5.
Furnace top and furnace feeding

A measured mix of sinter and coke is delivered into a weighed transfer hopper from separate feed bins
and the contents are dumped into the top of the furnace. Some furnaces can be fitted with fixed feed
hoppers and others use rail-mounted bottom dump transfer cars.
Most furnaces have a top open to the atmosphere with a central off-gas draft hood. The hood is
under suction and considerable dilution air is sucked in down through the top of the furnace charge.
The off-gas volume is consequently three to four times the blast air volume, depending on the hood
suction applied and in some cases can be significantly higher. The purpose of the open top is to
provide access for the regular cleaning of accretions from the furnace walls. It also facilitates the

FIG 5.5 - Port Pirie blast furnace design (Fern and Jones, 1980).

charging of large and irregular plant recycle materials, but has the major disadvantage that the
development of gas channels within the charge due to accretion build-up and uneven gas distribution
can locally overload the off-gas draughting and cause a blow-out of gas from the surface of the charge
directly to atmosphere. This gas carries a heavy load of lead and zinc oxide fume and is a significant
hazard and a serious environmental issue. Enclosure of the top of the furnace is possible, but impedes
access to remedy or prevent an impending or existing gas blow. A sealed top furnace such as the ISF
fully prevents this situation. However, the propensity to form accretions is far greater in the lead
furnace where zinc vapour is re-oxidised in the upper section, than is the case in the ISF. Doors are
often installed over the top and opened only during charging, but this does not provide a seal or
adequately control a major furnace blow. Some installations use multiple furnaces with one on
standby to allow a shutdown for accretion removal. However, this is a highly inefficient and costly
practice. This undesirable feature of the standard lead blast furnace is perhaps one of the reasons why
its use will be phased out, and it is unlikely to be applied in any new lead smelting operation.
Tapping
Tapping of lead bullion is usually continuous through an inverted lead siphon located at one end or on
the side of the furnace. This maintains a fixed level of molten lead in the crucible, which is important to
preserve the integrity of the base of the hearth and prevent attack from the higher temperature slag. Slag
may be separately tapped, intermittently or continuously, through an underflow-overflow weir
arrangement. For batch tapping the furnace is fitted with a water-cooled tapping breast containing the
tapping hole. The tapping hole is plugged with fireclay and is opened manually using a bar or an oxygen
lance and slag is directed into a settling forehearth before overflow to either a ladle or granulator.
Bullion is collected and siphoned from the base of the settler and fed to the bullion collection system.
For continuous tapping, the Asarco design of continuous tapper is commonly used and provides
for both bullion and slag tapping at the one point (Roy and Stone, 1963). A water-cooled steel tapping
breast contains an underflow weir to provide a furnace seal and is attached to a refractory lined
channel connected to a forehearth in which bullion and slag are separated by settling. Lining is
commonly chrome magnesite brick. The forehearth is a steel shell lined with castable refractory. It
contains an overflow and underflow weir for separation of lead and slag into two separate streams,
and a refractory lined cover fitted with gas burners to maintain a fluid slag surface. Since refractory
life is limited in this duty, the forehearth is usually removable and can be mounted on rails for rapid
changeover, which may take from two to eight hours.
With continuous tapping of slag it is necessary to balance the head of slag in the tapping device with
the weir height and gas pressure in the furnace. Factors such as erosion of the weir bricks, or a rise in gas
pressure due to changes in furnace conditions, or the nature of the charge can cause a blow-out of hot gas
from the tapper, and ventilation must be provided to accommodate this situation. This can be corrected
rapidly by reducing the blast rate. Fine adjustments to the weir height can be made by inserting or
removing thin (10 - 20 mm) slices of high quality brick into the ‘V-notch’ of the weir.
Lead bullion flows from the tapping facility via a Y launder into either of two steel ladles lined
with castable refractory and located in a pit adjacent to the furnace. The ladles are usually around 10 t
in capacity and are handled by overhead gantry crane, transporting the ladles to the copper drossing
operation.
Similarly, molten slag can be run into cast steel ladles or directly into a granulator. The usual form
of granulator is a launder carrying a large flow of water into which the slag stream is directed. The slag
stream is broken up by the water flow and chilled to form particles similar to coarse sand. The stream

flows into a pit where the slag settles out and can be recovered by scraper conveyor and elevated to a
hopper for drainage of retained water, and from where it can be trucked to disposal. Normal slags can
be granulated without difficulty, but in situations where matte, speiss or bullion is present, explosions
can occur in the granulation launder due to encasement and superheating of water. The ratio of the
mass flow of granulation water to the mass flow of slag is typically 30:1.
Gas handling system

Off-gas from the top of the furnace may be three to four times the blast air input and in addition an
equivalent volume of ventilation air can be drawn from around the furnace, covering tapping points,
slag granulation, transfer of bullion to ladles and drossing of bullion. Total ventilation air and off-gas
is usually cooled by water injection in a spray tower to around 150°C and is then filtered in a bag
house and the cleaned gas discharged to atmosphere. It is important to maintain the gas above its
dewpoint during filtration to prevent corrosion and bag failure. Solids loading of the gas to the bag
house can range from 2 to 10 g/Nm3. Using a modern bag house with reverse pulse cleaning, a filter
area of 30 m2 per 1000 Nm3/h is suitable. Collected dusts are pulped in water, filtered and the filter
cake added to sinter plant feed. If the dusts contain substantial amounts of impurities such as cadmium
or thallium, the filtrate may be processed to recover these metals. A feature of the traditional blast
furnace and sinter plant is the huge volume of dilute process and ventilation gases loaded with fumes
and dusts which need to be collected and cleaned.
Off-gas will contain some sulfur dioxide and, depending on its concentration, removal by scrubbing
could be necessary, although this is generally not the case (see section below on sulfur balance).
FURNACE OPERATION
Feed preparation and feeding methods

Both sinter and coke need to be correctly and closely sized for optimum performance of the blast
furnace. Sinter is delivered as predominantly -150 mm +50 mm lump material from the sinter plant
with undersize forming recycle within the sinter plant (‘return sinter’). Purchased coke normally
contains an excessive amount of fines as received and needs to be screened before use in the blast
furnace. The coke fines (‘breeze’) can be used as part of the sinter plant charge and for dross
conditioning during the refining operation. Furnace coke is sized similarly to sinter at +50 mm, but
fine coke at +10 mm may also be added to control coarse coke size retention into the lower shaft. Coke
and sinter may be added separately to the furnace in alternating layers or may be mixed together prior
to charging. Accurate weighing of the components as batches is the normal practice, often using
transportable hoppers on a weigh scale. The hopper is then moved to the top of the furnace and the
contents dumped in. Alternatively the charge may be dumped into a subsidiary hopper for controlled
feeding into the furnace.
Placement of the charge, in particular the rilling of coarse lump material towards the wall of the
furnace can cause segregation and a more open structure against the wall, thus affecting gas
distribution and encouraging accretion formation on jackets and wall sections. This will also
aggravate the formation of a central dead zone within the furnace as well as raising oxygen levels
close to the wall, and is an important consideration in the design of the charging system. Most
charging systems therefore add feed at the furnace walls, allowing the coarse material to rill towards
the centre of the shaft rather than the walls.

Furnace accretion removal

The formation of accretions within the charge and particularly on the walls of the furnace is a major
issue and can restrict gas flow and hence furnace throughput, as well as causing gas channelling and
surface eruptions or gas blows. Accretion formation is discussed above and the main areas of concern
are the wall accretions, the central accretion or ‘deadman’ or ‘sow’ and the hearth accretion.
One factor contributing to the formation of the central accretion or ‘deadman’ is the lack of
adequate penetration of the blast. This can be corrected by increasing blast velocity through reduction
in the diameter of the tuyeres and also by reducing the width of the furnace at the tuyere level. The
Naoshima Smelter in Japan reported an effective removal of the central accretion by these measures,
including reduction of furnace width from 1.66 to 1.42 m, and significantly increased furnace
capacity (Moriya, 1989).
The presence and location of accretions can be identified by temperature distributions and gas flow
patterns. Removal of wall accretions can simply be done by barring down with access through the top of
the furnace, either manually or by using mechanical hammering devices. For difficult accretions,
explosive charges are employed. In this case a pipe is driven down into the accretion and an electrically
detonated charge is dropped down the pipe and exploded. Damage to the jackets is always a risk with
this approach as well as the hazard to operators with the handling of explosives. In the extreme, the
furnace can be ‘burnt down’ by discontinuing feed, allowing the charge to drop down to just above the
tuyere level. Ready access to the walls is then possible for the removal of any remaining deposits as
necessary, and this approach will effectively remove the central ‘dead man’ or ‘sow’.
As indicated above, the hard hearth accretion forms relatively slowly and eventually causes
interruption to the tapping of the furnace. It requires a complete shutdown for removal.
Furnace capacity
Furnace capacity is ultimately the lead production rate as tonnes per day per square metre of hearth
area, but is basically controlled by the carbon burning capacity in tonnes of carbon burned per day per
square metre of hearth area. This in turn relates to the air blast or oxygen throughput that can be
achieved, as influenced by the permeability of the charge. Hence the importance of uniform sizing of
coke and sinter, and the retention of sinter structure without degradation.
Data of plant performance for a range of smelters are given in Table 5.3.
Carbon use is for reduction, but is mainly for the provision of process heat and appears in the heat
content of molten slag, lead bullion, exit gases and heat lost from the furnace walls in cooling water. In
this sense carbon demand is more closely related to sinter throughput than other factors. From
Table 5.3 fuel use is generally within the range of 90 to 100 kg of carbon per tonne of sinter processed,
whereas the carbon used per tonne of bullion varies over a much wider range of 170 to 370 kg/tonne.
This emphasises the advantage of maximising the lead content of sinter.
Actual fuelling requirements can be established from detailed heat and mass balances for a
particular furnace. However, for a typical lead blast furnace, a fuelling level of 90 kg/t of sinter would
appear to be a reasonable figure for efficient operation. If the top gas CO:CO2 ratio is 0.4 then
2.286 kg of oxygen are required per kilogram of carbon burned. This is supplied by reduction of sinter
and by the air blast.
For a sinter of 45 per cent Pb and ten per cent Fe the reduction oxygen supplied will be close to
4.9 per cent, hence one tonne of sinter will supply 49 kg of oxygen and consume 21.43 kg of carbon.
The remaining (90 - 21.4) = 68.6 kg of carbon will require 156.8 kg of oxygen to be supplied by the air
blast, representing 523 Nm3 of blast air.

82 TABLE 5.3

Data for commercial lead blast furnaces.
Plant Belledune Binsfeld- Chigirishima East Helena Glover Herculeneum Hoboken Mount Isa Nordenham Port Pirie Torreon
hammer
Number of operating furnaces 1 1 1 2 1 2 2 1 1 1 3
Lead production (t/a) 108 000 92 000 90 000 70 000 120 000 225 000 125 000 156 000 102 300 215 000 180 000
Sinter feed rate (t/h) 40 29 22 35 39 30 41 44 29 54 62.5
Coke feed rate (t/h) 5.1 2.8 3.15 4.6 2.66 5.8 9.73
Furnace dimensions (m × m) 1.68 × 6.4 1.7 × 5.5 2.05 × 7.93 1.9 × 7.74 1.76 × 8.5 1.3 × 7.5 1.83 × 7.02 1.2 × 7.6 1.5 × 10.7 1.52 × 6.4
2
Cross-section area (m ) 10.75 10.7 9.35 16.2 14.8 14.96 9.75 12.85 9.12 16.2 9.73
Number of tuyeres 36 32 42 40 46 + 32 21
3
Blast volume (Nm /h) 20 500 8400 16 500 13 600 25 500 26 000 27 000 20 000
Oxygen in blast air (%) 26 23 21 25 - 27 23.5 23 25 22.5 23.5 25 21
Coke cal value (kJ/kg) 7000 7600 6200 7000 6700

Coke fixed carbon (%) 90 93 93 82 83
Bullion (t/d) 360 280 228 220 365 700 347 510 290 650 500
S content (%) 1.3 <1 <2 0.09 0.15 0.4
Cu content (%) 2.5 0.03 0.02 2.2 0.06
Matte produced (t/d) 15 0 30 0 31 0 41 40
Slag produced (t/d) 430 85 - 110 280 330 760 350 650 150 - 200 690 600
Pb content (%) 3.5 1.25 3.6 1.8 2.2 2 2.5 2.6 1.75 2.6 1.3
FeO content (%) 36 33 28 25.8 30.8 33 32.5 22.8 32.5 26.3 31.4
CaO content (%) 15.5 17.5 20 19.6 15 12 16.3 24.5 20.5 15.1 20.5
SiO2 content (%) 20.5 20.5 21 22.3 27 22 24.9 21 19.5 21.6 19.9
Off gas volume (Nm3/h) 255 000 40 000 19 200 36 000 170 000 25 000 92 500 40 000 To 60 000
Off gas dust load (t/h) 1.25 0.8 0.8 2.5 0.4 0.5 3
Performance ratios
2
Carbon use (t/m .day) 10.2 5.2 4.2 4.7 7.0 7.0 7.1
2
Sinter input (t/m .day) 89.3 40.9 56.5 51.9 63.2 48.1 50.5 82.2 76.3 80 51.4
2
Bullion output (t/m .day) 33 33 24 14 25 23 18 40 32 40 17
3 2
Blast rate (Nm /h.m ) 1907 898 1019 919 1705 2023 1667 770
Carbon use (kg/t of sinter) 114 100 66 98 85 92 89
Common tuyere capacity is 700 Nm3/h and blast air supply from two opposing tuyeres is
1400 Nm3/h for a furnace length of around 450 mm (tuyere spacing), or a furnace cross-sectional area
of 0.765 m2 for a 1.7 m wide furnace. This represents 1830 Nm3/h of blast air per square metre of
hearth area. Hence 1 m2 of hearth can handle 1830/523 = 3.5 t/h of sinter (84 t/m2.day), and lead
bullion production will be around 1.5 t/h.m 2 (36 t/m2.day).
In this case the carbon burning rate is 84 × 90/1000 = 7.5 t of carbon/m 2.day.
For the above illustration the overall heat balance for the blast furnace will be as shown in Table 5.4.
TABLE 5.4
Blast furnace overall heat balance.
Heat supplied by coke combustion to CO2 2510 MJ/t of sinter 100%

Heat absorbed by metal reduction reactions 748 MJ/t of sinter 29.8%
Heat content of slag at 1200°C 778 MJ/t 31.0%
Heat content of bullion at 1200°C 82 MJ/t 3.3%
Heat content of exit gas at 220°C 133 MJ/t 5.3%
Heat absorbed by reduction of CO2 to CO 516 MJ/t 20.5%
Heat lost in cooling water 253 MJ/t 10.1%
Table 5.4 illustrates the general distribution of heat generated by the full combustion of carbon to
CO2 and the significant loss of potential heat by the formation of CO and its content in the exit gas.
Reduction in the CO:CO2 ratio in exit gas from 0.4 as assumed above to 0.2 would reduce coke
consumption for the same furnace operation and heat balance conditions from 90 kg/t of sinter to
81 kg/t of sinter.
By raising the lead content of sinter from 45 per cent to 48 per cent for the same assumed furnace
conditions, lead bullion production can be raised by seven per cent for the same coke consumption.
Although the above calculations are simplistic they can be used to clearly illustrate the impact of
key process parameters on furnace performance, such as the CO:CO2 ratio in exit gas, the Pb content
of sinter, the blast rate and the oxygen content of blast air. There are other practical limits on these
parameters to maintain practical operating temperatures at various regions in the furnace shaft, and to
minimise the formation of accretions and other obstructions.
Oxygen enrichment of blast air

Experience with oxygen enrichment of blast air is illustrated in Figure 5.6 (Fern and Jones, 1980),
which shows that furnace capacity is increased by five times the oxygen percentage increase. A
two per cent enrichment from 21 per cent to 23 per cent will raise furnace lead production by ten per
cent. Blast furnace production is thus directly proportional to the oxygen flow rate given a constant
tuyere volume and other furnace parameters.
There is some indication that oxygen enrichment can increase the level of lead in slag, but
according to Fern and Jones this can be counteracted by raising the CaO content of the slag. Most blast
furnaces today run with some level of oxygen enrichment of blast air to maximise furnace capacity
and this usually ranges up to 25 per cent oxygen content in blast air.
Using the above mass balance calculation as an example, by raising the level of oxygen in blast air
from 21 per cent to 23 per cent the blast air requirement per tonne of sinter would reduce from

45
40
35
East Helena
% Change in Production
30 Bunker Hill
Chimkent
25
Trail
Hoboken
20
Ust Kamenogorsk
15 Trend
Linear (Trend)
10
0
20 22 24 26 28 30
% Oxygen in Blast Air
FIG 5.6 - Effect of oxygen enrichment on furnace capacity at various lead plants (Fern and Jones, 1980).
523 Nm3 to 478 Nm3 and the quantity of sinter handled per square metre of hearth area would rise
from 3.5 t/h to 3.82 t/h or an increase of close to ten per cent for the same gas flow rate. This is in
agreement with observed practice.
Blast preheating
Blast preheating theoretically has the potential to significantly reduce the requirements for internal
heat generation and hence carbon consumption, and is commonly used in other blast furnace
operations. Blast air is usually preheated by heat exchange with hot off-gases directly, or after
combustion of the CO content to further raise their temperature. However, in the case of the lead blast
furnace, the open top arrangement leads to excessive dilution of the off-gas and leaves little
opportunity to use flue gases as the heat exchange medium to achieve significant blast air preheat
temperatures. The level of CO is also too low for use as a fuel for preheating as in other blast furnace
operations. The counter-current operation and low top temperatures also means that there is effective
recovery of heat from the furnace gases to the descending charge and hence it achieves charge
preheating rather than blast air preheating, which is more necessary with hot top operation such as
with the Imperial Smelting Furnace.
There is also the view that preheating of blast air and maintenance of bottom furnace temperature
will mean a reduction in the coke rate and hence the volume of gas flowing up through the furnace.
This will reduce the heat available at the top of the furnace to meet requirements of charge heating and
in the limit would necessitate charge preheating – as required for the ISF.
General operating practices

In general the blast furnace operates best at its maximum design blast rate. Any attempts to run at
reduced blast usually results in poor gas flow distribution with attendant problems of accretion
formation or central dead zone enlargement due to low blast penetration into the charge. Sinter quality
is of paramount importance in maintaining a high blast rate and good gas distribution and it is often

preferable to reject poor quality sinter for recycle in the sinter plant rather than attempt to treat it
through the blast furnace, since any upsets resulting from poor gas distribution and resulting in
accretion formation can take considerable time to correct.
Conditions at the tuyere level are also critically dependent on the coke supply rate as well as the air
supply rate, and if this is deficient temperatures will fall, reducing the smelting rate, even though the
blast rate has been maintained. Blast furnace condition at the tuyere level can be indicated to the
operator by ‘clear and bright’ tuyeres as observed through the sight glasses. Among other measures,
this can also indicate coking conditions or whether the furnace is receiving sufficient or excessive
coke supply at the tuyere level. Coking requirements are discussed above in the section on Coke
Consumption Reactions and Heat Balance.
A number of temperature measurements of the charge at various levels within the furnace is
beneficial in indicating imbalances and poor gas distribution, or in indicating inappropriate fuelling
conditions. However, this is seldom practised.
The condition of the slag is also a key indicator to the operator. A change in slag viscosity can
result from changes in slag temperature and from sinter compositional changes or from the formation
of magnetite as a result of excessive oxygen potential at the base of the furnace. High slag viscosities
can cause major difficulties with tapping and the separation of bullion from slag. It can cause a build-
up in slag levels in the furnace and interference with the operation of the tuyeres or even blockage of
the tuyeres. With continuous tapping, a reduction in slag viscosity can also result in excessive
lowering of the slag level and a blow-out of gas through the tap hole. Stable slag conditions are
therefore of major importance.
ENVIRONMENTAL ISSUES
Particulate lead emissions
The main environmental concern with lead blast furnace operation relates to the open top and the
emissions therefrom. As discussed above under ‘Furnace Top and Furnace Feeding’ ‘gas blows’ can
cause bypass of the venting system leading to emissions directly to atmosphere. The emitted gas
contains a heavy load of lead and zinc oxides. Although infrequent, this is becoming unacceptable and
means of capture or avoidance are necessary. Enclosure of the top of the furnace can contain
emissions, but will interfere with access for the management of accretions, particularly when a blow is
occurring. The removal of accretions is a constant need with the lead blast furnace and is generally
regarded as incompatible with an enclosed top.
Alternatively, extensive hooding and a high level of ventilation is necessary to capture ‘blows’ in
most situations, but carries the cost of a high volume of gas to be moved and filtered.
Apart from the furnace top there are a number of points of fume emission such as from tapping
operations as well as high lead dust from raw materials handling operations, which all require
extensive ventilation to capture such emissions.
Sulfur in off-gas and sulfur balance
As indicated in Chapter 4, sinter contains between 1.0 and 2.0 per cent sulfur and typically 1.7 per cent
for a lead content of around 45 per cent. This is the major input of sulfur to the blast furnace, although
coke can contribute of the order of five per cent of the total sulfur supply.

The sulfur content of blast furnace bullion is around 0.5 per cent and slag around 1.5 per cent. The
remaining sulfur reports to furnace off-gases. Some may be captured as a basic lead sulfate in fume,
which is recycled to the sinter plant, otherwise the remainder reports as SO2 in filtered off-gases and is
normally discharged to atmosphere.
Equilibrium conditions at the base of the furnace would suggest that the SO2 partial pressure
should be of the order of 10-7 to 10-6 atmospheres. Consequently the sulfur content of the gas stream
from the base of the furnace should be negligible and sulfur will be captured in the bullion and in slag.
It follows that the presence of SO2 in furnace exit gas results from reaction higher in the shaft,
probably the decomposition of sulfate according to Equation 5.10 and the reaction between
volatilised PbS and PbO according to Equation 5.11.
A typical balance may be as follows per tonne of product lead:
• sinter – 2.27 tonnes at 45 per cent Pb and 1.7 per cent S 38 kg of S per tonne of lead
• coke – 0.2 tonnes at one per cent S 2 kg/t
• bullion – 1.0 tonnes at 0.5 per cent S 5 kg/t
• slag – 1.2 tonnes at 1.5 per cent S 18 kg/t
• fumes – 35 kg at six per cent S 2 kg/t
• balance of sulfur reporting to blast furnace gas 15 kg/t
In this example 40 per cent of the sulfur reports to the blast furnace gas, but this proportion will
greatly depend on sinter composition.
Typical gas volumes emanating from the blast furnace operation are as follows:
• blast furnace gases 1200 Nm3/ t of lead
• furnace top dilution air 3500 Nm3
• ventilation air 5000 Nm3
Ventilation airflows in particular vary greatly from one plant to another depending on particular
configurations and design. If the total gas flows are handled collectively for fume separation the total
gas flow will be 9700 Nm3 per tonne of blast furnace lead and will contain 15 kg of sulfur or 30 kg of
SO2. This represents a concentration of 3.1 g of SO2 per Nm3 or approximately 0.11 per cent by
volume. Without dilution by ventilation air the concentration would rise to 6.4 g of SO2 per Nm3 or
0.22 per cent by volume.
Emission standards for SO2 vary widely, but a common concentration limit is 1.25 g of SO2 per
Nm3, which has to be met by sulfuric plant emissions. On this basis, sulfur emissions from the blast
furnace commonly exceed normal standards by a substantial margin. This has indeed resulted in the
closure of some European lead blast furnaces or the conversion to alternative technologies. The
alternative is to scrub the gas after fume collection with a lime slurry, which is capable of reducing
the SO2 concentration to 0.01 per cent by volume or 0.3 g per Nm3. Otherwise a combination of total
plant ventilation gases from sinter plant and refining operations with blast furnaces gases may be
able to meet overall emission concentration limits for sulfur, but at the expense of large gas volume
movements per tonne of lead produced (at around 12 000 Nm3/tonne of lead).
REFERENCES
Collins, H F, 1910. The Metallurgy of Lead (Charles Griffin and Co: London).

Fern, J H and Jones, R W, 1975. The development and operation of a continuous tapping lead blast furnace at
Port Pirie, in Proceedings AusIMM Annual Conference, pp 155-165 (The Australasian Institute of Mining
and Metallurgy: Melbourne).
Fern, J H and Jones, R W, 1980. Lead blast furnace smelting with oxygen enrichment at the BHAS plant, Port
Pirie, South Australia, in Proceedings Lead-Zinc-Tin 80 – World Symposium and 109th Annual Meeting of
the AIME, pp 321-332 (Metallurgical Society of American Institute of Mining, Metallurgical and
Petroleum Engineers: Littleton).
Grant, R M and Cunningham, B C, 1971. The relationship between sintering practice and lead blast furnace
performance at Port Pirie, TMS/AIME paper selection A71-1.
Green, F A, 1977. The Port Pirie Smelters (The Broken Hill Associated Smelters Proprietary Limited:
Melbourne).
Hoffman, H O, 1899. The Metallurgy of Lead, fifth edition (The Scientific Publishing Company: New York).
Hopkins, R J and Haney, L B, 1954. Thoughts on lead blast furnace smelting, Journal of Metals, March,
pp 1209-1213.
Iles, W M, 1902. Lead Smelting (John Wiley: New York).
Lumsden, J, 1971. The physical chemistry of the lead blast furnace, in Proceedings Metallurgical Chemistry
Symposium (ed: O Kubaschewski), pp 533-548 (National Physical Laboratory, HMSO: London).
Madelin, B, Sanchez, G and Rist, A, 1990. Investigation and modelling of the non-ferrous blast furnaces of
Metaleurop, in Proceedings Lead and Zinc 90 Symposium, pp 571-596 (The Minerals, Metals and
Materials Society: Warrendale and American Institute of Mining, Metallurgical and Petroleum Engineers:
Littleton).
Moriya, K, 1989. Achievement in lead smelting during a quarter century at Mitsubishi-Cominco’s Naoshima
smelter, in Proceedings Primary and Secondary Lead Processing Symposium, Halifax, August, pp 71-86.
Oldwright, G L and Miller, V, 1936. Smelting in the lead blast furnace, Trans AIME, 121:82-105.
Polyvyannyi, I R, Elyakov, I I, Gaivaronskii, A G, Ivakina, L P and Anan’ev, N I, 1971. Investigation into lead
blast furnace smelting with preheated oxygen rich blast by freezing the furnace, Trudy Inst Met i
Obogaschch Akad Nauk Kaz SSR, 43:54-84.
Rist, A and Meyson, N, 1967. A dual graphic representation of blast furnace heat and mass balances, Journal of
Metals, 19:50-59.
Roy, J T and Stone, J R, 1963. Lead blast furnace continuous tapping, Journal of Mining, 15:827-829.
Ruddle, R W, 1957. Difficulties Encountered in Smelting in the Lead Blast Furnace, 55 p (Institution of Mining
and Metallurgy: London).
Willis, G M, 1980. The physical chemistry of lead extraction, in Proceedings Lead-Zinc-Tin ’80 Symposium,
pp 457-476 (The Minerals, Metals and Materials Society: Warrendale, and American Institute of Mining,
Metallurgical and Petroleum Engineers: Littleton).
Winterhager, H and Kammel, R, 1961. Viscosity measurements in process slags from lead and copper recovery
processes, Erzmetall, 14:319-328.

CHAPTER 6
The Imperial Smelting Furnace (ISF)
GENERAL INTRODUCTION
The Imperial Smelting Furnace (ISF) was primarily developed as a blast furnace for the production of
zinc. It relies on the concept of reducing zinc oxide in a shaft furnace to produce zinc vapour in the
furnace gases. By maintaining high temperatures at the top of the shaft reversion to zinc oxide can be
prevented. The hot furnace gases are ducted from the furnace to a condenser where they are chilled
using a spray of molten lead at around 500°C, which condenses and absorbs the zinc from the gas
stream. This concept requires close control of furnace gas composition and a sealed top furnace.
A key advantage of the ISF is that it can simultaneously produce lead bullion as well as zinc and
can therefore treat mixed lead and zinc concentrates. Lead production is normally 40 to 50 per cent of
the zinc production, and the fuel required in addition to that used for zinc production alone is
relatively small, within the normal operating range. Volatilisation of lead is minimised by lowering
the residual sulfur content of sinter. The combination of lower sulfur in sinter and a more strongly
reducing environment in the crucible of an ISF than a lead blast furnace means that bullion is lower in
sulfur than bullion produced from the standard lead blast furnace. The aim is also to produce a slag
substantially lower in zinc than the standard lead blast furnace at around six to seven per cent Zn, and
requiring more reducing conditions at the base of the furnace and greater interaction of coke and blast
air with the slag pool in the furnace hearth.
The ISF was developed from the standard lead blast furnace, but with evolutionary change to a
more intensive operation, more akin to the iron blast furnace conditions at the tuyere level. The
standard ISF design had an upper shaft cross-section of 17.2 m2 and a cross-section at tuyere level or
hearth area of 13.2 m2. Data for the standard ISF is compared with the lead blast furnace in Table 6.1
and demonstrates the higher intensity operation.
TABLE 6.1
Comparison of the Imperial Smelting Furnace and lead blast furnace.
Furnace type Lead blast furnace Imperial Smelting Furnace
Air blast (Nm3/h per m2 hearth area) 785 2500
Carbon use (t/d per m2 hearth area) 7.4 15.5
2
Lead output (t/d per m hearth area) 36 8.3
Zinc + lead (t/d per m2 hearth area) 36 27
Carbon used kg/t of sinter 90 375
ISF plants operating in 2000 are listed in Table 6.2. A number of these plants have subsequently
closed.
PROCESS DESCRIPTION
A general process flow sheet is shown in Figure 6.1.
Furnace feed is prepared from sulfide concentrates, oxide feeds and residues as sinter using a
standard updraught sintering machine with attached sulfuric acid plant. As for the lead blast furnace,
high-quality sinter in terms of uniform coarse sizing and strength is essential for good performance
and efficient operation of the blast furnace. Details of sintering operations are given in Chapter 4.

CHAPTER 6 – The Imperial Smelting Furnace (ISF)
TABLE 6.2
Imperial Smelting Furnace smelters in operation in 2000.
Location Country Shaft area Year started Max zinc output Max lead output
(m2) (t/yr) (t/yr)
Avonmouth UK 27.2 1967 105 700 51 200
Chanderiya India 21.5 1991 61 400 31 000
Cockle Creek Australia 24.2 1961 97 300 40 700
Copsa Mica Romania 17.2 1966 34 100 17 100
Duisburg Germany 19.3 1966 97 400 45 100
Hachinohe Japan 27.3 1969 114 400 52 100
Harima Japan 19.4 1966 88 900 28 600
Miasteczko Poland 19.0 1972 84 600 36 000
Noyelles Godault France 24.6 1962 115 700 48 300
Porto Vesme Italy 19.0 1972 84 600 36 000
Shaoguan No 1 China 18.7 1975 81 500 34 800
Shaoguan No 2 China 17.2 1996 70 900 31 900
Veles Macedonia 17.2 1973 59 700 30 500
Coke
Sinter
Sinter Hopper Coke Coke Hopper

Preheater
Charge Bucket
Gas Scrubber
Gas
Bell Seals LCV Gas

Condenser
Air Preheater
Furnace
Lead Pumps
Cooling Launder
Separation
Bath
Tuyeres Blue Powder / Liquor
ISF Zinc
Forehearth
Slag Lead Bullion
FIG 6.1 - Schematic layout of the imperial smelting process.

The standard furnace is a rectangular shaft constructed of a steel casing cooled externally by water
shower and lined with refractory brick. Original dimensions were 6.3 m × 3.2 m at the outer steel
casing and 17.1 m2 upper shaft cross-section within the brick lining. The furnace width narrows
progressively to the hearth. Above the hearth are two opposing rows of tuyeres (one row on each side
of the furnace), inclined towards the hearth and with around eight tuyeres in each side. Tuyere nozzles
are made of copper with annular water-cooling channels. Air injected through the tuyeres is generally
preheated to between 800 and 1000°C using Cowper stove recuperators and heated by combustion of
the CO from furnace off-gases. Preheat is an important means of increasing furnace capacity and it
has been reported that 100°C of preheat is equivalent to a three to five per cent increase in furnace
capacity (Lee, 2000).
The top of the furnace is sealed and gases are taken through a side off-take to the condenser
chamber. The standard furnace has one condenser chamber whereas the larger Avonmouth furnace
design incorporated two condenser chambers located at opposite sides of the furnace.
Furnace feed consists primarily of sinter of the appropriate composition to give the required slag
formulation, and coke preheated to around 700°C. Other feed materials such as briquettes made from
zinc oxides, and metallic scrap can also be added to the furnace feed. Feed is charged to the furnace
using weighed buckets, which are dumped into a double ‘bell seal’ hopper arrangement located in the
furnace roof. The bell seals are water-cooled steel construction and efficient sealing is very important.
At the tuyere zone of the furnace, carbon combustion takes place predominantly forming CO and
generating most of the heat required to operate the furnace. Temperatures up to 1600°C are generated
in the blast zone or tuyere raceways. As gases rise through the shaft, zinc and lead oxides are reduced
by CO, and carbon is consumed by the CO2 so generated to reform CO. These reactions are
endothermic and temperatures decline towards the top of the shaft.
When the sinter melts it trickles into the slag pool contained in the furnace hearth from where
further zinc reduction takes place but at a lower rate. A higher temperature assists and most ISFs
operate with a slag melting temperature of above 1200°C and a lower oxygen potential than the lead
blast furnace. Increasing the lime content of the slag can be used to raise the melting point of the slag
and increase the activity of dissolved ZnO. Sinter composition ratios are commonly targeted at:
• FeO: SiO2 2.7:1
• CaO: SiO2 1.4:1
• FeO: (CaO+SiO2+Al2O3) 1.1:1
Coke will usually add significant quantities of silica (up to 50 per cent of sinter feed amounts) and
will alter these ratios for blast furnace slag, which is the ultimate target.
Slag and bullion are tapped from the furnace hearth into a forehearth where they are separated. Slag
flows from the forehearth into a granulation launder and lead bullion flows to a lead ‘kettle’ of around
100 tonnes capacity either directly or via batch ladles. The bullion is allowed to cool in the kettle to
separate a copper-lead dross, reducing the copper content to around 0.2 per cent. The resulting lead
bullion is then cast into blocks of up to four tonnes each for transfer or sale to a lead refinery.
Lead reduction tends to occur in the top zone of the furnace by reaction of lead oxides with zinc
vapour and with CO. The reactions are mildly exothermic.
To ensure that the temperature of the gas stream leaving the top of the furnace does not fall below a
critical level where re-oxidation of zinc occurs, some air is introduced to burn CO and generate
additional heat (‘top air’). Generally the critical temperature to prevent re-oxidation is around 950°C.

Although the action of air injection does generate higher CO2 concentrations and increases the
potential for zinc re-oxidation, this is offset by the effect of the temperature increase achieved. Top air
can represent of the order of 12 per cent of the air volume injected through the tuyeres.
Gas leaving the furnace generally has the composition of five to seven per cent Zn vapour, 16 to
18 per cent CO, ten to 13 per cent CO 2 and should have a temperature of close to 1000°C.
The lead splash condenser consists of a chamber approximately 8.5 m long × 5.5 m wide × 1.15 m
high, and contains a pool of lead 0.4 m deep. Vertical baffles divide the chamber into four sections.
Each section is fitted with two rotors located at the surface of the lead pool and driven by a vertical
shaft projecting up through the roof to the electric motor drives. The inclined blades of the rotor throw
up a spray of lead droplets into the gas stream, scrubbing out zinc and cooling the gas from around
1000°C at the inlet to around 500°C at the outlet. Molten lead is continuously circulated through the
condenser, exiting at a temperature of 550°C and containing approximately 2.5 per cent zinc. The hot
lead flows through a cooling launder where the temperature is reduced to 450°C, at which point the
solubility of zinc is reduced to 2.1 per cent (see Table 11.3). The lead flows to a settling bath where
excess zinc floats to the surface and is separated using an overflow/underflow weir arrangement.
Separated liquid zinc at 98.6 per cent zinc content is pumped to a holding furnace prior to refining,
while the cooled lead is circulated back to the condenser.
Gases exiting the condenser pass through a scrubbing system where solids containing zinc
escaping the condenser are collected as ‘blue powder’. The gas with its high CO content is used as fuel
for the preheating of blast air in Cowper stoves and for the preheating of coke.
SLAG COMPOSITION
There are limits to the level of zinc in final slag, because as the oxygen potential is lowered to reduce
more zinc, the tendency to reduce FeO and form iron is increased. At slag temperatures of 1350°C the
presence of metallic iron can cause considerable difficulties in the tapping process. Generally zinc
levels are not reduced much below six per cent in final slag for this reason.
Apart from the zinc content, slag composition is important for control of the appropriate melting
point and viscosity of the slag, to ensure suitable operation of the hearth, and the ability to tap the
furnace and achieve good separation of slag and bullion. Composition adjustment is made by the
addition of fluxing components to the sinter feed, but can also dictate the concentrate feed mix and
place limits on the intake of particular feed materials. Ratios of major components are targeted in
sinter as indicated above, but additional amounts of some components such as silica will be sourced
from the coke and shift these ratios for slag. Slag compositions will vary depending on available feeds
to the smelter, but are typically as shown in Table 6.3 with a liquidus temperature of around 1220°C.
The chemistry of slags, the various phases which can be present, and their interactions is complex
and minor variations of some components can have significant effects. For instance Al2O3 at high
levels results in the precipitation of Hercynite (FeO.Al2O3), which raises the liquidus temperature of
the slag but lowers the potential to form metallic iron. At low concentrations of Al2O3 there is
increased potential to form metallic iron with associated problems. Such subtle effects can have a
significant impact on the hearth and tapping operations.
EVOLUTION OF FURNACE DESIGN AND OPERATION

As indicated above, there has been progressive improvement in the design and capability of the
standard blast furnace and considerable expansion in its capacity.

TABLE 6.3
Typical Imperial Smelting Furnace slag composition.
CaO 18.5%
SiO2 19.5%
FeO 41.5%
ZnO 9.5%
PbO 1%
Al2O3 8%
MgO 0.5%
Other 1.5%
Component ratio Typical value Range in values

CaO: SiO2 0.95 0.8 to 1.4
FeO: SiO2 2.1 1.8 to 2.9
FeO: (CaO+SiO2+Al2O3) 0.9 0.7 to 1.2
The original standard furnace had an upper shaft cross-section of 17.1 m2 constructed of a
refractory lined steel shell (6.3 m × 3.2 m), which was cooled externally by means of a water shower.
The lower shaft narrowed at the tuyere level and was constructed of two rows of water jackets.
Twenty-six tuyeres as two opposing rows (each of 13) were used at relatively low intensity or blast
rate, in keeping with standard lead blast furnace designs. Figure 6.2 illustrates the general vertical
cross-section of the original furnaces.
FIG 6.2 - Original imperial smelting process furnace configuration water jackets in lower shaft.
The formation of accretions in the shaft was a particularly serious problem with the early design,
aggravated by water leaks from the jackets forming the lower shaft. This problem became more
significant as attempts were made to increase the blast intensity and productivity of the furnace. It was

recognised that the required characteristics of the furnace were more akin to the higher intensity iron
blast furnace than to the lead blast furnace. These characteristics are:
• the higher carbon requirements per unit of metal produced,
• the highly reducing conditions required,
• the use of blast air preheat for fuel efficiency, and
• the higher blast rates required for furnace productivity.
It was recognised that the narrow hearth configuration as shown in Figure 6.2 was unsuitable for
high intensity operation and for maximum retention of slag in the hearth in order to minimise the final
zinc content of slag. This latter requirement followed from the recognition that a significant level of
ZnO reduction occurred from the slag pool held in the hearth. As a consequence of these issues the
hearth of the furnace was widened, water jackets in the lower shaft were replaced with a shower-
cooled steel casing, the number of tuyeres was increased and the blast rate was increased. Raceways
developed at the tuyere level as in the iron blast furnace, creating greater mobility of coke at the tuyere
zone and greatly increasing the interaction with the slag pool. The general cross-section of the furnace
changed to that shown in Figure 6.3.
FIG 6.3 - Later configuration of the lower shaft.
The formation of a zone of solid fused material in the centre of the furnace just above the tuyere
zone (or ‘deadman’) provides support for the charge column above, but if excessive restricts the flow
of material and gases, thus limiting the capacity of the furnace. The extent of this formation is
controlled by limiting the separation between opposing tuyeres, as dictated by the blast velocity and
hence, blast volume and the number of tuyeres installed. The lower sections of the ‘deadman’ may be
composed of relatively high melting point iron and speiss, as well as unreacted coke.
As the blast rate is increased, the raceway size increases and greater separation is required to
prevent excessive overlap of adjacent raceways. Hence, for a given furnace the number of tuyeres
must be reduced. To limit excessive overlap of opposing tuyere raceways, it is necessary to reduce

velocity by increasing the diameter of the tuyeres. However, it is necessary to ensure that there is a
minimum degree of overlap under all operating conditions. There are thus a number of complex
interactions in furnace design and a balance between the blast rate, tuyere diameter, the number of
tuyeres, and the furnace width, which determine capacity and the efficiency of zinc recovery from the
feed material. Assessment of raceway coverage is an important tool in design and can be done using
an equation developed by Wlodarczyk, as published by Harris (1981).
The standard furnace now has typically 16 tuyeres as single rows of eight on each side. The angle
of the tuyeres to the horizontal is also a parameter of some importance, although it varies between
individual plants. High angles will give greater interaction with the slag pool, but will induce high
wear rates on the furnace hearth refractories. Initial furnace designs had a tuyere angle of 10° but this
has increased to between 15 and 20°.
Accretions
Accretions form in the ISF as zinc oxide deposits by reoxidation of zinc vapour in colder areas of
the furnace, which essentially means the furnace walls. However, critical areas are above the upper
surface of the charge, and include the furnace roof and condenser entry. Accretions grow and
progressively reduce the cross-sectional area and capacity of the furnace. Extensive growth can also
generate significant hoop stresses on the furnace and can result in splitting of the casing and lifting
of upper sections of the shaft. Movements in the upper shaft can affect the attachment to the
condenser and if movement is transferred to the condenser can severely impact on its performance
by affecting the level of the lead pool in the condenser. Regular shutdown time for the cleaning of
accretions is consequently necessary, and is usually on a three to six week cycle. Explosives may be
used to remove accretions from the furnace shaft, but in other areas manual cleaning using
jackhammers is necessary. As an alternative to blasting, the furnace may be burnt down to tuyere
level with a high coke charge and the offtake temperature is allowed to rise so as to remove
accretions. This action tends to marginally reduce the life of shaft refractories and may risk damage
to the furnace casing.
Slag and bullion tapping

The original ISF design was based on batch tapping with a variable level of slag and bullion in the base
of the furnace, and most operating furnaces remain with this configuration. However, as indicated
above, the interaction of the slag pool with the tuyere raceways is important in maximising the reduction
and elimination of zinc from the slag. Hence, it can be argued that control of the slag level has important
implications and steady control can only be achieved with continuous tapping. Varying levels of slag
caused by intermittent tapping will also cause varying back pressure on the blast air supply, thus varying
the blast rate. There are also implications for the separation of lead from slag. When tapping is at a high
rate and flow through the forehearth is high, losses of lead, copper and precious metals in slag will be
higher. There are thus significant advantages in adopting continuous tapping. However, experience has
shown that although the above advantages can be achieved, a different flow regime and phase
distribution occurs within the furnace, and this can lead to difficulties with the discharge of speiss from
the furnace with slag. Iron speiss can be solid within the hearth and form a layer between the lead and
slag at the end of the hearth opposite the tapping position. To avoid this it is necessary to achieve a high
level of mixing and hence, strong interaction of the tuyere raceways with the slag pool, in turn requiring
increased inclination of the tuyeres (Holliday et al, 1987).

The higher pressure operation of the ISF compared with the lead blast furnace means that weir
heights in the forehearth are greater. The combination of taller weirs, lower bullion and slag flows,
and higher heat losses around the weir in the ISF, results in more difficulty in maintaining the tapping
hole open compared with a lead blast furnace.
COKE USE AND FURNACE CAPACITY
Coke quality and uniformity is of importance and needs to be sufficiently strong to avoid degradation
during handling and passage through the preheaters and furnace shaft. Volatile content should be low
to avoid the presence of hydrogen, and reactivity should be relatively low, within the range of cokes
normally available. The presence of hydrogen results in the formation of water vapour, which can
react with zinc vapour in the upper shaft as the temperature falls to reform zinc oxide, and hence,
volatiles should be low.
As with the lead blast furnace a highly reactive coke causes the reduction zone to move to higher
levels in the furnace and reduces the amount of carbon reaching the tuyere zone, thus lowering the
temperature at the base of the furnace. This lowers the reduction of zinc from the slag pool and raises
the loss of zinc in slag. The lower temperatures can also create difficulties with slag viscosity and the
tapping of slag from the furnace. These effects can be overcome by increasing the coke consumption,
but it is preferable to use a low reactivity coke.
As indicated, coke is preheated to 700 or 800°C in a shaft in countercurrent flow to combustion
products from the burning of condenser exit gas. Since the exit gas conditions for the furnace are
relatively well defined in terms of temperature, CO and CO2 contents, the carbon consumption of the
furnace will be directly related to oxygen input in blast air and top air. The furnace can in fact be
defined closely in terms of its coke burning capacity. This can be increased per unit of oxygen
supplied by preheating of the blast air and coke, and by oxygen enrichment of blast air, but a typical
figure given average conditions as indicated above, is 1.2 kg of carbon per 1000 Nm3/h of oxygen
input in blast air.
The maximum blast air input volume for the standard furnace of 17.2 m2 upper shaft cross-section
is close to 34 000 Nm3/h. The typical furnace blast maximum intensity is close to 2000 Nm3/h/m2 of
shaft area. On this basis such a standard furnace has the capacity to burn:
34 000 × 24 × 21 per cent × 1.2 × 10 -3 = 205 tonnes per day of carbon
For coke with a fixed carbon content of 85 per cent this represents close to 240 tonnes per day of
coke as the maximum burning rate. Practical rates will be below this figure due to plant intensity and
availability issues.
The manner in which carbon is utilised for zinc production is affected by heat balance issues as
well as chemical requirements for metal reduction. The heat balance is influenced by the amount of
slag produced, the blast preheat and the preheat achieved in coke and sinter. Apart from the quantity
of zinc oxide reduced, the chemical factors include the lead and iron contents of sinter and the
moisture entering the furnace in blast air and in sinter or additives. Based on typical operating
conditions as indicated above and a lead production of close to 50 per cent of the zinc production, the
empirical formula used to relate carbon consumption to zinc production is given by Equation 6.1:
Carbon consumed = 0.655 × zinc produced + 0.152 × slag produced (6.1)

For a typical slag production of 0.9 tonne per tonne of zinc produced, Equation 6.1 indicates a
carbon to zinc ratio of 0.8 or a zinc to carbon ratio of 1.25. Hence, the maximum zinc production from
a standard furnace would be 205 × 1.25 = 256 tonnes per day. This represents the zinc which can be
produced in furnace gases to the condenser and is reduced in practice by inefficiencies, loss of plant
availability for cleaning and breakdown, and by reduced intensity of operations for various reasons.
For 92 per cent recovery of vaporised zinc to product metal and 90 per cent plant utilisation this will
equate to an annual capacity of 77 400 tonnes.
Fuel can be injected through the tuyeres either in the form of coke fines, or as pulverised coal, fuel
oil or gas. This basically replaces lump coke and is done as a cost saving measure, rather than
affecting production capacity. However, there can be offsets with the use of hydrogen containing
fuels such as oil, natural gas and coal, which give rise to problems during condensation due to the
reaction of zinc and water vapour, which is much faster than the oxidation of zinc vapour by CO2. As
an adjunct to this, the presence of water in blast air due to natural humidity can be a significant
problem, firstly in consuming carbon in the lower shaft and later in causing condensation problems
due to the presence of water vapour. Dehumidification of blast air can be justified in some
circumstances. The impacts of a number of these factors were reviewed and modelled by Kellogg
(1990).
Oxygen enrichment of blast air gives a marginal reduction in carbon use per tonne of zinc
produced but a significant increase in capacity of the furnace of the order of four per cent extra zinc
production per one per cent oxygen enrichment in blast air.

Harris, C F, 1981. Imperial Smelting Furnace hearth and raceway considerations, in Proceedings International
Blast Furnace Hearth and Raceway Symposium, pp 13/1-13/8 (The Australasian Institute of Mining and
Metallurgy: Melbourne).
Holliday, R J, Fitzgibbons, D P, Arthur, A F and Bath, R A, 1987. Development of a continuous tapping system
for the Imperial Smelting Furnace, in Proceedings Pyrometallurgy ’87 Symposium, pp 521-535 (Institution
of Mining and Metallurgy and Institute of Metals: London).
Kellogg, H H, 1990. A practical model of the imperial smelting zinc-lead blast furnace, in Proceedings
Lead-Zinc ’90, pp 549-569 (The Minerals, Metals and Materials Society: Warrendale).
Lee, R W, 2000. The continuous evolution of the imperial smelting process, in Proceedings Lead-Zinc 2000,
pp 455-466 (The Minerals, Metals and Materials Society: Warrendale).
Temple, D, 1980. Zinc-lead blast furnace – the key developments, Metallurgical Transactions B, 11(3):343-352.

CHAPTER 7
Direct Smelting Processes
PRINCIPLES
The sinter plant–blast furnace technology for lead production is highly capital intensive with a large
amount of mechanical equipment, and generates large volumes of process gas and ventilation air to
capture dusts and fumes generated from many points in the process. It is not simple to control or
maintain at maximum efficiency and places a high reliance on experienced operators. In fact the sinter
plant–blast furnace technology has not been economically viable for a new ‘greenfield’ smelter for
many decades and alternative technologies have been sought to significantly reduce both capital and
operating costs. Apart from excessive capital costs, the particular operating cost item of concern has
been the use of metallurgical coke. Control of environmental emissions and occupational health
matters are also significant issues and the meeting of strict environmental standards can be extremely
difficult and costly for sinter plant and blast furnace technology.
The sinter plant–blast furnace process involves two stages, firstly fully oxidising sulfides to
oxides, followed by reduction of lead oxide to metal, as shown in Equations 7.1 and 7.2. The same end
point can be reached by partial oxidation only, as indicated by Equation 7.3.
PbS + 1.5O2 = PbO + SO2 (7.1)
PbO + CO = Pb + CO2 (7.2)
PbS + O2 = Pb + SO2 (7.3)
PbS + 2PbO = 3Pb + SO 2 (7.4)
The reaction given by Equation 7.3 may in fact proceed by first oxidation of PbS to PbO (or PbSO4
at lower temperatures), followed by reaction of PbO (or PbSO4 ) with PbS, which is termed the ‘roast
reaction’ as given by Equation 7.4. This approach was used in the earlier hearth processes for the
smelting of high-grade lead material, but was never complete. Significant amounts of PbO were
formed and lost in flue dusts, slags and residues, particularly if lower grade concentrates were
processed. Complexities also arose with the presence of zinc, which formed zinc oxide and had to be
removed in slag. Slag formation required the addition of silica as well as lime and iron. Silica tended
to react with any oxidised lead to form stable silicates, further reducing the efficiency of the process.
For reasons of poor metal recovery as well as serious emission problems, the hearth process was
replaced by the sinter plant–blast furnace process. However, there are significant inherent energy
savings in the use of this approach and attempts have been made to utilise the ‘roast reaction’ in the
development of new smelting processes treating concentrates directly to produce lead metal.
In the separate sinter plant–blast furnace process the heat of combustion of sulfides in the sinter
plant is only utilised for drying and preheating feed before combustion, but is otherwise lost. If it
could be effectively captured and transferred into the reduction stage then a substantial decrease in
carbon fuel use could be achieved. A typical heat balance is shown in Table 7.1 for the sinter plant and
blast furnace, together with a hypothetical balance for a single stage direct smelting process with the
same end point slag and bullion conditions from an identical concentrate feed.

CHAPTER 7 – Direct Smelting Processes
TABLE 7.1
Heat balances for lead smelting (megajoules per tonne of lead produced).
Component Sinter plant Blast furnace Overall sinter (BF) Direct smelting
Inputs
Heat in feed 35 240 35 35
Heat in air/oxygen 25 80 105 6
Heat of reaction
Sulfides 4570 4570 2850
Fuels 3040 3040 581
Total input 4630 3360 7750 3471
Outputs
Heat lost from sinter 2210 1970
Heat lost in slag 1670 1670 1670
Heat lost in bullion 150 150 150
Heat lost in gases 2190 690 2880 1351
Equipment heat loss 230 850 1080 300
Total output 4630 3360 7750 3471
Note: Heat balances are based on processing a concentrate containing 60 per cent Pb, 20 per cent S, seven per cent Fe and six per
cent Zn.
As shown in the illustration in Table 7.1, heat requirements from fuel can be substantially reduced
if the separate stages can be combined.
The characteristics of direct smelting can be simply demonstrated by reference to the equilibrium
phase diagram for the Pb-S-O system as shown in Figure 7.1 for a temperature of 1200°C. This is the
practical temperature required to achieve molten and free flowing reduced slags. (Oxidised slags with
a high lead content are still fluid at temperatures below 1100°C.) As well as the equilibrium lead
phases the diagram shows the equilibrium partial pressure of SO2 and indicates that even in a pure SO2
atmosphere at 1 atmosphere (atm), metallic lead can exist. An oxygen-based smelting process is
required to produce SO2 at 1 atm partial pressure, whereas an air-based system will produce a partial
pressure of SO2 closer to 0.1 atm.
Some dissolution of sulfide in bullion will occur with a merging of the boundary between lead metal
and lead sulfide. Lead sulfide contains 13 per cent S as the extreme, and two other positions of three per
cent S and 0.3 per cent S in bullion are shown, as influenced by the partial pressure of free sulfur alone.
As temperature is reduced the Pb to PbO and PbSO4 boundary moves down and to the left of the
diagram to lower O2 and S2 equilibrium partial pressures, thus restricting the region where metallic
lead can be formed and favouring the formation of lead sulfate or basic lead sulfates. In reality and
under high temperature direct smelting conditions, sulfate phases shown in Figure 7.1 do not exist,
and only two immiscible phases are present – namely sulfur containing bullion and a sulfur containing
oxide slag (Willis, 1980; Ward, 1985).
A lower oxygen potential will favour lower levels of PbO in slag, but for a given SO2 partial
pressure such a change will result in higher levels of sulfur in bullion. Similarly higher oxygen
potential will produce higher lead slags and lower sulfur levels in bullion.
The normal regions for direct smelting as well as sintering and the blast furnace are also shown in
Figure 7.1.

FIG 7.1 - Equilibrium diagram for the Pb-S-O system at 1200°C (Yazawa and Nakazawa, 1998;
Matyas and Mackey, 1976).
Pure direct smelting utilising Equation 7.3 alone thus tends to produce high lead slags and a high
sulfur content bullion in comparison with the sintering–blast furnace approach. The key issues for any
direct smelting process are then the adequate elimination of sulfur and the production of a residual
slag of low lead content.
The principal reaction to be considered is Equation 7.4 for which the equilibrium constant is given
by Equation 7.5:
a Pb . p SO 2
K= (7.5)
a PbO . a PbS
where:
aPb = the activity of lead metal
p SO 2 = the partial pressure of SO2 in equilibrium with the melt
aPbO = the activity of PbO in the slag
aPbS = the activity of PbS in the slag
Assuming aPb = 1.0, then Equation 7.5 can be rewritten as:
p SO 2
K. aPbO =
a PbS
indicating that the activity of PbO in slag is inversely proportional to the activity of PbS, or sulfur in
the bullion, for a fixed temperature and partial pressure of SO2. Figure 7.2 illustrates a form of this
relationship between the lead content of slag and the sulfur content of bullion, taken from a range of
actual smelting plant data (Zaitsev and Margulis, 1985).

45%
40%
35%
30%
Lead in slag
25%
20%
15%
10%
5%
0%
0.00% 0.50% 1.00% 1.50% 2.00% 2.50% 3.00% 3.50%
Sulfur in bullion
FIG 7.2 - Relationship between S in bullion and Pb in slag for single stage direct smelting
(after Zaitsev and Margulis, 1985).
It should be noted that the equilibrium constant K in Equation 7.5 is temperature dependent, as are
the activity coefficients of PbO and PbS, which has ramifications for the yield of volatiles from the
direct smelting process. For a slag of given PbO and PbS contents, the activity of PbO will increase
slightly with temperature while that of PbS will decrease significantly – as demanded by changes in
the equilibrium constant and activity coefficients with temperature. Calculated activities for a slag
containing 33.3 per cent Pb are illustrated in Figure 7.3. This also shows that a slag of this composition
cannot exist below 1070°C where the calculated activity of PbS is greater than 1.0, an actual
impossibility since a separate liquid PbS phase would have formed below this temperature.
1.6
1.4
1.2
1
Activity
Act. PbO
0.8
Act. PbS
0.6
0.4
0.2
0
1000 1050 1100 1150 1200 1250 1300
Temperature (°C)
FIG 7.3 - Slag activities at 33.3 per cent Pb in slag (Ward, 2007).

The volatilisation of a particular species (Pb, PbO, or PbS) is determined by the vapour pressure of
the species and its activity as a function of temperature. The vapour pressure of individual pure
components are given in Table 7.2 and the actual calculated vapour pressures of components above a
slag containing 33.3 per cent Pb, as illustrated in Figure 7.3, are given in Table 7.3 for temperatures
above the limiting minimum for a single slag phase.
TABLE 7.2
Vapour pressures of lead compounds (vapour pressures in atm).
Temperature ( C) 900 1000 1100 1200 1300
PbS 0.0036 0.0223 0.106 0.4087 1.327
PbO 0.00060 0.00357 0.01632 0.0608 0.1915
Pbl 0.00048 0.0019 0.0066 0.0192 0.0488
TABLE 7.3
Vapour pressures of lead compounds above a 33.3 per cent Pb slag (vapour pressure in atm).
Temperature C) 1100 1200 1300
PbS 0.072 0.098 0.173
PbO 0.0016 0.0064 0.0208
Although the activity of PbS in the slag decreases with temperature there is still an increase in
vapour pressure and there will be a marked increase in volatilisation with an increase in temperature
from 1200 to 1300°C leading to the generation of fumes and dusts. This will favour smelting at the
lowest practical temperature, conducive to the formation of fluid slag and above the critical point of
separation of a separate PbS matte phase as indicated above.
Minimisation of gas volumes will reduce losses of lead from the smelting bath by volatilisation,
and hence oxygen based smelting or high levels of oxygen enrichment are desirable. It also follows
that low-grade concentrates with substantially higher S to Pb ratios will yield correspondingly higher
SO2 generation and gas flows. Hence volatilisation of lead will be proportionally higher and in some
direct smelting processes may result in excessive losses or circulating loads. Low-grade concentrates
will also generate more slag resulting in greater losses of lead as a result of high lead slags.
Direct smelting process configuration

Meeting the requirements of high sulfur elimination, low lead slags and minimal volatilisation in a
direct smelting operation utilising the ‘roast reaction’ alone in a single stage is relatively impractical,
and involves unacceptable compromises between these requirements.
The only practical approach is the use of a two stage process, in which extensive oxidation of
sulfide occurs in the first stage (oxidation stage) to eliminate sulfur, followed by reducing conditions
in the second stage (reducing stage) to lower the level of lead in slag. Carbon must be used for
promoting reducing conditions in the second stage if the level of sulfur in bullion is to be low. The use
of oxygen can also minimise the amount of lead volatilisation. The oxidation stage can be structured
to produce a lead-rich slag and some lead bullion by utilising the roast reaction to some extent. The
lead-rich slag can be subsequently reduced to recover the remaining lead as bullion. With integration
of the two stages, significant fuel savings can be achieved. These principles form the basis of a
number of direct smelting processes.

The Boliden lead process was the first of the direct smelting processes in which the first stage
attempted to utilise the roast reaction to the maximum extent and was carried out in an electric furnace as
an alternative heat input device to minimise gas volumes and lead volatilisation. Sulfur elimination was
poor, giving high levels of sulfur in bullion, which was subsequently oxidised in a converter to lower the
sulfur content. The slag remained high in lead as well as zinc and was treated in a slag fumer. Lead
volatilisation was high and the process was effective only for the smelting of high-grade concentrates.
Subsequent direct smelting developments have aimed for higher sulfur elimination in the first
stage to give high lead first stage slags and include the Kivcet process, the Queneau-Schuhmann-
Lurgi (QSL) process, the Kaldo process and top submerged lancing (TSL) used in the Isasmelt and
Ausmelt processes, and are detailed in the following sections of this chapter.
The role of iron in refractory protection

The equilibrium composition of iron in the slag is also of importance and is controlled in bath
smelting processes to ensure some precipitation of magnetite (or zinc ferrite) onto the refractories in
order to ameliorate the effects of highly aggressive litharge slags, produced under the oxidising
conditions of the first direct smelting stage. To provide effective protection, the refractory surface
temperature should be below the magnetite liquidus temperature. Although special grade refractories
such as fused chrome magnesite are used for these applications, they are not completely inert to
litharge attack. The chrome magnesite spinel itself is virtually immune to litharge attack, but any
residual magnesite or traces of silica will accumulate at grain boundaries and will be vulnerable,
leading to disintegration of the refractory structure.
The phase diagram for the Fe-O-S system is shown in Figure 7.4, corresponding with Figure 7.1,
and indicates that the direct smelting region does have the potential to produce magnetite. Figure 7.4
is, however, a simplification since it does not account for the solubility of Fe3+ in slags and the
presence of solid species with highly variable Fe2+ and Fe3+ contents (Jak, Zhao and Hayes, 2000).
FIG 7.4 - Equilibrium diagram for the Fe-O-S system at 1200°C.

At the required oxygen potential for the formation of magnetite to occur and provide refractory
protection there will generally need to be some compromise between the PbO content of slag and the
residual sulfur level in bullion.
THE BOLIDEN LEAD PROCESS

The Boliden lead process applied the ‘roast reaction’ in a liquid slag phase in an electric furnace. It
was part of a copper and lead smelting complex at the Ronnskar smelter in northern Sweden. It was
also integrated with a slag fumer to recover zinc and lead and later to some degree with the Kaldo top
blown rotary converter (TBRC) discussed below, which was initially used to treat dust and fumes
containing lead that could not be handled by the electric furnace (Elvander, 1965).
The process was developed to smelt local high-grade concentrates and was not competitive for the
smelting of low-grade materials, as indicated above for application of the roast reaction. Design
concentrate feed for this process was 70 - 75 per cent Pb, 14 per cent S, one to three per cent Zn, two per
cent Fe, five to six per cent SiO2. The smelter was closed when supply of these high-grade concentrates
was exhausted and smelting continued using the Kaldo TBRC alone. Figure 7.5 illustrates the original
configuration of the integrated lead smelting operations at the Ronnskar smelter. The electric furnace
has subsequently been closed with lead operations confined to the TBRC.
Lead concentrate
Fluxes
Dryer
Air/oxygen
Electric Gas Gas to

Furnace Cleaning Sulfuric Acid
Air Bullion
Converters Slag Fumer
Gas Clinkering
Cleaning Kiln
Lead Slag to
Bullion waste
Dusts Zinc oxide to
Zinc Smelter
Lead fume
Gas to
Lead scrap
Sulfuric Acid
Copper plant dusts
Slag
Kaldo Gas
TBRC Cleaning
Dusts
Dusts
FIG 7.5 - Original lead smelting at Boliden – Ronnskar smelter.

The electric furnace was a 6 MW unit with four in line Soderberg electrodes. High-grade
concentrates, limestone, iron cinders and recycle dusts and fumes were predried to two per cent moisture
and fed into the electric furnace via two flash burners located between electrodes one and two and
between electrodes two and three. The solids entered through a central vertical pipe surrounded by
tangential jets of oxygen enriched air creating a vortex and flame at around 1150°C. Oxygen input
was less than stoichiometric and around 70 per cent of sulfur was oxidised in the burners. Reactions in
the flame formed lead bullion and a slag/matte, which fell into the slag bath contained in the bottom of
the electric furnace where they separated into an upper slag and lower bullion layer. Further oxidation
of sulfur continued in the slag bath according to Equations 7.6 and 7.7:
PbS + 2PbO = 3Pb + SO 2 (7.6)
PbS + PbSO4 = 2Pb + 2SO2 (7.7)
Coke was also added to the furnace as fines at one per cent of the concentrate input to assist in
reducing the lead level of slag, which contained around 4.1 per cent Pb as well as zinc. Carbon was
also added from the electrodes and represented around 1.3 per cent of the concentrate input.
Gas from the furnace contained copious fumes and dusts at around 40 per cent of concentrate feed,
and around eight per cent SO2. Dust and fume collected from gas cleaning was returned to the electric
furnace and represented a significant recycling load.
Bullion was tapped continuously via a siphon from the centre of the furnace and slag was tapped
intermittently from one end. Lead bullion contained around three per cent S, which was transferred to
either of two small batch operated Pierce Smith converters, blown with air to remove sulfur. Slag
from the converters and dusts collected from converter gases were also returned to the electric
furnace. A copper matte was periodically recovered from the converters and the bullion was sent to
the lead refinery.
Slag from the electric furnace was too high in lead (and zinc) for disposal and was further
processed in a conventional slag fuming furnace, where zinc and lead were fumed off by the addition
of coal. The fume produced was unsuitable as feed for a zinc smelter and was treated in a clinkering
kiln to fume off halides and lead and leave a zinc oxide clinker now suitable as feed to an electrolytic
zinc plant. The fume produced from the clinkering kiln contained over 50 per cent Pb, but was
unsuitable for recycling to the electric furnace due to the high concentration of impurities. This
material was processed in the Kaldo process utilising a batch operated top blown rotary converter
(TBRC), and was later installed at the Ronnskar smelter. This plant also treated lead-rich converter
dusts from the copper smelter.
Capacity of the electric furnace was around 55 000 t/a of lead bullion and electrical energy
consumption was around 900 kWh per tonne of lead bullion produced.
THE KALDO PROCESS

(TOP BLOWN ROTARY CONVERTER – TBRC)
The Kaldo process was also an innovation developed at the Boliden Mineral AB – Ronnskar smelter
for the processing of difficult fumes and dusts from copper smelting and from the lead slag fuming
operation as shown in Figure 7.5. The process proved to be highly flexible and capable of handling a
wide variety of lead bearing materials including sulfate residues and was later adapted to the smelting
of low-grade concentrates. It is now predominantly used for the processing of secondary materials.

Gas to Acid Plant Fluxes
Lead concentrate Filter Venturi

or lead rich dusts Scrubber
Rotary
Dryer
Oxygen
Screen Rotary Converter
Air
Pnuematic
Conveyor
FIG 7.6 - Layout of Boliden Kaldo process plant.
A layout of the Kaldo plant is given in Figure 7.6 (Nystedt, 1980; Pazour, 1982).
The Kaldo furnace is a batch operated rotary converter vessel with an inside diameter of 2500 mm
and a length of 6500 mm, with a working volume of 12.5 m3. It is lined with refractory brick and the
working volume increases as the brickwork wears. The initial charge is around 90 tonnes. The brick
lining consists of a 120 mm backing layer plus a 450 mm wear layer of chrome magnesite brick (15 -
18 per cent Cr2O3), which reduces back to 50 mm before replacement. Thickness is regularly
measured using a laser beam and rebricking frequency is every two to three months, representing lost
time of around five per cent. The relatively low lost time is due to the use of changeover converter
shells to allow re-bricking off-line.
Oxygen or enriched air is blown through a lance and impinges on a pool of material in the vessel.
The main lance is water-cooled and designed with multiple inner tubes to inject solid feed material
with air as well as 98 per cent oxygen. A flame is formed which impinges on the slag pool within the
vessel. Smaller lances are used to inject flue dusts or fuel oil. For concentrate smelting the
concentrates are pneumatically fed through the inner pipe of the main lance with air and oxygen fed
through the outer pipe.
The converter spins around its longitudinal axis at a variable speed of between 0.5 and 30 rev/min,
but normal speeds are in the range of five to 15 rev/min. The vessel is held within a frame which can
be tilted for filling and emptying. The whole assembly is enclosed within a box-like enclosure fitted
with top and front access doors. Material can be charged into the vessel in a vertical position either
from a batch hopper or skip by overhead crane. Fluxes, coke, return slag and scrap are added this way.
The lower part of the enclosure houses a number of flat top rail cars carrying ladles for either slag or
bullion. The total enclosure is vented through a bag house at around 80 000 Nm3/h and is maintained
at a negative pressure.
Process gas at around 20 000 Nm3/h is cooled and scrubbed in a venturi before transfer to a
sulfuric acid plant. The processing of an intermittent gas stream, both in terms of volume and SO2
content is a major problem for an acid plant, but is uniquely handled at the Ronnskar smelter by the
use of a cold sea water absorption system, as shown in Figure 7.7.

To Stack To acid plant
Bypass during smelting
Bypass for
heating stage
Wet Absorption column Stripping column

electrostatic
precipitator
SO2 – water
storage
Hot air or
Lime air + steam
Neutralisation
Cold water supply
FIG 7.7 - Gas handling system for discontinuous SO2 production.
This system absorbs SO2 from the variable gas stream into cold water, which is stored and then
continuously stripped by heating to 60°C before return to the sea. The system is only practical because
of the unlimited supply of cold low-salinity sea water available to the smelter. Alternative processes
are available using amine solutions for the absorption of SO2, which can be recovered by steam
stripping. However, the inventory cost of the amine reagent can be quite high. In other situations the
handling of intermittent gas flow is a major impediment for the Kaldo Process.
The furnace operating sequence involves charging the furnace with pelletised feed, recycled slag
and lime, and firing with an oil–oxygen burner. The charge is heated slowly under slow speed
rotation. The melting stage is completed when the SO2 content of the off-gases declines. The
reduction stage follows with fine coke injected through the lance and with the oil burner continuing to
operate. The reduction stage is completed when the lead content of slag falls below one per cent. The
temperature is then raised to 1150°C and most of the slag is emptied from the furnace while retaining
the lead bullion. A new charge is then added and the above sequence repeated.
After discharge of the second slag load, the bullion is partially refined by the addition of iron
turnings to combine with arsenic and copper to form a speiss. Oil burning is continued to retain the
temperature above 1000°C. This stage is relatively rapid and is completed when suitably low levels of
arsenic and copper are reached in the bullion. The speiss containing 30 per cent As, 50 per cent Fe,
12 per cent Cu, 3.5 per cent Pb and 1.0 per cent Sn is separately poured from the furnace. The lead
bullion is then poured into ladles and is allowed to cool to 500°C, at which point any residual speiss
settles to the top of the molten lead as a crust. The underlying lead bullion is poured into a second ladle
for transfer to the lead refinery. The composition of lead bullion at this stage is <0.1 per cent As,
<0.1 per cent Cu, 0.1 - 0.5 per cent Bi and 0.2 per cent S. Close to 50 per cent of the arsenic input and
90 per cent of the copper input reports to speiss. Of the arsenic input 35 per cent reports to smelter gas,
and 15 per cent to slag.

Final slag is below one per cent Pb and contains between seven and 15 per cent Zn and around
22 - 29 per cent Fe, 23 - 25 per cent SiO2 and 20 per cent CaO, and is sent to a slag fuming furnace to
recover zinc.
The total smelting cycle described above takes 12 hours with the order of two hours for each stage
of smelting (two stages), reduction (two stages) and refining (one stage). The remaining time is used
for various transfer operations.
Dusts produced contain of the order of 65 per cent Pb and six to ten per cent Zn, and can contain
around 20 per cent of the lead input.
Capacity of the standard furnace has been given as close to 55 000 t/a of lead bullion from average
lead concentrates at 62 per cent Pb, with typical fuel and consumption data as:
• oxygen use (m3/t of concentrate feed) 120
• coke use (kg/t of concentrate feed) 30
• oil use (L/t of concentrate feed) 6.5
• power use (kWh/t of concentrate feed) 70
The TBRC is a highly flexible process with the capability of handling a wide range of primary and
secondary materials. It is also possible to use the converter for fuming zinc from lead slags. The
disadvantages are the high level of mechanical equipment with attendant maintenance issues, and the
intermittent nature of SO2 rich gas production, which significantly adds to capital equipment
requirements.
THE KIVCET PROCESS
The Kivcet Process (an acronym in Russian for oxygen flash cyclone electrothermal process), was
developed by the Vniitsvetmet Institute in Kazakhstan in 1967 for the treatment of both copper and
lead concentrates (Sychev et al, 1985). A 25 t/d pilot plant was built and operated for a number of
years followed by a plant to treat 500 t/d of mixed copper-zinc concentrates at Glubokoe in 1970. That
plant produced a copper matte and zinc rich slag for slag fuming in the electric furnace to recover zinc
oxide.
Initial developments were based on the use of a cyclone smelting chamber mounted on the top of
the electric furnace in which the principal reactions take place in a thin slag film running down the
walls of the chamber. Because of the aggressive nature of lead rich slags towards refractories and the
much slower burning rates of lead concentrates compared with copper, attention was shifted to the use
of the flash burner shaft. A low sulfur bullion was achieved by chilling the furnace hearth to lower the
bullion temperature to about 500°C, giving rise to the formation of a lead–copper matte phase as well
as slag and bullion. The first full size commercial lead furnace was constructed for Kazzink at Ust
Kamenogorsk in 1985, treating 450 t/d of lead concentrates. Apart from a small furnace built in
Bolivia but never operated, two other lead units have been built, one at the Porto Vesme smelter
complex in Sardinia in 1987 (Perillo et al, 1990) and one at Teck-Cominco’s Trail smelter in BC
Canada, completed in 1997 (Walker, 1998).
The Kivcet furnace design is a combination of an oxygen based flash smelting shaft and an electric
furnace for slag cleaning and settling. Significant features are the partition wall between the smelter
shaft and the electric furnace, and the gas off-take shaft and waste heat boiler, which are designed to
handle high loads of sticky dusts. A schematic of the furnace is shown in Figure 7.8.

Gas Off-take Shaft
Boiler
Convective Section
Feed Blend
Coal or Coke
To Gas
Cleaning
Oxygen
Coke
Gas to ZnO
Flue Dusts for Collection
Recycle
Smelter
Shaft Afterburner
Coke ‘Checker’ Electric Furnace

Slag layer
Bullion layer
Partition Wall
Slag /Matte Lead Bullion
FIG 7.8 - Schematic of the Kivcet furnace.
Feed consists of lead concentrates, lead sulfate or oxide residues, fluxes and some coal or coke.
There are no constraints on the proportion of sulfides and oxides in the feed mix and fuel value can be
adjusted by the addition of coal or coke. High levels of oxidised lead in feed requires a substantial
increase in the fuel load.
It is found necessary to prepare feed materials by wet mixing followed by drying in a rotary kiln
dryer. This produces micro agglomerates of the feed components in close physical contact, which
promotes reactions between PbS and oxidised components of the feed mix such as PbO and PbSO4. In
so doing it minimises the volatilisation of PbS and the generation of fine dusts as it is oxidised in the
furnace atmosphere. Generally the target moisture level of the feed is around one to two per cent.
Where a high proportion of residues are used in the feed, carbon addition is needed for reduction,
particularly of ferric iron. This should be included in the wet feed mix prior to drying, whereas
additional coal as fuel should be added separately to the burner.
Coke is only added to the electric furnace if zinc fuming is required. The gas stream would then
require afterburning, cooling and filtration to recover zinc oxide.
Smelting shaft
The feed is dropped into a cyclone flash burner into which industrial grade oxygen (95 per cent) is
injected tangentially, surrounding the feed. A flame is produced projecting downwards into the
smelting shaft, with a temperature between 1350 and 1420°C, controlled by varying oxygen or feed
flow rates. Within the flame and reaction shaft, carbon is partly burnt, sulfides are oxidised fully,
sulfates are decomposed in accordance with Equations 7.8 to 7.14, and the oxides are formed into a
molten slag phase.

PbS + 1.5O2 = PbO + SO2 (7.8)
ZnS + 1.5O2 = ZnO + SO2 (7.9)
FeS + 1.5O2 = FeO + SO2 (7.10)
PbSO4 = PbO + SO2 + 0.5O2 (7.11)
ZnSO4 = ZnO + SO2 + 0.5O2 (7.12)
C + O2 = CO2 (7.13)
CO2 + C = 2CO (7.14)
There is a view from the process developers that lead metal is initially formed on the galena
surfaces and is then oxidised to PbO, although other mechanisms can result in the same outcome. The
composition of particles in the burner shaft as a function of residence time or height in the shaft would
then be expected to show a progressive decrease in the PbS content, and initial rise then decline in the
metallic lead content and a progressive rise in the PbO content as oxidation is completed. Figure 7.9a
illustrates measured composition as a function of shaft height. Figure 7.9b shows the corresponding
temperature (Lyamina and Shumskii, 2006). This demonstrates that lead is mainly oxidised to PbO in
the shaft.
Depending on the form of lead-rich residues in the feed there may be varying amounts of complex
materials such as ferrites and jarosite from zinc plant leach residues, which also need to be
decomposed, and as indicated above coal as a reductant to the feed mix is required in addition to coal
as fuel. The rate of decomposition is generally lower than the sulfide oxidation reactions and longer
residence times are required in the smelting shaft with the treatment of these materials. Residence
times are set by the gas velocity, hence cross-section of the shaft and the length of the shaft. The
original Kazzink lead furnace was extensively modified to handle a high proportion of residues
(75 per cent), and the shaft length extended from 3 to 5 m.
In general the ratio of feed rate to smelting shaft cross-section or ‘specific feed rate’ is relatively
fixed at between 45 and 50 t/d per square metre of shaft cross-section. There can be up to four burners
at the top of the shaft and the feed rate per burner is of the order of 300 to 350 t/d.
Gas offtake system

The molten phase produced in the smelting shaft falls to the bottom and separates from the gas phase,
which passes under a dividing wall and into the vertical off-take shaft. The off-take shaft is lined with
a membrane boiler wall, heated by radiation from the gas. Gas is normally cooled to around 700°C,
but preferably less than 800°C before entering the convection section of the boiler.
Although the oxygen potential in the smelting shaft is sufficiently high to minimise excessive lead
sulfide volatilisation, there is still a significant level of volatilisation of lead in various forms with the
high flame temperature. As a result, as the gas is cooled a significant dust and fume load is developed.
It is estimated that 75 per cent of the lead in dusts arises from volatilisation in comparison with
mechanical entrainment of feed material. As the gas cools, molten PbO will be condensed in the shaft
and will be sulfated by surplus oxygen in the flue gas (or injected into the uptake shaft) forming sticky
material, which will readily adhere to the colder boiler walls. The uptake shaft is designed to handle

PbS Pb PbO
A
40
35
30
Composition (%)
25
20
15
10
0
0 0.5 1 1.5 2 2.5 3
Shaft height (m)
1800
B
1700
1600
Temperature (°K)
1500
1400
1300
1200
1100
1000
0 0.5 1 1.5 2 2.5 3
Shaft height (m)
FIG 7.9 - Lead deportment in shaft material (A) and temperature (B) as a function of shaft height.
this by the use of spring hammers to dislodge deposits, causing them to fall back into the slag bath at
the base of the shaft. Gas below 800°C is no longer able to form sticky accretions and can be handled
in the convection section of the boiler where it is cooled to around 350°C.
The high dust loadings at the base of the uptake shaft act as a scrubber for volatile species (such as
arsenic and tin) in the flue gas, which can drop out and enter the bath as involatile species (eg lead
arsenate) and thus report to lead bullion. A dust drop-out section is also included between the uptake
shaft and the convection section.
It is important that there are no horizontal flat sections where fume can collect and especially
where the temperature is high enough so that the PbO content can fuse the fume and dusts into
inaccessible accretions.
Total dusts passing through the boiler and collected in the gas cleaning train typically represent
between five and 15 per cent of the feed and contain over 50 per cent Pb, around ten per cent Zn
depending on feed composition, eight per cent S and relatively high cadmium. Recirculation of all the
dust would cause cadmium levels to build up and hence part of the dusts are separated and leached to
remove cadmium before return to the furnace.

The SO2 content of the gas will vary widely depending on the proportion of lead concentrates in
the feed compared with residues. With a concentrate feed the gas may be 45 per cent SO2, whereas
with predominantly oxide residues as feed the level will fall to 15 per cent.
Steam production is around 0.4 t/t of feed.
Gases leaving the boiler are passed through an electrostatic precipitator before scrubbing prior to
transfer to a sulfuric acid plant. The electrostatic precipitator usually contains four fields in series,
with two parallel lines.
Coke layer or ‘coke checker’

A key feature of the Kivcet furnace is the layer of incandescent coke floating on the slag bath at the
base of the smelting shaft. The molten phases from the flash burner impinge on the coke layer and
trickle through into the slag bath beneath. Reduction occurs within this layer and the main reactions
involved are shown in Equations 7.15 to 7.18. Also shown below is the heat of reaction at 1200°C.
PbO + CO = CO2 + Pb -72.7 kJ/mole (7.15)
Fe2O3 + CO = CO2 + 2FeO -35.7 kJ/mole (7.16)
ZnO + CO = CO2 + Znv +182.7 kJ/mole (7.17)
C + CO2 = 2CO +170.9 kJ/mole (7.18)
It has been demonstrated that the reaction mechanism is basically via gaseous reduction of the
PbO slag with CO to form CO2, which in turn reacts with the coke to form more CO. The overall
reduction is mildly endothermic even at high CO2:CO ratios in the gas phase. Hence the maintenance
of the coke temperature must come from a combination of excess heat in the melt and coke arriving on
the surface of the layer, from combustion of CO immediately above the layer by means of excess
oxygen in the furnace atmosphere or by deliberate oxygen injection, and from the underlying slag
bath temperature by circulation from the electric furnace.
The coke layer is maintained at about 100 to 150 mm thick with a temperature of 1100 to 1200°C.
The thickness can be measured on a regular basis using a steel bar probe.
Extra carbon is added to the coke layer as unburned coke from the burner to make up for
consumption by the reduction reactions. Coal or coke at a particle size in excess of 5 mm is usually
added for this purpose, and is carbonised in the shaft but is not burned to any significant extent. Since
the shallow coke layer has minimal strength requirements, as distinct from a shaft furnace, it is not
necessary to conform to normal rigid coking coal specifications. On the other hand it is still necessary
for the carbon to arrive at the coke layer in granular form. If it decrepitates to a fine powder under the
thermal shock of entering the burner flame, it is more likely to be carried out in the gas stream than
enter the coke layer. It would appear that any low volatile coal with reasonable coking properties is a
suitable reductant for the Kivcet process.
Lead oxide reduction is relatively rapid and efficient, whereas zinc oxide is much slower and only
a small proportion forms zinc vapour to report in dusts and fumes. Ferric oxide reduction is more
endothermic than PbO reduction, and if present in significant amounts such as from zinc plant leach
residues, will lower the temperature of the coke layer and reduce the efficiency of PbO reduction. To

compensate, additional finely divided coal can be added to the feed to both raise the flame
temperature and achieve some further reduction before the coke layer. Also, oxygen can be injected
just above the coke to burn emitted CO to CO2 (Slobodkin and Kluev, 1998).
Electric furnace
Metallic lead formed in the coke layer rapidly falls through the slag to form a bullion layer on the
hearth of the furnace. The slag and bullion flow under a water-cooled copper partition or curtain
wall immersed into the slag bath, then into the electric furnace. Electrical energy input maintains the
slag temperature at around 1200 to 1300°C and power input is controlled by the depth of immersion
of the electrodes into the slag layer. Slag circulates from the electric furnace into the base of the
burner shaft and thus also provides heat to the coke layer, helping to maintain its operating
temperature. The original Kazzink furnace had six in line electrodes and it was intended that a
significant level of zinc fuming would be carried out. Since this was not particularly efficient in
comparison with a separate slag fuming furnace, subsequent designs have substantially reduced
electric furnace bath volume with three electrodes in line. Small quantities of coke are added to
complete lead reduction, some zinc fuming can occur and a zinc oxide fume is collected from
electric furnace off-gases. Power input is of the order of 150 kWh per tonne of furnace feed through
prebaked graphite electrodes; coke addition can be up to 5 kg/t of furnace feed and electrode carbon
used is between 1 and 2 kg/t of furnace feed.
The total bath depth in the electric furnace is between 1500 and 2000 mm, with the lower bullion
layer at around 900 mm. The bullion is kept at a significantly lower temperature than the slag to
protect the hearth, and is tapped through an underflow siphon at the end of the furnace. Slag is tapped
intermittently.
In some operating conditions a copper matte can be formed and can be tapped separately as in
Russian plant practice. This requires the temperature of the bullion to be lowered to around 500°C, but
enough copper remains in the bullion to still require a copper drossing operation and there are
significant losses of copper in slag. In addition the tapping of matte can be difficult. If the recovery of
copper is a significant economic issue then it is preferable to operate at higher bullion temperatures to
avoid matte formation and retain copper in the bullion for subsequent recovery by copper drossing.
As an example, the Teck-Cominco plant operates at bullion temperatures at 850 to 950°C in order to
prevent matte formation (Ashman et al, 2000).
Electric furnace gases generally pass through an after-burner to burn CO and to oxidise any zinc to
zinc oxide fume, are then cooled and cleaned by passing through a scrubber or bag house filter.
Although it is possible to recover the zinc content of the slag by fuming in the electric furnace with
coke additions, this requires a much larger furnace volume and is not generally regarded as
competitive with separate conventional slag fuming.
Comparative plant details
Table 7.4 provides details of a number of Kivcet furnaces and operating conditions.
From Table 7.4 bullion with less than 0.5 per cent sulfur can be achieved as well as slags
containing around one per cent lead. However, where slag fuming facilities are available for zinc
recovery, low lead levels can be sacrificed for furnace throughput as in the case of the Teck-Cominco
owned Trail plant. The lead content of slag will be almost fully recovered with the zinc oxide fume
and will be recycled in the form of zinc plant leach residues containing lead as lead sulfate.

TABLE 7.4
Kivcet furnace details.
Plant Kazzink Kazzink Porto Vesme Trail

(original) (upgraded) (Teck-Cominco)
Dimensions
Hearth area (m2) 86 57 88 120
Length (m) 19.2 13 20 24
Width (m) 4.5 4.5 4.5 5
2
Smelting shaft area (m ) 12 12 14 30
Shaft height (m) 3 5 6.2 7.2
Number of burners 2 2 2 4
2
Uptake shaft area (m ) 10 10 11 25
Electric furnace area (m2) 62 34 54 55
Number of electrodes 6 3 3 3
Electrode diameter (mm) 600 600 800 900
Performance
Feed rate (t/d) 480 600 720 1400
Specific feed rate (t/d.m2 of shaft area) 40 50 51 47
Feed (% concentrates) 72% 25% 73% 27%
Oxygen (Nm3/t of feed) 185 268 165 208
Coke use (kg/t of feed) 17.5 25 45 110 (coal)
Electrode power (kWh/t) 275 160 170 110
Other power (kWh/t feed) 60
Electrode carbon (kg/t) 2.1 1.0
Product streams
Lead bullion (t/d) 280 300 350
%S 0.4 1.0
%Cu 0.8 2.1 0.6 2.0
Matte (t/d) 10 9
%Pb 12 11.4 40 31.4
%Cu 23 35 25 45.8
%Fe 20 5 0.33
%S 21 20 12 15.8
Slag (t/d) 120 650
%Pb 0.4 - 2.0 1.2 4 5
%FeO 30 26 28
%SiO2 22 22 21
%CaO 14 20 12.7
%Zn 12 - 18 11.4 9 17.8
Smelter gas volume (Nm3/t of feed) 200 - 250 400 360
%SO2 40 - 50 15 - 17 22 - 25 12 - 15

Furnace construction
The furnace is built within a steel frame to support the side walls. Structural support and expansion
forces are transmitted to the frame through metal springs allowing for movement from thermal
expansion.
The hearth is an inverted arch constructed on a steel plate base and composed of a lower graphite
brick layer and an upper chrome magnesite brick layer, separated by a stainless steel sheet. The lower
support plate is cooled by a series of channels supplied with air from variable speed fans. Air cooling
is used rather than water which would present a significant danger. The lower refractories are cooled
to below the melting point of lead so that leakage cannot occur.
The side walls of the furnace are made up of water-cooled copper jackets, lined with chrome
magnesite brick. Each jacket is individually cooled and outlet water is kept below 50°C. The furnace
roof is a suspended arch made from chrome magnesite brick.
The internal separation walls are similarly constructed of water-cooled copper elements lined with
brick. The gap between the slag layer and the bottom of the wall separating the smelting and gas
off-take shafts is critical, and accretion build-up at this point is a significant issue.
The Kivcet process is robust and highly flexible in the range of possible feed materials, from
high-grade concentrates through to secondary leach residues. It produces a low volume of smelter gas
rich in SO2 and suitable for sulfuric acid production. It is also well contained with minimal opportunity
for environmental emissions, particularly in comparison with sinter plant–blast furnace technology.
THE QUENEAU-SCHUHMANN-LURGI (QSL) PROCESS

As discussed in ‘Principles of Direct Smelting’, a significant problem with direct oxygen smelting
using the roast reaction (Equation 7.3) has been the volatility of lead sulfide at reaction temperature
and the associated lead content of the slag produced. One means of overcoming these difficulties was
proposed by Queneau and Schuhmann (1974), in which the reactions are conducted within a molten
slag bath overlying a layer of molten lead. Oxygen is injected into the base of the reactor in much the
same way as in a bottom blown converter. Oxygen rapidly reacts with the molten lead to form PbO,
which transfers to the slag layer and reacts with added lead sulfide to form SO2 and lead metal as in
Equation 7.19:
PbO + PbS = 2Pb + SO2 (7.19)
The slag formed is further treated by carbothermic reduction in an effective second stage to reduce
its lead content before discharge from the reactor.
A long cylindrical reactor was proposed with feed and oxygen injection at one end and coal injection
at the other end. Slag flowed from the oxidation end to the reduction end and out of the vessel, whereas
lead bullion flowed in the reverse direction to exit at the oxidation end. The process was developed by
Lurgi Chemie und Huttentechnik and hence the name QSL Process. A demonstration unit was
constructed in Duisburg, Germany in 1981, followed by the construction of commercial plants for
Berzelius Metalhutten at Stolberg, Germany, for Korea Zinc at Onsan in South Korea and at Baiyin in
China. A fourth unit was constructed for Cominco at Trail, British Columbia but was unsuccessful and
was replaced by a Kivcet unit. The failure of the Cominco plant has been attributed to the attempted use
of natural gas for slag reduction rather than coal as used for the other plants.
A schematic of the QSL reactor is given in Figure 7.10.

Boiler
Feed hopper
Gas to
Acid plant
Air or enriched air
Gas Off-take
Shaft
Slag layer
Bullion layer
Bullion output Oxygen Coal and oxygen

Slag
Oxidation Section Reduction Section
FIG 7.10 - The Queneau-Schuhmann-Lurgi (QSL) reactor.
Metallurgy and reactor design

In the oxidation section of the reactor, feed materials including concentrates, residues, fluxes such as
silica and lime, and coal as an auxiliary fuel are dropped into the slag bath. Predrying of these
materials is unnecessary. Oxygen is injected into the base of the furnace through tuyeres, which have
a surrounding shroud of nitrogen to protect the tuyere from the corrosive effects of the PbO formed.
Oxygen passes into the molten lead layer, rapidly forming PbO and heat. The PbO rises into the slag
layer where it reacts with sulfides and sulfates from the feed to produce SO2 and metallic lead, which
falls back into the bullion layer. The lead bullion under highly oxidising conditions is relatively low in
sulfur and can be directly tapped from the vessel at around 1100°C through an inverted siphon. Sulfur
levels in bullion of less than 0.5 per cent can be achieved. The slag at this point is high in PbO at
around 40 per cent and flows to the reduction section of the reactor.
The oxidation section temperature is controlled by varying the input of oxygen and auxiliary fuel
as required. The PbO content of the slag at this point is adjusted by the feed to oxygen ratio. Oxygen,
or oxygen enriched air is added to the gases leaving the oxidation section to remove any volatilised
sulfides. The gas then passes through an uptake shaft lined with a membrane boiler wall, which serves
to cool the gases to below 700°C before entry to the convective section of the waste heat boiler.
Sulfated sticky lead dusts are collected in the offtake shaft and removed by rapping equipment,
causing the collected dusts to dislodge and fall back into the reactor. Following the boiler, gases at
around 350°C are cleaned in an electrostatic precipitator with four fields in series, followed by further
cooling and scrubbing prior to supply to a sulfuric acid plant. Gas composition is normally in the
range of 12 to 20 per cent SO2, but with high levels of CO2 at around 15 per cent and high levels of
moisture from the concentrates also at around 15 per cent. Oxygen can be of a similar level to SO2 and
the balance is nitrogen.

Dusts from the boiler and gas cleaning system are recycled back to the reactor, but depending on
the cadmium content part may be removed and leached to extract cadmium before recycling to
prevent development of a large circulating load.
Slag from the oxidation section flows over a weir separating the two sections to the reduction stage
where coal and oxygen are injected to reduce the lead content. Metallic lead formed by reduction
flows back in the reverse direction to the oxidation section. Slag flows out of the reactor via an
overflow weir and is targeted to contain less than five per cent Pb. It was initially proposed that the
reduction section with five coal injectors would form a series of well mixed cells giving a gradation in
the lead content of slag along the reactor to a low final value. To some extent this could be assisted by
baffles; however, it has been found that diffusion rates at the operating temperature of around 1250°C
are so high that it is difficult to achieve any gradation in slag composition and the achievement of low
lead slags has been difficult. However, levels of 2.5 per cent lead in slag have been achieved. To assist
in settling entrained metallic lead in slag, an area without injectors is provided at the slag discharge
end of the reactor to allow metallic lead to separate before the slag is discharged.
Slag composition as set by flux additions is targeted at close to blast furnace slag composition with
a typical slag from the Stolberg smelter reporting: two to three per cent Pb, 25 to 28 per cent FeO, 21 to
23 per cent SiO2, 21 to 23 per cent CaO and seven to eight per cent Zn (Pullenberg and Rohkohl,
2000).
Part of the zinc content of slag is also reduced and reports as zinc vapour to the reduction gases
together with some lead. Air or oxygen enriched air is added to oxidise the zinc to an oxide fume and
the gases are then cooled and finally cleaned in a bag filter to recover the zinc fume. Although
oxidation and reduction gases can be separated, this is not necessary provided mix gas strength in
terms of the SO2 content remains suitable for acid production. It should be borne in mind that a
significant quantity of nitrogen is added as shroud gas around each injector and represents around one
quarter of the oxygen volumetric flow.
The length of the reduction section of the reactor is at least twice the length of the oxidation section
but is of reduced diameter. The relative slag volumes and residence times are the critical parameters
and are determined by the relative amounts of sulfides and oxide lead materials in the feed mix,
particularly the amount of lead to be reduced. The lead pool maintained in the reduction zone is
minimal and merely provides a channel for the lead to flow back to the oxidation section.
The cylindrical reactor can be rotated through 90° when the process is interrupted to lift the
injectors clear of the slag bath. This also allows access to the injectors for maintenance or
replacement. Injector life is relatively short and has been quoted for the Stolberg unit at 800 hours for
the oxidation section and 1300 hours for the reduction section. Overall plant availability was given as
85 per cent.
The reactor is constructed in much the same way as a rotary kiln but with limited rotation. It is
generally lined with chrome magnesite brick. The experience with refractory wear has been a
problem, with particular areas opposite the injectors and at the slag/gas interface line showing high
wear rates. Improved cooling of refractories and profiling of the refractory surface has progressively
improved and prolonged refractory life.
Comparative plant design data
Table 7.4 lists comparative design data for the four commercial plant designs to date. Note that the
Cominco plant did not achieve design expectations and was replaced.

TABLE 7.5
Design data for Queneau-Schuhmann-Lurgi (QSL) smelters (Mager and Schulte, 1989).
Plant Stolberg Korea Zinc Bayin Cominco

Lead production (t/a) 80 000 60 000 52 000 120 000
Reactor diameter
Oxidation (m) 3.5 4.5 3.5 4.5
Reduction (m) 3.0 4.0 3.0 4.0
Reactor length (m) 33 41 30 41
Oxidation section length (m) 11 13 10 13
Reduction section length (m) 22 28 20 28
3
Slag volume in oxidation (m ) 24 47 21 47
Slag volume in reduction (m3) 30 74 26 74
% concentrates in raw material 63 53 100 53
% lead in raw material 45 35 66 34
Total feed (t/h dry) 27.34 34.5 16.0 81.7
Raw materials (t/h) 20.8 22.7 11.0 52.0
Silica (t/h) 0.04 0.4 1.0
Limestone (t/h) 0.3 2.7 0.7 6.3
Recycle oxidation fume (t/h) 4.3 5.0 2.2 15.4
Recycle leach residue (t/h) 1.3 1.5
Recycle fumed slag (t/h) 1.2
Coal fines (t/h) 1.9 2.8 0.5 5.5
Oxygen to oxidation (Nm3/h) 4700 7300 2250 13 000
Coal to reduction (t/h) 0.9 1.4 0.7
Natural gas to reduction (Nm3/h) 400 1,750
3
Off gases (Nm /h)
Oxidation 22 400 31 000 14 000 44 000
Reduction 65 000 25 300
Slag production (t/h) 7.1 8.8 4.0 28.4
Bullion production (t/h) 9.6 7.9 7.2 33.8
Steam production (t/h) 14.3 19.0 6.0 33.0
Oxidation slag (%Pb) 50 40 40 35
Reduction slag (%Pb) 2.5 2.0 2.5 5.0
The QSL process has significant advantages over sinter plant–blast furnace technologies. It is a
single step smelting process, is well contained with low emissions and can accept a wide range of feed
materials. It does not require dry feed as with the Kivcet process; however, in its early stages it did not
prove to be as robust or as flexible as the Kivcet process, particularly with attempts to use natural gas
for reduction and in its ability to handle quantities of zinc plant residues.
TOP SUBMERGED LANCE (TSL) – SLAG BATH PROCESSES

The top submerged lance–slag bath reactor for injection of gases and fuel into a slag bath was
developed in Australia by the Commonwealth Scientific and Research Organisation (CSIRO), and
was termed the SIROSMELT Process. The original aim was to avoid the refractory problems

associated with submerged injection tuyeres by using a submerged lance separated from the
refractory lining of the reactor and which could be withdrawn and readily replaced in the event of
maintenance problems. The key development was the design of the lance, which relied on the
formation of a frozen slag layer on its outer surface to protect the steel from attack by aggressive slags,
such as those high in PbO content or molten metals. The lance consisted of an outer steel tube
containing one or more inner tubes for the injection of fuel or feed materials. Cold air is blown down
the outer tube which is fitted with helical baffles to impart a swirl to the airflow and increase the heat
transfer coefficient to the tube wall. Superficial gas velocity is around 100 m/s and the outer tube is
cooled sufficiently to freeze a layer of slag on its outer surface. The lance is in fact initially slowly
lowered into the slag bath to sufficient depth to cause enough splashing to form the frozen slag coating
before it is fully immersed.
The reactor can be a simple vertical cylindrical vessel lined with refractory brick. The slag bath is
highly turbulent as a result of the gas injection by the lance, requiring the vessel to be relatively high in
comparison with the slag bath depth, due to the high degree of splashing and the need to avoid
carryover of spray into the gas offtake, where it can freeze on the walls and cause accretions and
eventual blockage. For this reason top burners can be used to ensure that freeboard gas temperature is
high enough to melt accretions and prevent build-up.
Initial application of this process to lead (and copper) was developed by Mount Isa Mines and was
termed the Isasmelt process. Other applications and later also tin, copper and lead smelting and zinc
fuming were developed by Ausmelt Limited, both as licensees of the Sirosmelt technology.
THE ISASMELT PROCESS

The Isasmelt lead process was developed as a two-stage process for the smelting of lead concentrates.
The first stage is a continuous oxidation stage to eliminate sulfur as SO2 and form a lead-rich slag, and
in some cases lead bullion. The second stage involves the reduction of the lead rich slag by the
addition of carbon to form lead bullion and a slag with a low lead content. Gases from each stage are
separately handled through waste heat boilers and gas cleaning equipment. The oxidation stage gas
can be passed to a sulfuric acid plant.
A small demonstration unit was constructed at Mount Isa but was only operated for a short time and
then only the oxidation section appeared to have been routinely operated. In that case the lead-rich slag
was solidified and crushed for use as a replacement for return sinter in a standard sinter plant. This
increased the lead throughput of the sinter plant accordingly. Product sinter was reduced in a blast
furnace. No applications of the full Isasmelt lead process to the smelting of lead concentrates have been
implemented, although it has been applied to the smelting of secondary materials, but using a batch
operating mode rather than a continuous process as originally envisaged (Matthew et al, 1990).
Figure 7.11 shows a schematic of the two-stage Isasmelt lead process.
Oxidation stage
Concentrates and fluxes are mixed in a paddle mixer and fed via a weigh feeder directly into the slag
bath reactor. Wet feed is satisfactory, eliminating any need for drying, but high moisture will consume
more fuel and increase the volume of smelter gases.
Flux additions are set to provide a slag with an FeO:SiO2 ratio of 2:1 and an FeO:CaO ratio of 5:1.
Higher levels of CaO will increase the activity of PbO and hence will aid subsequent reduction, but
this will be offset by the increased volume of slag and greater lead loss at the same final lead in slag
value.

Concentrates
Silica
Lime Recycled dusts
Boiler
To acid plant
Electrostatic
precipitator
To stack
Mixer Fuel
Boiler
Gas off-take
Air + shaft
oxygen
Coal
Fuel
Air Bag filter
Cooling tower
Oxidation stage
Reduction stage
Bullion Slag
FIG 7.11 - Isasmelt lead smelting process.
Air enriched to around 30 per cent oxygen is injected through the lance, and fuel in the form of
pulverised coal, oil or natural gas is also injected as required to maintain the bath temperature at
around 1150 to 1200°C.
Off-gas containing eight to 12 per cent SO2 passes through a vertical membrane cooled offtake
shaft to a waste heat boiler, electrostatic precipitator, gas scrubber and sulfuric acid plant.
Lead sulfide volatilisation is largely suppressed by rapid incorporation of the feed into the molten
slag bath under oxidising and highly turbulent conditions. Nevertheless approximately ten to 15 per
cent of the lead in feed can be volatilised and appear in sulfated form in dusts collected from the boiler
and gas cleaning plant.
Oxidation rates are quite rapid and as a guide, smelting rates equivalent to about 1.3 t/h of sulfur as
sulfides in feed can be processed per cubic metre of slag bath volume.
The lead content of oxidation stage slag is in the range of 40 to 55 per cent Pb and the balance of
lead from feed can form bullion. The amount of bullion formed will depend on feed composition, but
can be controlled to some extent by the stoichiometric excess of oxygen supplied for the smelting
reactions. At 105 per cent stoichiometric oxygen supply a maximum amount of bullion will form,
whereas at 125 per cent bullion formation can be eliminated, producing a high lead slag only.

Slag and any bullion formed can continuously overflow from the reactor into the second reduction
reactor, or it may flow into a settler to separate bullion and slag, if bullion separation at this point is
required. Bullion from the oxidation stage can contain higher levels of precious metals and bismuth,
and lower levels of sulfur, arsenic and antimony than bullion from the reduction stage; copper levels
are similar. For this reason there may be advantages in separating the two bullions.
Conditions in the oxidation reactor favour the formation of magnetite and zinc ferrite, which tend
to precipitate and coat the surface of the refractories (chrome magnesite brick) and the lance. This
provides an effective protection layer, leading to relatively long refractory life for this stage. The
reduction stage, however, does not have this protection and consequently has a much shorter
refractory and lance life. To enhance this effect the operating temperature can be held just below the
liquidus temperature of the slag.
Reduction stage
Slag reduction takes place in a similar vessel to the oxidation reactor, but with the injection of fine
coal and air. Lump coal can also be directly added but reduction rates appear to be favoured by the
injection of fine coal through the lance. The operating temperature of the reduction is higher than the
oxidation stage since the liquidus temperature of the slag rises as the level of PbO is lowered. Typical
operating temperatures are 1200 to 1250°C.
There have been no long-term commercial operations of a continuous reduction stage and details
of a preferred mode of operation and performance are quite unclear. However, it would appear that
this operation has been problematic due to the difficulty with attainment of low final lead levels and
excessive fuming of lead. Tail slags with less than two per cent lead have been demonstrated in pilot
plant operations, but at long residence times and practical operating levels for typical slags may be
well above five per cent. Lead fuming, expressed as a proportion of input lead, is higher for low lead
content slags; gas volumes are also high compared with other direct smelting processes, aggravating
this problem. Zinc fuming also increases as the lead level in slag is lowered and can be of the order of
50 per cent. It is substantially increased with the operating temperature of the reduction stage. Fuming
during reduction is understood to be a significant issue for this process, and can develop a large
circulating load.
Gases from the reduction reactor pass through an uptake shaft, waste heat boiler, quench cooler
and bag house filter to recover fume. The fume may need to be partly leached to separate cadmium
and zinc before recycle.
Slag overflows from the reactor into a forehearth to separate bullion, and good settling is essential
for the achievement of low final lead levels in discard slag.
It would appear that there could be advantages in operating the slag reduction stage in a batch
mode rather than continuously. This approach may allow a progressive change in reducing conditions
to minimise fuming, but few details of this practice are available.
In general the oxidation stage of the Isasmelt process appears to be robust and practical but there
are clearly difficulties with the reduction stage, which has yet to be satisfactorily demonstrated.
Indeed the application of the Isasmelt process to secondary lead processing at the Britannia Lead
refinery in the United Kingdom smelts battery paste materials to produce bullion and a high lead slag
at around 50 per cent Pb, which is separated and reduced in a rotary furnace rather than in the Isasmelt
furnace with its substantially higher gas flows. An Isasmelt furnace is also used at Metal Reclamation
Industries in Malaysia with a capacity of around 50 000 t/a of lead bullion.

The ISA-YMG smelter in Qujing, China uses an Isasmelt first stage furnace to smelt concentrates
with partial recovery of lead as bullion. The high lead slag is cast into biscuit moulds producing a
lump slag that is then smelted with coke in a specially designed blast furnace. The blast furnace has
modifications in the crucible area to allow intensive tuyere blast interaction with the pool of slag and
coke in the hearth so that target levels of lead in final slag can be achieved. This smelter configuration
replaces the sinter plant and is being proposed as a future direction for primary lead smelting
technology.
THE AUSMELT LEAD PROCESS

The Ausmelt lead process is similar in principle to the Isasmelt process above but differs in detailed
design (Mounsey and Piret, 2000). Ausmelt supply a broad range of top submerged lance
technologies and have constructed four primary lead smelters using this approach, including a
140 000 t/a of bullion plant for Metaleurop at Nordenham in Germany, a plant for Goldfields of South
Africa at Tsumeb in Namibia, an 80 000 t/a of bullion unit for Korea Zinc at Onsan, South Korea and a
60 000 t/a smelter for Hindustan Zinc at Chanderiya, India.
Ausmelt offers a highly flexible arrangement with one, two or three furnaces in series, operating in
either batch or continuous mode or in any combination thereof. In the smelting of sulfide concentrates
it is usually preferable to have the first oxidation stage operating continuously in order to supply SO2
to any associated sulfuric acid plants, which are unable to handle large variations in throughput. Slag
reduction can be operated in either batch or continuous mode and a third stage can be added if it is
required to recover zinc by fuming. A batch operated oxidation stage may be suitable for processing
secondary materials, oxides or leach residues. In fact all the above installations operate with only one
furnace each, which is used for differing duties on a campaign basis.
Smelting or oxidation stage

Of prime importance in this stage is the deportment of lead to bullion, slag and fume. Ausmelt data
has substantially defined this relationship as highly dependent on the lead concentration in the
feed as well as the stoichiometric oxygen:concentrate ratio. Table 7.6 summarises the typical lead
distribution for high, medium and low-grade feed materials.
TABLE 7.6
Deportment of lead in the smelting stage.
Feed grade Smelting Smelter slag Deportment of Deportment of Deportment of
(% Pb) temperature ( C) grade (% Pb) lead to bullion (%) lead to slag (%) lead to fume (%)
60 - 80 1000 - 1100 40 - 60 75 - 85 5 - 15 5 - 15
45 - 60 1100 25 - 40 36 - 60 25 - 45 15 - 20
<45 1150 - 1250 20 - 30 20 - 50 30 - 50 20 - 30
Note: refer to Mounsey and Piret (2000).
The variation of these distributions with oxygen supply for one particular feed is shown in
Figure 7.12.
The deportment of lead to bullion can be increased by increasing the lead in feed as in Table 7.6,
by increasing the oxygen enrichment of the air, by decreasing the temperature and by decreasing the
sulfur in feed (which strongly corresponds with higher lead grade concentrates).

100
90
80
Lead deportment (%)
70
60
To bullion
50 To slag
To fume
40
30
20
10
0
60 70 80 90 100 110 120 130 140
Oxygen Stoichiometry (%)
FIG 7.12 - Effect of oxygen stoichiometry on lead deportment.
Reaction rates in the oxidation stage are very high and largely limited by the capacity of the gas
handling system.
Slag reduction stage

Slag from the smelting or oxidation stage is carried out in a separate second stage by the addition of
coal and air. As the PbO content falls the liquidus temperature of the slag rises and this stage generally
operates above 1200°C. The higher temperature will produce increased quantities of fume and from
this viewpoint batch operation can be beneficial in progressively raising the temperature as the slag is
reduced. Final slags containing less than three per cent lead are feasible. However, the deportment of
lead to fume or bullion has not been defined in a generalised way as for the oxidation stage above, but
is a significant issue and based on operating plants does not appear to be a particularly attractive
option. The Metaleurop smelter at Nordenham uses a single furnace and was initially designed to
campaign oxidation and reduction stages, granulating and stockpiling high lead slags from the
oxidation stage for later campaign reduction. However, the unit operates only as the smelting stage
and lead-rich slags are sold to other smelters (as a sinter feed supplement). The Tsumeb smelter was
similarly a single reactor with campaign operation of smelting and reduction stages but ceased
operation in 1998 due to closure of the mine complex.
In the situation where the zinc content of feed is relatively high, slags can contain up to 18 per cent
zinc, and recovery can be considered. Although some zinc will fume during slag reduction down to
two per cent lead, the bulk will remain and can be fumed in a third stage with coal addition and
operating at higher temperatures of between 1250 and 1300°C. This stage may be operated
continuously in a third furnace or on a batch campaign basis using the reduction furnace. If extensive
zinc fuming is practised, allowance must be made for secondary air input above the bath to oxidise
zinc vapour to an oxide fume, and for the high level of heat so generated. Gas cleaning facilities must
also be capable of collecting and handling the zinc fume generated. Ausmelt reactors operating in this
mode are in use at the Onsan plant of Korea Zinc.

Reactor design
The conventional design has been a steel shell lined with refractory brick and cooled by shower sprays
on the outer surface. The upper section on reduction reactors where afterburning occurs can operate at
quite high gas temperatures and are subject to severe refractory conditions, requiring additional shell
cooling. More recent designs for the Korea Zinc fuming reactors have used a water jacketed section
for the top of the reactor and the roof as part of the boiler system. This allows a protective frozen slag
layer to form.
THE OUTOKUMPU LEAD PROCESS
The Outokumpu flash smelting process for lead is an extension of the successful flash smelting
technology developed by Outokumpu for copper and nickel and applied to lead concentrates. It was
developed and piloted at a 5 t/h treatment rate in the late 1980s but has not been commercially
applied.
Lead concentrates are dried and fed to a flash burner with 95 per cent oxygen gas, located at the top
of a smelting shaft. A high lead slag and some bullion are produced and collect in the base of the
furnace. Gases rich in SO2 pass up through a separate off-take shaft to cool and allow volatile lead
compounds to sulfate and be separated as a fume for subsequent collection in the waste heat boiler and
electrostatic precipitator.
In common with other direct smelting processes the smelting stage aims to achieve high sulfur
elimination and hence requires oxidation conditions, which will necessarily result in the formation of
a high lead slag of between 20 and 60 per cent lead. The higher the grade of the concentrate feed, the
higher will be the proportion of lead in concentrates reporting to bullion. For low-grade concentrates
all the lead can report to slag with no or minimal bullion formation in the smelting stage. The slag and
bullion are continuously tapped from the smelting furnace into a separate electric furnace where the
PbO in slag is reduced to lead bullion by injection of coal with nitrogen through lances. Pilot tests by
Outokumpu showed that the rate of reduction of PbO by a floating coke layer was slow and could be
increased five times by injection of coal into the slag bath.
Off-gas from the electric furnace can contain significant amounts of lead and zinc, which are
oxidised to a fume by the addition of air in an after burner chamber. If high zinc recovery is required
from the slag the electric furnace temperature must be raised, but this will cause a substantial increase
in the amount of lead to fume. Bullion and slag are separately and continuously tapped from the
electric furnace.
The efficiency of the electric furnace for reduction and the degree of fuming of lead are the key
areas of concern with this process, but no commercial scale data is available to demonstrate
performance. Indicative consumption figures for a high-grade lead concentrate of 76 per cent Pb have
been given as:
• oxygen use 120 Nm3/t of concentrate
• propane fuel use 5 kg/t of concentrate
• coal for reduction 18 kg/t of concentrate
• power use 100 kWh/t of concentrate
(Weenink, de Puy and Duyvesteyn, 1990).

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Sychev, A P, Kuenov, A S, Sannikov, Y I, Slobodkin, L V, Lysenko, V A and Grinin, Y A, 1985. Completion of
an important stage in the implementation of the Kivcet-TSS process at the Ust Kamenogorsk lead-zinc
combine, Tsvetnye Metally, 29(1):11-15.
Walker, M, 1998. Kivcet smelter on-stream at Trail, Mining Magazine, 178(4):256-263.
Ward, D H, 1985. Scientific and technical developments in lead smelting and refining, in Proceedings Scientific
and Technical Developments in Extractive Metallurgy, G K Williams Memorial Volume, pp 25-32 (The
Australasian Institute of Mining and Metallurgy: Melbourne).
Ward, D H, 2007. Personal communication.
Weenink, E M, de Puy, E R and Duyvesteyn, W P C, 1990. Computer modelling of mass and energy balances for
the Outokumpu lead flash smelting process, in Proceedings Lead-Zinc 90, The Minerals, Metals and
Materials Society (TMS) Symposium, Anaheim, pp 597-606.

Willis, G M, 1980. The physical chemistry of lead extraction, in Proceedings Lead-Zinc-Tin ’80, The Minerals,
Metals and Materials Society (TMS) – AIME Symposium, pp 457-476.
Yazawa, A and Nakazawa, S, 1998. Comparison between copper, lead and nickel smelting processes from
thermodynamic viewpoints, in Proceedings Sulfide Smelting Symposium ’98, pp 39-48 (The Minerals,
Metals and Materials Society (TMS): Warrendale).
Zaitsev, V Y and Margulis, E V, 1985. The Metallurgy of Lead and Zinc (translation by D H Ward, 1992).

CHAPTER 8
Smelter By-Products and Treatment Processes
INTRODUCTION
Apart from lead bullion the smelting process produces slag, which often contains residual lead and
recoverable quantities of zinc. Flue dusts are also produced in varying quantities and, depending on
the operating conditions of the smelter, a matte and speiss can also be produced. Matte can be
produced as a means of separating copper, but can also capture a significant portion of the precious
metals, silver and gold. The following details processes used to treat these streams and recover
valuable by-product metals.
SLAG CLEANING
Reduction of slag in the blast furnace to below 1.5 to 2.0 per cent Pb is uncommon and will raise coke
consumption. In the extreme at lead levels at or below one per cent in slag there is potential for the
formation of metallic iron and the production of speiss phases, which cause accretions and tapping
difficulties. On the other hand, with more oxidised slags solid phases can form, raising slag viscosity
and impeding tapping and lead separation from the slag in the forehearth. Such solid phases may be
magnetite, or melilite arising from a high zinc content. Operating the smelter at moderate residual lead
levels in slag to avoid these problems will incur lead and precious metal losses and thus a separate slag
cleaning stage to effect further reduction and lead separation can be justified. Lead is present in slag
both as fine droplets, which have not settled out, and as dissolved PbO. Apart from using a separate
slag cleaning stage for additional reduction of PbO, simply raising the temperature and providing
extended settling time can then be a significant benefit.
Such slag cleaning is best done using an electric furnace where high slag temperatures can be
achieved without large gas volumes and consequent heat losses. With residence times of the order of
eight hours and the addition of coke, lead in slag can be reduced down to 0.5 per cent. As well as
bullion, an alloy phase can be produced rich in iron and copper, depending on the copper levels in
smelter feed. Often the higher temperature alone will reduce slag viscosity and allow fine droplets of
lead to settle, significantly reducing the lead content of the final slag.
An installation of this type was installed at the Umicor Hoboken smelter in Belgium (Van Negen,
Maes and Cocklebergs, 1990). In that operation 20 per cent of the charge was cold slag and reported
operating data is as follows:
• blast furnace slag charge 2.45 per cent Pb, 1.28 per cent Cu, 7.2 per cent Zn,
118 g/t Ag
• cleaned slag 0.55 per cent Pb, 0.37 per cent Cu, 5.77 per cent Zn,
10 g/t Ag
• flue dust (3.4 per cent of charge) 18.1 per cent Pb, 54.1 per cent Zn
• bullion (0.4 per cent of charge) 88.6 per cent Pb, 5.21 per cent Cu, 4243 g/t Ag
• alloy (3.6 per cent of charge) 26.3 per cent Pb, 25.5 per cent Cu, 1.99 per cent Zn,
19.2 per cent Fe, 2460 g/t Ag
• coke consumption two per cent of charge

CHAPTER 8 – Smelter By-Products and Treatment Processes
• power use 280 kWh/t of charge

• electrode carbon use 12 kg/MWh
ZINC RECOVERY FROM SLAGS
Process chemistry and thermodynamics

Depending on the zinc content of raw material feeds to the smelter, slag can contain up to 17 per cent
zinc. This is a practical solubility limit beyond which solid zinc containing melilite phases tend to
precipitate raising the viscosity of the slag. Higher zinc levels also contribute to significant accretion
problems in the blast furnace. Use is made of the relatively high vapour pressure of zinc to recover it
from slags by reduction and vaporisation into a gas stream, usually followed by oxidation of the
vapour to form zinc oxide as a fine particulate fume. It is theoretically possible to condense zinc metal
from the gas stream, but in practice this is difficult due to impurities present and to re-oxidation of zinc
vapour by CO2 and water vapour. The presence of sulfur in lead smelter slags arising from the need to
retain some sulfur in bullion, also means the PbS will volatilise during fuming operations. This will
react with zinc vapour as the gas is cooled to form ZnS and metallic lead. Because of these
complications the concept of direct condensation of zinc from slag fuming gases has not been applied
commercially to the treatment of lead smelter slags, although some process developments incorporate
this concept – see electric furnace slag fuming, below.
The most common approach uses the injection of coal with air and oxygen into a molten slag bath
at around 1200°C. Zinc oxide is reduced to zinc vapour according to Equations 8.1 to 8.3:
ZnO + CO = Zng + CO2 (8.1)
CO2 + C = 2CO (8.2)
Overall reaction ZnO + C = Zng + CO (8.3)
The vapour pressure of zinc above a slag bath relates to the CO/CO2 partial pressure ratio in the
gas and the activity of ZnO in the slag according to Equation 8.4:
K1 . p CO . a ZnO
pZn = (8.4)
p CO 2
where:
aZnO is the activity of ZnO dissolved in the slag
K1 is the equilibrium constant of Equation 8.1 at the particular temperature
The activity of ZnO can be related to the mole fraction of ZnO in the slag by the activity coefficient
as in Equation 8.5:
aZnO = γZnO . NZnO (8.5)
where:
γZnO = activity coefficient of ZnO
NZnO = the mole fraction of ZnO in the slag

A review and assessment of ZnO activity coefficients on this basis was given by Grimsey et al
(1993), and is illustrated in Figure 8.1. This data is for a slag of 8.5 per cent Al2O3 content at 1300°C
and the slag composition has been condensed so that ZnO + CaO + SiO2 + FeO equals 100 per cent.
Isobars have been constructed for constant ZnO activity coefficients, and are shown as dotted lines. It
is clear that the activity coefficient largely depends on the CaO/SiO2 ratio and increases as the ratio
increases.
10 60
20 50
30 40
wt% CaO wt% SiO 2
3.0
2.5 2.0 1.5
40 50 60 70 80
wt% ZnO+FeO
FIG 8.1 - Activity coefficient for zinc oxide in slag at 1300°C.
At a fixed CaO/SiO2 ratio the activity coefficient also increases as the Al2O3 content is increased.
For example, a typical lead blast furnace slag may have an activity coefficient of 2.0 at 8.5 per cent
Al2O3 and this will increase to around 2.5 at 22.5 per cent Al2O3. This is a significant simplification of
a complex system and more detailed thermodynamic modelling of the ZnO-PbO-FeO-Fe2O3-
CaO-SiO2 system with slag liquidus phenomena, component activities and the effect of precipitating
phases on viscosity under various conditions has been given by Jak and Hayes (2002).
Liquid zinc cannot be formed in the slag unless the vapour pressure is above the saturation vapour
pressure of liquid zinc at the operating temperature. The saturation vapour pressure is given by
Equation 8.6, and under atmospheric pressure conditions at around 1200 to 1300°C the saturation
vapour pressure well exceeds the vapour pressure derived from reduction. Hence liquid zinc cannot
form in the slag bath.
6163
Log pZn = 5.227 − (8.6)
T
where:
pZn is in atmospheres
T is in K

The equilibrium constant for zinc oxide reduction according to Equation 8.4 is given as a function
of temperature in Table 8.1, together with the partial pressure of zinc vapour in equilibrium with a slag
containing four per cent ZnO, as the end-point slag fumer composition, and a reduction gas ratio of
CO:CO2 of 2:1. Also shown is the saturation vapour pressure of liquid zinc metal according to
Equation 8.6.
TABLE 8.1
Equilibrium constant for ZnO reduction.
Temperature (K) 1100 1200 1300 1400 1500

Equilibrium constant (atm) 0.00167 0.00901 0.0305 0.130 0.374
Zn partial pressure (atm) 0.0002 0.001 0.0046 0.0156 0.045
Zn saturation vapour pressure (atm) 0.42 1.233 3.064 6.68 13.13
There has been conjecture about the principal mechanism for reduction from a molten phase and
whether the process is in chemical equilibrium or is controlled by reaction kinetics and mass transfer.
Initial studies of the reduction reactions in slag fuming (Bell, Turner and Peters, 1955; Kellogg, 1957)
assumed that reaction rates were sufficiently high at operating temperatures above 1000°C for
equilibrium conditions to prevail. Kellogg (1967) developed a mathematical model of the slag fuming
process on this basis, and this was subsequently further developed and applied successfully at Port
Pirie (Grant and Barnett, 1975) and at Boliden (Bygden et al, 1985).
Empirical models were also developed for fuming processes, indicating an approach to a first
order reaction with respect to zinc concentration in the slag as indicated by Equation 8.4 (Izbakhanov
et al, 1990). Application of the models developed for one operation did not necessarily apply to
another and slag properties such as viscosity clearly had a significant influence. Some operations
more closely followed a zero order reaction in which the zinc reduction rate was independent of the
zinc concentration in the slag, at least above a level of around four per cent Zn in slag (Richards,
Brimacombe and Toop, 1985). This work indicated that solid carbon within the melt was significant,
and the kinetics of the process may be controlled by the injection of coal particles into the slag bath as
opposed to retention as a suspension in the gas phase. The kinetics can therefore be enhanced by high
velocity injection. In practice neither temperature nor oxygen potential (or CO:CO2 ratios) remain
constant and hence there can be significant departure from first order with respect to ZnO activity with
rates to some degree dependent on heat and mass balance issues.
The rate of reduction of zinc oxide in slag is also influenced by the FeO (or the ferrous to ferric
iron ratio) and the sulfur contents of the slag. Rates are progressively increased as the FeO content
increases. This is attributed to the reduction of zinc oxide by ferrous iron and the subsequent reduction
of the ferric iron formed by CO. Rates may also be reduced by the presence of sulfur in the slag, thought
to be caused by surface blockage of the gas–slag interface due to the surface active nature of sulfur in
the slag, but may also be due to the impact on ZnO activity (Dal, Jahanshahi and Rankin, 1997).
There are clearly a number of parallel reduction reactions and it would appear that their
predominance depends on physical conditions and the operating conditions of the furnace. Some
reactions may have low resistance and are not rate limiting, and others such as those involving solid
carbon in the melt are kinetically controlled and can be enhanced by giving attention to carbon particle
sizing and injection methods. Slag properties, particularly viscosity can have a bearing on the kinetics
and can also change as the zinc concentration is depleted. However, it is now accepted that with an
adequately deep slag bath limiting the opportunity for gas bypassing, equilibrium is essentially
achieved so that the Kellogg model can be applied (Ward, 2000).

In most practical slag reduction operations coal is used as the source of carbon. Hydrocarbons are
present and hydrogen can be formed giving rise to water vapour in reduction gases, which can result
in re-oxidation of zinc vapour as the temperature is lowered. This will make condensation of metallic
zinc from reduction gases difficult, but is not a disadvantage for fuming operations producing ZnO.
The use of natural gas should therefore be a suitable fuel, but it was found that reduction rates fell
significantly when coal was replaced by natural gas. Work at the Chimkent Lead Smelter in Russia
(Izbakhanov et al, 1990) attributed this to the slow decomposition of the hydrocarbons, which then
tended to pass through the molten slag and burn above it. Oxygen potential in the injected gas was
therefore high and tended to oxidise iron in the slag to magnetite. This precipitated as a solid phase
and raised the viscosity of the slag, further reducing reduction rates, or in the extreme caused the bath
to freeze. Cracking and precombustion of the natural gas to CO and hydrogen in external chambers
before injection into the slag bath overcame most of these difficulties (Polyvyanni, 1976).
Processes utilising molten phase reduction usually employ in situ combustion of fuel to maintain
operating temperature and to provide the necessary heat to balance endothermic reduction reactions
and heat loss through the furnace walls. The gas phase is thus further diluted with nitrogen as well as
having high levels of CO2 for maximum fuel utilisation efficiency. The thermal efficiency of the
process can be improved by preheating input air to reduce the combustion fuel required and by the use
of oxygen enrichment to reduce the volume of gas to be heated. However, the flow of gas does serve
to enhance the removal of zinc vapour from the bath and there are limits to the positive impact of
oxygen enrichment.
An issue in some of the processes used for the reduction of zinc oxide from slags operating at
extreme reducing conditions is the control or avoidance of the formation of metallic iron. Iron has a
wide melting range depending on the carbon content. The minimum liquidus temperature of 1130°C
corresponds with a eutectic at 4.3 per cent carbon. This rises to 1535°C for pure iron with no carbon
content. For carbon contents above 4.3 per cent the liquidus temperature again rises. From usual
reduction processes it would appear that the carbon content of iron formed can be around three per
cent, melting at 1250°C. If the iron is decarburised by moving to reaction zones of higher oxygen
potential, it can freeze and cause severe accretion problems. Therefore, operating conditions are often
selected to avoid or minimise the formation of metallic iron.
Iron formation results from the reaction given in Equation 8.7:
FeO + CO = Fe + CO2 (8.7)
The equilibrium constant for the reaction 8.7 can be expressed in Equation 8.8:
p CO 2 × a Fe ∆G
K= = exp( − ) (8.8)
p CO × a FeO R× T
where:
aFe is the activity of the iron formed taken as 1.0
aFeO is the activity of FeO dissolved in the slag
The activity of FeO in ternary system slags is shown in Figure 8.2, from which it can be deduced
that typical slags of around 35 per cent FeO will have an activity of around 0.4. This need not
necessarily apply to a more complex multi-component system, but illustrates the possible variation
and range of FeO activity coefficients.

SiO 2
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
CaO FeO
FIG 8.2 - Activities of FeO in system FeO-CaO-SiO2 at 1600°C (Elliot, Gleiser and Ramakrishna, 1963).
The competing reduction of ZnO and FeO can be illustrated by the equilibrium ratios of CO:CO2
as a function of the temperature at which reduction occurs. These equilibrium curves are shown in
Figure 8.3 for zinc at levels in a typical slag of 2.5 per cent and seven per cent, and for iron reduction at
FeO levels in slag of 15 per cent and 45 per cent. Reduction will occur for CO:CO2 partial pressure
ratios in regions above the equilibrium curves. For regions above all curves, both ZnO and FeO will
be reduced and iron will be formed. For regions at high temperatures above the zinc equilibrium
curves and below the iron curves, ZnO will be reduced without the formation of metallic iron. Raising
the zinc content or lowering the iron content will extend this region of no iron formation to lower
operating temperatures. At low temperatures FeO will be reduced in preference to ZnO.
3.5
Zn 2.5%
3
Zn 7%
2.5
FeO 15%
Log(Pco /P co2 )
2
FeO 45%
1.5
1
0.5
0
-0.5800 1000 1200 1400 1600
-1
Temperature ( C)
FIG 8.3 - Equilibrium curves for ZnO and FeO reduction.

For typical situations with slags containing around 35 per cent FeO, zinc can be fumed to levels of
2.5 per cent in final slag without iron formation if the temperature is above about 1250°C. For higher
iron slags, such as the typical ISF slag, this temperature must be above 1300°C, or if the slag contains
seven per cent zinc, above 1200°C. The tendency to form metallic iron during fuming is significantly
greater for ISF slags than for normal blast furnace slags, where few such related problems are normally
encountered.
As well as removing zinc, fuming will also remove most of the lead content of the slag and if this is
recycled by return of zinc smelter residues to the lead smelting stage, then almost complete lead
recovery can be achieved in an integrated operation. This ability of lead to fume is illustrated by the
vapour pressure of lead compounds at 1250°C:
• PbS vapour pressure at 1250°C 0.987 atm
• PbO (liquid) 0.154 atm
• Pb (liquid metal) 0.040 atm
THE CONVENTIONAL SLAG FUMING FURNACE

The conventional slag fuming furnace was developed for the injection of coal into hot blast furnace
slag, with secondary air injection above the slag bath to oxidise zinc, and included equipment for gas
cooling and fume collection. Slags which typically contain between ten and 18 per cent Zn and around
2.5 per cent Pb, 30 per cent FeO, 25 per cent SiO2 and ten per cent CaO are suitable. Zinc recovery is
economic only at high levels of zinc in slag, and hence slag fuming furnaces are now only applied
where the zinc content of slag is at the upper end of the range at around 16 per cent or more. In fact
when such a facility is in place it benefits the lead smelter to source concentrates containing zinc in
order to optimise the levels in slag. No payment is required for such zinc content in lead concentrates
and it is ‘free metal’ to the lead smelter.
The first commercial installation of the standard slag fuming furnace was at the Asarco, East
Helena lead smelter in Montana in 1927, and this furnace design has subsequently been applied at a
number of other major lead smelters. Copper smelter slags rich in zinc are also processed in
conventional slag fumers such as at Boliden’s Rönnskär smelter in Sweden, and at the Flin Flon
smelter of Hudson Bay Mining and Smelting Company.
The standard furnace is constructed as a long narrow rectangular box of steel water-cooled panels.
A row of tuyeres is fitted to each long side just above the furnace floor level so that a suspension of
fine coal in air is blown into the molten slag through the tuyeres. A schematic of the slag fuming
furnace is shown in Figure 8.4.
A typical furnace has cross-sectional dimensions of 2.4 m wide by 6.4 m long and 6.4 m high. The
walls are made of rows of water jackets, with three rows each of seven jackets making up each long
side for the typical size. The floor is also made up of water-cooled panels. There are three tuyeres in
each lower jacket, giving 21 tuyeres per side. Furnaces may vary in size by varying the number of side
wall panels, but the width is usually constant and dictated by the depth of penetration of the blast from
the tuyeres into the melt (Hancock, Hart and Pelton, 1970; Ashman et al, 2000).
The water-cooled panels or jackets freeze a protective layer of slag on their inner surface, which
can be studded to assist in adherence of slag. This form of containment rather than refractories has
been chosen because of the aggressive conditions and the high turbulence and abrasive nature of the
bath, and has been highly successful with jacket life extending well over ten years and up to 20 years.

Water Tube Boiler Section
Membrane Wall
Gas to
Shaft
Cooling and
Fume Collection
Feed Slag
Dust Collection
Fuming Furnace
Slag Level Tap Hole
Spent Slag to Granulation

Tuyeres
FIG 8.4 - Conventional slag fuming furnace.
The price of this form of containment is the additional fuel required to compensate for the relatively
high heat loss through the jackets to maintain the protective slag layer. Water is circulated through the
jackets and is flashed to low pressure steam.
Furnaces are normally operated in a batch mode and the typical size with a 15.4 m2 cross-section
will hold approximately 45 to 50 tonnes of slag. Slag is charged as molten blast furnace slag using a
ladle and also as cold slag or as residues containing zinc. In the first part of the batch cycle, air and
pulverised coal are blown into the furnace to fully melt the bath and to raise the temperature of the
contents to around 1250°C. The air rate for this part of the cycle is set to provide sufficient oxygen for
complete combustion of coal and maximum heat generation. Some fuming of zinc occurs, but at a rate
which is about one third of the rate under reducing conditions. The time taken for the heating phase
depends on the proportion of cold material charged and the temperature of the molten slag feed.
The second phase of the cycle is the fuming phase in which the coal rate is increased, but the air
rate is reduced to ensure that the oxygen supply is sufficient for 60 to 70 per cent of complete
combustion. Fuming is completed when the zinc content of the slag is reduced to between two to three
per cent and the furnace is then tapped to complete the cycle. Bath temperature falls during fuming but
rises at the end of the cycle and can be purposely raised at the end of the batch by raising the air rate to
assist in furnace tapping by lowering slag viscosity and hence reduce the time required for tapping.
Alternatively lowering the coal addition rate for a fixed air rate at the end of the cycle will also allow
complete combustion to CO2 and will raise the slag temperature in preparation for tapping.
During the initial heating-oxidation stage of a batch slag fuming process the ferrous:ferric iron
ratio decreases and if this stage is extended too long it can result in magnetite formation, which can
precipitate from the slag. Reduction of magnetite will occur first in the fuming phase in preference to

ZnO reduction, acting as a buffer that limits the initial rate of zinc reduction. Because of this effect
close control of the heating cycle of a batch fuming process to minimise magnetite formation is an
important issue.
Overall cycle times are generally of the order of two to three hours, giving an effective fuming rate
within the range of 200 to 280 kg of zinc per hour per square metre of furnace cross-section. A typical
metal elimination curve is given in Figure 8.5 showing the zinc concentration in the slag bath with
time. This relates to the fuming phase of a cycle only, starting from an initial slag composition of
17 per cent Zn. If an initial heating phase is used then some fuming will occur during this part of the
cycle at lower rates.
Fuming rates may be taken from Figure 8.5 and expressed as per cent decline in zinc content per
hour. This is shown in Figure 8.6.
18
16
14
Zinc Content %
12
10
8
6
4
2
0
0 50 100 150 200
Time - minutes
FIG 8.5 - Typical zinc in slag reduction during fuming.
8
7
6
Fuming Rate %/h
5
4
3
2
1
0
0 5 10 15 20
Zinc Content %
FIG 8.6 - Typical zinc fuming rate versus slag composition.

For a furnace with a 50 tonne initial charge the corresponding fuming rates in tonnes of zinc per
hour are shown in Figure 8.7 as a function of furnace slag composition.
5
Fuming rate - tonnes Zn/hour
4.5
4
3.5
3
Instant
2.5
Average
2
1.5
1
0.5
0
0 5 10 15 20
Zinc in Slag %
FIG 8.7 - Zinc fuming rate versus slag composition (50 tonne capacity furnace).
Two curves are given in Figure 8.7: the lower curve representing the instantaneous fuming rate at
the particular slag composition during the cycle, and the upper curve representing the overall average
fuming rate to that particular tail end slag composition. As illustrated, the rate declines significantly as
fuming proceeds and the zinc content of slag is reduced.
For a total cycle, including time allowances for charging and heating and for tapping of the
furnace, the tonnes of zinc fumed will be averaged over an extended time period, only part of which
will cover high fuming rates. By way of example, for a total cycle, including 30 minutes for furnace
charging and 15 minutes for tapping, the overall average zinc fuming rate as a function of final tail
slag composition is shown in Figure 8.8.
3.00
2.50
Av. Zinc Fuming rate t/h
2.00
1.50
1.00
0.50
0.00
0 2 4 6 8 10 12 14 16
Residual Zn in slag %
FIG 8.8 - Average overall fuming rate versus tail slag composition (50 tonne capacity furnace – batch operation).

The curve in Figure 8.8 is relatively flat with little difference in overall furnace capacity when
operating between three and nine per cent residual zinc in slag from a feed of 17 per cent zinc.
However, zinc recovery is maximised at the lower residual zinc level and it is common practice to
operate at a tail slag composition of around 2.5 to three per cent zinc. Below this there will be a
significant fall-off in furnace capacity.
If the fuming furnace can be charged with hot slag, then the average fuming rates over the total
cycle can be increased by eliminating the heating phase. An electric slag holding furnace may be used
for this purpose and indeed Teck-Cominco’s Trail smelter feeds hot slag directly at 1340°C from an
electric furnace associated with its Kivcet lead smelter (Ashman et al, 2000). In the situation with hot
slag feed, the optimum tail slag composition can be lower and Teck-Cominco operate to a tail slag of
close to 2.0 per cent.
Zinc is vaporised from the slag bath as zinc metal but is oxidised above the bath by the
introduction of secondary air. Secondary air also burns CO to CO2 and any fine coal particles in
suspension in gas emitted from the bath, and is controlled to achieve an oxygen level of five per cent
in furnace flue gas. As a result the temperature of furnace gases above the bath can rise to 1600°C. The
furnace gases pass up through a shaft composed of a water-cooled membrane wall to a water tube
boiler where the temperature is reduced to around 650°C. The membrane wall is integrated within the
boiler system.
Accumulation of dust on the boiler tubes and walls is a significant problem and soot blowing is
extensively required, usually using saturated steam.
Gases from the boiler are further cooled to below 200°C and are filtered using bag filters to capture
the zinc oxide fume. Gas cooling is commonly by air coolers and by humidification in water spray
towers. Air cooling by exchange with furnace combustion air to achieve a preheat of up to 600°C is a
useful way to improve thermal efficiency and reduce coal consumption. However, in the total gas
handling system there are major issues with the accumulation of sticky dust deposits and the need for
constant cleaning of heat exchange surfaces and ducts to prevent flow restriction. Typical plant
availability is 88 per cent and is largely dictated by the need for cleaning parts of the gas train rather
than the fuming section. Downtime can vary significantly and is critically dependent on the design of
the gas handling system.
Coal is usually pulverised to 90 per cent minus 200 mesh and is transported in a fluidised state
using cold air to the tuyeres, where it is injected with blast air into the slag bath. Coal consumption is
of the order of 16 to 25 per cent of the slag charge where the slag contains around 17 per cent Zn, and
represents between 1.1 and 1.7 tonnes of coal per tonne of zinc recovered. The lower end of this range
requires full preheating of blast air, but variations also depend on the extent of charge heating required
and the proportion of cold feed, as well as the length of the fuming cycle.
The presence of hydrocarbons should theoretically increase zinc fuming rates. However, in
practice there have been mixed messages. In some cases softer high volatile coals are beneficial, but at
the Trail smelter coal consumption was found to be proportional to the fixed carbon content with little
effect from the volatile content. This is said to be due to slower reaction rates of volatiles, which tend
to burn above the slag bath (Yurko, 1970), but may be an artefact of mass balance control and
departure from equilibrium conditions.
Ash from coal dissolves in the slag and dilutes the zinc content. This tends to reduce zinc recovery
and hence low ash coals generally give higher zinc recovery. The use of high ash coal at the expense
of zinc recovery may, however, be justified by the lower price of that coal.
As with zinc, lead will fume efficiently, possibly assisted if some sulfur is present in the slag. A
slag containing 2.5 per cent Pb will be reduced to less than 0.05 per cent with a lead recovery in excess

of 98 per cent. Lead is fumed ahead of zinc during the first part of the cycle. Cadmium, halides and
arsenic will also be fumed with high recovery. Germanium, indium, thallium, antimony and tin are
fumed to varying degrees.
Operation of slag fuming furnaces in a continuous rather than batch mode has been practised, but
is not common. A notable exception was at the Non-ferrous Metallurgical Works at Plovdiv in
Bulgaria. If operated continuously, the composition of the slag in the furnace must be that of the tail
slag. Since fuming rates reduce as the zinc content falls, the fuming rate for continuous operation will
be at the minimum. The reduced fuming rate needs to be offset by the time eliminated from the cycle
for charging, heating and batch tapping. The initial experience with the Plovdiv plant has shown
reduced capacity with continuous operation, but each case needs to be evaluated for its particular
circumstances.
Details of operating conventional slag fuming furnaces are given in Table 8.2.
TABLE 8.2
Representative conventional slag fuming furnaces (Grant, 2004).
Plant Chihuahua Chimkent Flin Flon Plovdiv Port Pirie Ronnskar Trail
Company Asarco Kazakhstan Hudson Bay Dimiter Nyrstar Boliden Teck
Blagoev Cominco
Year commissioned 1952 1974 1952 1970 1966 1964 1998
Number of furnaces 1 1 2 1 2 1 1
Operation Batch Batch Batch Continuous Batch Batch Batch
Length × width (m) 6.4 × 2.44 8.48 × 2.41 6.4 × 2.44 2.3 × 2.54 4.57 × 2.44 8.1 × 2.4 6.4 × 2.44
Height (m) 7.32 7.2 7.32 6.25 9.00
Hearth area (m2) 15.61 20.45 15.61 5.85 11.15 19.4 15.61
Tuyeres per side 14 14 21 11 15 26 21
Slag charge (t) 39 120 72 - 75 25 @ 13 t/h 40 - 45 105 70 - 85
Slag – Zn% 11.7% 11 - 17% 8 - 10% 12.5 - 14% 16 - 18% 9.5% 16 - 18%
Slag – CaO/SiO2 0.88 0.7 - 0.8 0.047 0.61 0.7 1.33 0.61
Slag depth (m) 1.02 1.5 1.2 - 1.3 1.1 0.97 - 1.09 1.44 1.13 - 1.36
Tail slag (Zn%) 1.9% 1.9% 0.7 - 1.0% 2.0 - 2.5% 2.2% 1.0% 2.5%
Cycle time (min) 80 130 - 150 180 110 - 200 120 150 - 180
Slag rate (t/day) 646 1100 560 312 380 1200 650
Fuel type Coal Nat gas Coal Oil Coal Coal Coal
Fuel use (t/t zinc) 2.1 - 2.3 1.56 1.06 - 1.10 2.8
Productivity (tZn 4.05 6.50 2.94 5.86 5.04 5.25 6.04
per m2 day)
There are opportunities to increase fuming rates for a continuously operated furnace by dividing it
into a series of compartments with progressively lower levels of zinc in each. However, the general
conclusion appears to have been that the best capacity is achieved by batch operation.
TOP SUBMERGED LANCE SLAG FUMING

As an alternative to the conventional slag fuming furnace, a top submerged lance slag bath reactor
may be used for zinc fuming. In this process fuel as gas, oil or pulverised coal is injected with oxygen

enriched air through a vertical submerged lance into a molten slag bath contained in a refractory lined
vertical cylindrical vessel. Lump coal can also be added as a reductant. The high degree of turbulence
generated by the injected gas promotes reaction rates and heat transfer.
The principles of the submerged lance rely on the cooling effects of the injected air passing down
through the lance to freeze a protective layer of slag on its outer surface, otherwise the lance would be
rapidly consumed at the operating temperature of around 1300°C. These principles were developed
by the Commonwealth Scientific and Industrial Research Organisation (CSIRO) in Australia with
early application to tin fuming in 1978. Further development of application to zinc fuming was by
Ausmelt with commercial application at the Onsan Smelter of Korea Zinc and by Mitsui at the
Hachinohe ISF smelter. The process has also been applied to copper smelting and to lead smelting by
Mount Isa Mines (Isasmelt process), as discussed in Chapter 7. One key part of these processes is the
design of the lance so as to achieve stable operation and long life (Floyd and Swayn, 1998).
A schematic of the submerged lance slag bath process is shown in Figure 8.9.
To Atmosphere
Gas Cooler
Fuel
Bag Filter
Primary Air
Secondary Air Fan

Feed
Boiler
Lance
Slag Fume
FIG 8.9 - Schematic of submerged lance slag bath reactor.
Feed materials together with fluxes and lump coal are directly fed into the bath through a port in the
reactor lid. Fuel is injected with air enriched with up to 45 per cent oxygen into the bath through a lance,
which is supported on a hoist so that it can be lowered into the bath and raised free of the reactor for
cleaning or replacement. The need to have an adequate volume of gas flowing through the lance to
provide cooling limits the degree of oxygen enrichment possible. Secondary or after-burning air is also
supplied through the lance assembly but exits from the lance above the bath level. Additional secondary
air enters through the feed and lance ports, but these are normally as constricted as possible to limit this
uncontrolled input. The vessel is maintained under slight suction from the gas handling system. The slag
bath is highly turbulent and the reactor vessel needs to be tall (at about three times the vessel diameter) in

order to prevent blockages in the gas outlet duct due to splashing. Since the lance needs to be fully
withdrawn from the reactor, a relatively high structure is required to accommodate the plant.
Secondary combustion can generate elevated temperatures in the gas above the bath, and adding to
the required cooling load before the fume is separated. As shown in Figure 8.9, gas is cooled firstly in
a waste heat boiler consisting of a membrane wall shaft to drop the temperature to below the point
where fume is sticky. It then enters the convective water tube section of the boiler. Additional cooling
is by humidification using water sprays to drop the temperature below 200°C so that fume can then be
collected using bag filters. For a small plant the cost of a boiler may not be justified and cooling by
humidification alone can be used. Collection of fume using an electrostatic precipitator is also
practical and will allow collection at a higher temperature than a bag filter (400 - 500°C), thus limiting
the degree of cooling required. If an electrostatic precipitator is used it should contain at least three
fields in series to ensure efficient removal of fume to low levels. To ensure that fume is removed and
exhaust gas meets environmental standards, the use of a bag filter often has been preferred.
The gas handling and fume collection facilities are essentially the same as for the conventional
slag fuming furnace, although in this case it is possible to significantly reduce the volume of furnace
gases by a higher degree of oxygen enrichment. Gas volumes are also reduced by fewer opportunities
for gas leakage and air ingress.
Top-submerged lancing (TSL) – slag bath reactor operating principles and

construction
The chemical principles are the same as those described for the conventional slag fuming furnace and
fuming rates are of a similar order. However, it is usually preferable to operate the TSL slag bath
reactor continuously rather than in batch mode. This can avoid the need for feed slag holding facilities
and larger gas handling volume capacity, which is the primary cost of the plant. The cost of the reactor
is relatively small in comparison with the conventional fuming furnace and extended residence time
can be more readily accommodated.
Zinc is fumed from molten slag as metal vapour and is oxidised to ZnO fume above the bath by
secondary air. Considerable heat is generated by secondary combustion, and can be partly captured by
the bath as molten slag is projected into the gas space by the turbulence generated by the lance. This
heat capture by the bath reduces the actual fuel needs within the bath and improves fuel efficiency.
The high level of turbulence is in the centre of the reactor around the lance and well away from the
reactor wall, unlike the conventional slag fuming furnace where injection tuyeres are located in the
furnace wall and gas can rise along the wall. In the case of the conventional furnace, refractory lining
of the furnace walls is not possible and the water jacket containment design is necessary. For the
submerged lance reactor refractory lining is possible, but even so there is sufficient turbulence to
severely impact on refractory life. In some installations refractory life was less than three months with
plant availability under 80 per cent. However, this has generally improved with experience, and
refractory life exceeding two years can be achieved using chrome magnesite fused grain re-bonded
bricks for typical iron silica slags. Backing the refractory layer with water-cooled panels can also
assist in increasing refractory life.
The use of a water jacketed system alone places a limit on the operating temperature, which cannot
be much above the liquidus temperature of the slag. This limitation can be relaxed with refractory
lining provided critical temperatures for degradation of the bricks are not exceeded. With the use of
water jackets, the formation of metallic iron during fuming must be avoided. This will limit the
reducing conditions which can be applied, and the final level of zinc in tail slag should be above

two per cent. This is not so critical for the refractory lined reactor and final slags of one per cent Zn or
below are practical. The selection of the final zinc content of slag will be determined largely by
fuming rate considerations, but increased temperature can assist in comparison with the conventional
furnace. Although the risk to the integrity of the furnace associated with iron formation is reduced
with refractory lining, it may need to be avoided over long periods of operation with particular slags,
such as ISF slag, since it can give rise to severe accretion formation and blockage of the furnace.
Figure 8.10 illustrates the effect of reducing conditions as indicated by the final level of zinc in
slag, on the formation of metallic iron. This data relates to the fuming of ISF slag and shows the
combustion stoichiometry required to avoid metallic iron formation.
6
Zinc and Iron in Fumer slag %
5 Metallic Iron
Zinc
4
0
20 30 40 50 60 70
Combustion stoichiometry %
FIG 8.10 - Metallic iron and zinc content of slags versus reducing conditions (Sekiguchi and Azuma, 1998).
Due to the heat developed by secondary combustion of zinc vapour and CO above the bath, high gas
temperatures can be developed in the upper section of the reactor. This can also affect refractories by
exceeding their critical breakdown temperature. In this situation the use of a water-cooled wall has
benefits, particularly as loss of heat at this point assists in gas cooling. Following these principles, Korea
Zinc has proposed the use of cooling water circulating through copper sets within the refractory in the
lower part of the reactor and in contact with the slag bath, and a water-cooled membrane wall with
frozen slag layer protection for the upper section (Kim and Lee, 2000; Mounsey and Piret, 2000).
These questions of containment and refractory life are the primary concerns in the application of
this process and are still in an evolutionary phase at the time of writing. Otherwise the approach has
the advantage of relative simplicity.
Operation of the slag bath reactor in a continuous mode is feasible and in this case it is practical to
use multiple stages in series with slag flowing from one reactor to another. This can increase the
overall fuming rate for a given reactor volume but is also useful to separate gas streams if the feed
material contains sulfur.
When operated in batch mode, fuming rates for the submerged lance slag bath reactor are
comparable with average rates achieved in the batch operated conventional fuming furnace as
detailed above. This gives an indicative average decline in zinc content of six per cent per hour
between 17 and three per cent zinc content. From Figure 8.6 the continuous fuming rate at a slag
composition of two per cent zinc is equivalent to around four per cent decline in zinc content per hour.

For a reactor containing 1 m slag depth, the slag contained is approximately 3 t/m2 of cross-section
and the zinc depletion rate is thus of the order of 0.12 t of zinc fumed per hour per square metre of
furnace cross-section. This represents a crude indication of reactor capacity only, as gas flow rates are
also a major determining parameter and can differ significantly from the conventional slag fumer in
relation to bath cross-sectional area.
HIGH INTENSITY FUMING PROCESSES

These processes generally involve the injection of zinc containing material into a high temperature
reducing flame. Zinc oxide is reduced to zinc metal vapour reporting to the gas stream. Slag as a
suspension in the gas stream is separated either in a settling or impingement chamber or in a cyclone.
Secondary air is added to the gas stream after slag separation to burn CO to CO2 and zinc vapour is
oxidised to form zinc oxide fume, which is separated after cooling by gas filtration. Principles are the
same as described above for other fuming processes, with the exception that the reduction step is
conducted at high temperatures, with very high reaction rates and hence small equipment volumes.
High levels of oxygen enrichment are also used so that gas volumes and subsequent gas handling
equipment size is considerably reduced.
A number of variants of this approach have been proposed and evaluated but there are no full-scale
commercial operations solely for the purpose of zinc recovery. Two processes closest to commercial
development for zinc applications are the Horsehead Flame Reactor and the Contop Flame Cyclone
Reactor.
FUME TREATMENT
Crude zinc oxide fume produced by the fuming process contains a range of other volatile impurities,
particularly lead and halides, but also contains fine particulate slag and some coal ash carried over
from the fuming furnace with the gas stream. The carry-over depends to a large extent on the process
used but is generally less than one per cent of slag produced for the conventional fuming furnace and
between two and five per cent for submerged lance furnaces.
The presence of other volatile elements can be significant, depending on the application of the
fume and the process used for conversion to zinc metal. If the fume is to be used as feed to a retorting
process or to a blast furnace (ISF) then the requirements are not so critical, other than the need for
densification or briquetting, and either a secondary clinkering kiln or a hot briquetting process is
commonly used. If the fume is to serve as feed to an electrolytic zinc process there is a need to remove
halides, which are only tolerated in limited amounts in sulfate electrolytes, due to the detrimental
effects on electrodes during electrolysis, as well as the occupational health risk associated with
chlorine generation from open electrolytic cells. It is therefore usual to treat fume to remove halides
prior to feeding to an electrolytic zinc process.
Raw fume may be washed with water to remove halides. To prevent loss of zinc and other metals
into the wash solution it is usual to use sodium carbonate solution for fume washing. This converts
soluble zinc and other metal chlorides and fluorides to sodium chloride or fluoride and insoluble metal
carbonates which are retained with the fume. Wash solutions are generally maintained at a pH of 9.0
to 9.2. Alternatively the fume can be first washed with water and the resulting solution treated with
sodium carbonate or caustic soda to precipitate zinc (Chabot and James, 2000).
Halides may be removed by heating the fume in a gas or oil fired rotary kiln to around 1200°C with
a residence time of more than 12 hours. This can remove over 90 per cent of the chlorine content and

95 per cent of the fluorine content of raw fume. Secondary kiln treatment can also be used to remove
significant amounts of lead, but higher temperatures are required. Removal is achieved in part by
volatilisation of species such as PbCl2, PbF2 and ZnCl2. Complex fluoro-chlorides, PbClF and ZnClF
are also known to be present. The hydrolysis reaction given in Equation 8.9 also takes place, with the
water vapour being derived from the combustion of fuel and may be the main route for removal of
halogens from the fume.
ZnF2 + H2O = ZnO + 2HF (8.9)
In general halogen removal improves with higher firing and exit temperatures.
Rotary kilns used for de-halogenation require a capacity of the order of 0.6 m3 per tonne of raw fume
processed per day, and typical kilns are of the order of 2.0 to 2.5 m OD and 20 to 30 m in length. Kiln
slope is around 4° and refractory lining is typically 150 to 250 mm thick. Examples of commercial
operations are given in Table 8.3.
TABLE 8.3
Dehalogenation kiln installations (Grant, 2004).
Plant year Company No kilns Kiln Rotation Firing end Exit gas Feed rate
Length O diameter (rev/min) (°C) (°C) (t/d)
(m) (m)
Chihuahua 1952 Asarco 1 22.86 2.13 1.43 1400 650 - 740 100 - 112
El Paso Asarco 2 18.29 2.44 1.3 1384 - 1440 705 - 755 130 - 140
Kellogg 1943 Bunker Hill 1 22.86 2.13 0.94 - 1.05 1290 - 1370 600 - 760 68 - 77
Ronnskar 1964 Boliden 1 39.6 2.38 700 127
Port Pirie 1966 Nyrstar 2 27.5 2.44 To 2.5 1150 - 1200 400 - 650 200
Selby 1953 Asarco 1 22.86 2.13 1.3 1260 90
Tooele International 1 21.34 2.13 1.1 1260 704 - 815 73
smelting and
refining
Kiln gases pass through cyclones to remove dusts and are then scrubbed with a sodium carbonate
solution before discharge to atmosphere. Scrubbing liquor can be around 20 g/L Na2CO3 at a pH of
8.5. The carbonate scrubbing liquor precipitates zinc, lead and cadmium carbonates and leaves the
halides in solution. The collected and precipitated solids from the scrubber are separated by
thickening and filtration and are returned to the kiln feed.
Fuel consumption is of the order of 3000 MJ/tonne of fume processed.
Product fume from a dehalogenation kiln is usually cooled in a rotary drum cooler. The raw fume
will greatly increase its bulk density and particle size, and will require grinding before feeding to a
leaching operation. The presence of some impurities in the fume can influence the densification, for
instance the presence of silica derived from dust carry-over from the fuming operation can be of concern
if above 0.5 per cent in raw fume, since it tends to form a hard clinker, which is difficult to grind.
Generally kiln processing will be more efficient in removing halides to low levels, but is more
expensive than washing.
The dehalogenated zinc oxide fume is then sold to and processed in a zinc smelter for reduction to
zinc metal.

ELECTRIC ARC FUMING FURNACE

If the oxidation of zinc vapour from a fuming process can be avoided, and zinc can be recovered
directly by condensation, then considerable costs can be avoided and the viability of the zinc recovery
process can be significantly improved. This requires the use of a sealed system to maintain a low
oxidation potential and minimum volume of gas. The conventional slag fuming furnace is not suitable
for this purpose and a sealed electric arc furnace is most appropriate. The concept has been applied at
the Duisberger Kupferhutte smelter in Germany (Dietrich, 1962), at the Toho Zinc smelter at
Chigirishima, Japan (Itoh, Yamakita and Yoneoka, 1980) and at the Glubokoe smelter in Kazakhstan,
but more recently developed by Mintek in South Africa as the Enviroplas Process, using a high
temperature DC plasma arc furnace rather than an AC submerged arc, operating at 1400°C and
connected to a conventional lead splash condenser from the Imperial Smelting Furnace. This
arrangement is shown in Figure 8.11.
Slag + Coke Feed
Electrodes
Splash Condenser
LCV gas to scrubber
Zn vapour
Discard slag Cooler
Pb-Fe alloy
Zinc metal
FIG 8.11 - Electric furnace slag fuming and direct zinc recovery.
Slag and coke fines are fed into the furnace through a seal, and residual slag and an iron rich alloy are
tapped continuously at a temperature of around 1350°C. This approach has been applied to lead blast
furnace slag from the Belledune smelter of the Brunswick Mining and Smelting Company, containing
14 to 20 per cent ZnO, with a CaO:SiO2 ratio of 0.8 and a FeO:SiO2 ratio of 1.0 to 1.5. The single pass
zinc recovery achieved was generally above 70 per cent (LeClair, Hancock and Hickey, 1998).
The zinc condenser will produce zinc metal, but also a small quantity of matte and ‘Blue Powder’
as a mixture of surface-oxidised fine zinc particles as well as zinc/lead oxide dross. Condenser
efficiency to metal was around 70 to 80 per cent. Excessive production of Blue Powder and condenser
drosses is often a significant problem with these systems.
Zinc fuming rates in the electric furnace were directly proportional to the power input, with 180 kg
of zinc per hour per square metre of furnace area obtained at a power density of 1000 kW/m2 of
furnace area. The zinc level in residual slag could be reduced to less than three per cent and lead to less
than 0.2 per cent. Zinc fuming rates for other previous fuming operations using AC submerged arc
resistance furnaces range from 10 to 70 kg of zinc per hour per square metre of furnace area.

TREATMENT OF LEAD SMELTER MATTES

Normally copper in lead smelter feed is sufficiently low to fully dissolve in bullion and be recovered
by copper drossing as part of the refining stage. However, in the case of high copper feeds (above five
per cent of the lead content), a matte can be formed during smelting. This will require retention of
sufficient sulfur to form the matte, which tends to be a mixture of lead, iron and zinc sulfides as well as
copper sulfide.
With direct smelting processes such as Kivcet, matte can be tapped directly from the furnace at the
appropriate level, separate from bullion and slag. Where matte is separately produced from the blast
furnace it is usual to separate slag first and then separate matte from bullion in a separate forehearth or
settling pot where it can rise to the surface and freeze. Speiss can also form as a separate phase at this
stage, as a frozen layer from cooled bullion. Speiss is usually a waste product, but depending on the
smelter feed composition can be a point of concentration of nickel.
Smelter mattes may contain:
• 20 to 35 per cent Cu
• ten to 25 per cent Pb
• 20 to 35 per cent Fe
• five to nine per cent Zn
• 18 to 25 per cent S
The main method of processing matte is by oxidation with oxygen in a converter. Initially zinc and
iron sulfides are oxidised first to ZnO and FeO respectively, followed by PbS oxidation and then Cu2S
to copper metal and SO2.
The oxidation of PbS can be to metallic lead as well as PbO, and the lead bullion so formed can
dissolve in the copper up to four per cent. Excess lead metal can also dissolve copper. Alternatively
lead can be separated from the matte by deliberate fuming or by adding a flux such as silica to the
converter to enhance lead slagging. To minimise these complications it is preferable to raise the level
of copper in matte to 50 per cent or more before converting. This can be done by processing low-grade
matte back through the blast furnace, either as a recycle stream or as a separate campaign, as was the
practice at the Hoboken smelter, recovering lead bullion and an upgraded copper matte. Alternatively
with smaller quantities, a rotary furnace can be used, particularly with the addition of iron turnings to
displace lead from the matte and form lead bullion.
Any lead bullion recovered from matte treatment will be rich in copper and can form a significant
circulating load through the lead bullion refining stage (see Chapter 12 – Copper Removal or Copper
Drossing).
Converting of copper matte will produce ‘blister copper’, which can be cast into anodes for
subsequent electrolytic refining. Converter dusts are predominantly lead oxides and basic sulfates
containing zinc and can be recycled to the lead smelting operation.
In general the control of these operations and the handling of a range of side and recycle streams
can be difficult and a separate matte is rarely produced.
SINTER PLANT AND SMELTER DUSTS

Flue dusts and fumes collected from sinter plant and smelter gases can contain concentrations of
volatile metals as well as lead and zinc. Elements which tend to concentrate in sinter plant dusts are

cadmium, thallium and selenium. Usually these dusts are simply recycled and find an outlet in slag,
but if a high circulating load develops it can be necessary to provide a bleed by leaching these
elements from the dusts before recycling.
Apart from lead, blast furnace dusts are often enriched in cadmium, zinc and indium, and can be a
source for recovery. Again separation before recycle may be necessary to provide an outlet and
prevent the development of heavy circulating loads.
In direct lead smelting with no sintering operation, some of the volatile elements will be retained and
captured by lead bullion and may need special removal procedures. In particular this applies to thallium.
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CHAPTER 9
Electrochemical Reduction Processes
BACKGROUND
The possibility of electrowinning lead from primary concentrates has been investigated for well over a
century without the development of a robust and sustainable commercial operation. There are
attractions in reducing the large number of separate stages involved in conventional smelting and
refining operations, but there are considerable difficulties in handling a wide range of impurities,
extreme variations in the levels of minor impurities, and in the corrosive environment often encountered
with appropriate systems, such as in chlorine metallurgy.
Most of the early development attempts centred on the use of chloride systems that relied on the
reaction of lead sulfide with chlorine to produce lead chloride and elemental sulfur, followed by
electrolysis of the lead chloride to produce lead metal and chlorine for recycle.
PbS + Cl2 = PbCl2 + S0 (9.1)
Cathode Pb2+ + 2e = Pb (9.2)
Anode 2Cl2- = Cl2 + 2e (9.3)
The simplicity of the concept was attractive and early work was undertaken by Ashcroft at Cockle
Creek, Australia in the 1890s amongst others, on a dry system with electrolysis of molten lead
chloride. Lead concentrates were dry chlorinated with chlorine gas and the resulting molten lead
chloride was electrolysed in a heated cell using graphite electrodes. The build-up of impurities in the
molten salt electrolyte was a major issue. Subsequent developments focused on multi-metal complex
concentrates, producing mixed chlorides of zinc, lead and copper. Copper and lead metal were
recovered by displacement from the melt by the stage addition of molten zinc, leaving zinc chloride
for electrolysis in a molten salt cell. This approach may have produced a reasonable quality lead metal
but the impurity problems remained and were perhaps more difficult to handle with zinc
electrowinning from a molten salt (Ashcroft, 1933).
The alternative line of investigation was the use of an aqueous chloride system rather than molten
salts. Early work was based on a chloridising roast of the sulfide concentrates with the addition of salt.
The resulting calcine was leached with hot brine to give a lead chloride–sodium chloride solution.
This was purified by cementation with lead powder to remove more noble impurities and electrolysed
in a diaphragm cell. The cathode deposit tends to be crystalline and dendritic or even spongy, and
must be constantly removed by scraping or it will grow across to the anode, causing a short circuit.
The cathode lead collects in the base of the cell, is removed, compacted to minimise oxidation, and is
then melted and cast into lead ingot. Some early plants used rotating cathodes to effect continuous
removal of the lead deposit.
Chlorine gas is recovered from the anode compartment and in early plants with a chloridising
roast, was used to make calcium hypochlorite (bleaching powder). Later operations recycled chlorine
to the leaching operation for direct extraction of lead from the sulfide concentrate – eliminating the
roasting step and producing elemental sulfur. In the period 1918 to 1925 five commercial plants using
these methods were constructed in the USA, with one each in Canada, Australia and England. The

CHAPTER 9 – Electrochemical Reduction Processes
extreme corrosion problems encountered with the generation and handling of chlorine was a serious
complication, and this, together with problems associated with impurities, saw the demise of these
operations within a short period of time.
In more recent development efforts, and to avoid difficulties associated with handling chlorine, an
alternative has been the use of ferric chloride for direct oxidation of lead sulfide to lead chloride and
elemental sulfur. The resulting leach solution can be electrolysed in a diaphragm cell to deposit lead at
the cathode and re-oxidise ferrous iron back to ferric iron at the anode. Indeed ferric chloride is a most
effective leachant for PbS with almost complete attack in less than 15 minutes at 100°C, to form lead
chloride and elemental sulfur.
Other hydrometallurgical systems are limited due to the need for soluble lead salts. The normal
sulfate system used for other base metals is not applicable since lead sulfate is insoluble. Nitrate is
unacceptable because nitrate ions are reduced at the cathode to give NO2, NO and NH3. Suitable
electrolytes with high lead solubility and high conductance have been well developed for
electrorefining of lead and include:
• Fluosilicic acid H2SiF6
• Fluoboric acid HBF4
• Sulfamic acid HNH2SO3
• Dithionic acid H2S2O6
Dithionic acid tends to decompose at normal cell operating temperatures to H2SO4 and SO2. The
sulfate will then precipitate lead and SO2 will be reduced at the cathode to H2S, which in turn will
precipitate PbS. Sulfamic acid is also unstable at higher current densities and tends to break down to
form ammonium sulfate, in turn precipitating lead sulfate. Hence, the most suitable practical
alternative electrolytes are fluosilicic and fluoboric acid systems.
One significant issue for these alternative systems, where the anion does not take place in the
anode reaction, is the tendency to form PbO2 at the anode in competition with the formation of oxygen
in accordance with Equations 9.4 and 9.5:
Pb2+ + 2 H2O = PbO2 + 4H+ + 2e (Eo = -1.46 volts) (9.4)
2H2O = 4H+ + O2 + 4e (Eo = -1.23 volts) (9.5)
Although Equation 9.5 has the lower equilibrium potential there is a significant overpotential of at
least 0.5 volts depending on the nature of the anode. This then favours the formation of PbO2 over
oxygen. In the case of chloride the standard potential for chlorine formation is -1.36 volts with little
overpotential and hence this reaction is favoured. If ferrous iron is present then oxidation at the anode
in accordance with Equation 9.6 has a standard electrode potential of -0.7 volts and this reaction will
predominate.
Fe2+ = Fe3+ + e (Eo = -0.70 volts) (9.6)
The formation of PbO2 in significant amounts reduces the recovery of metallic lead from the process
and may require recycle of PbO2 by reduction and re-solution. However, it has been found that various
additives can suppress the formation of PbO2 on graphite anodes, such as the presence of 1.5 g/L of
phosphorus in solution as H3PO4. A disadvantage is that phosphorus can result in an increase in the
impurities in cathode lead. Arsenic at around 75 mg/L added as sodium arsenate will also suppress PbO2
formation on graphite anodes. The use of different anode materials can also be effective.

The use of iron to effect the direct leaching of lead from sulfide concentrates and its part in the
anode reaction is attractive in both providing an effective leaching reagent and in minimising the
voltage of the electrowinning cell, at the same time avoiding the formation of PbO 2.
PROCESSES BASED ON MOLTEN SALT ELECTROLYSIS
Electrolyte composition
The attractiveness of molten salt systems is the ability to produce high purity metal in molten form
ready for direct casting into ingots. The cells should therefore operate at temperatures above the
melting point of lead (327°C). Lead chloride melts at 501°C and hence is suitable, but it also has a
high vapour pressure at practical temperatures – 2.8 mm Hg at 550°C. This leads to significant fuming
from the cells, and creates problems by condensing on cold surfaces in the chlorine gas handling
system. Lead metal has some solubility in molten lead chloride and hence cathode lead will dissolve to
some degree into the electrolyte and will react with chlorine at the anode to reform lead chloride. This
effectively reduces the current efficiency of the cell to around 85 per cent. The addition of alkaline
earth metal chlorides to the molten salt mix can substantially lower the melting point and operating
temperature as shown in Table 9.1, as well as the solubility of lead metal.
TABLE 9.1
Liquidus temperatures for various salt mixes (Wong and Haver, 1977).
Mole % in mixture Liquidus temperature (°C)

100% PbCl2 501
28% NaCl + 72% PbCl2 410
36% LiCl + 64% PbCl2 400
49% KCl + 51% PbCl2 410
34% LiCl + 39% KCl + 27 PbCl2 320
Magnesium is generally avoided since it causes severe attack of graphite anodes.

PbCl2 forms complexes in the molten salt mix with KCl, NaCl and LiCl in decreasing order of
strength, and hence KCl will have the greatest effect on reducing fuming. In a tertiary salt mix, LiCl
will have a major impact on lowering the melting point, allowing lower temperature operation, which
also reduces fuming. LiCl also increases the conductivity of the melt to a greater extent than KCl due
to its smaller cation size. Work by the US Bureau of Mines (USBM) determined an optimum salt mix
of LiCl, KCl and PbCl2 as shown in the last row of Table 9.1. The operating temperature selected for
an electrolytic cell was 450°C for low cell voltage, low lead solubility and relatively low fuming
(Wong and Haver, 1977).
Other developers have used different salt mixes with NaCl replacing LiCl or even KCl because of
the cost associated with recovery from electrolyte bleed to control impurities.
Cell design
A number of different cell designs have been proposed, but these are based on the use of a brick-lined
cell with graphite electrodes. Major differences arise from the configuration of the electrodes. It is
possible to use vertical electrodes or horizontal electrodes or even slanted electrodes. Vertical

electrodes have a higher risk of contact between the falling lead and rising chlorine gas, particularly
with narrow electrode spacing. This will result in re-formation of lead chloride and loss of current
efficiency. Horizontal electrodes allow better separation of the two product streams, and tilting of the
electrodes will facilitate escape and prevent blanketing of the anode with chlorine gas.
The simplest form consists of a flat cathode located just above and electrically connected to a pool
of molten lead, which collects in the base of the cell. This in turn is connected through a steel bar to the
power supply. The anodes are graphite plates held above the cathode using ceramic spacers and
provide for the escape of chlorine gas to collect in the upper sealed space of the cell. The cell is fed
with dry lead chloride, which is controlled by the density of the electrolyte, and lead metal is
periodically tapped from the cell via a siphon.
A schematic of the USBM cell is shown in Figure 9.1.
FIG 9.1 - Molten salt cell for lead chloride (US Bureau of Mines).
Provision is made to supply alternating current to the cell to maintain a molten electrolyte
whenever electrolysis was discontinued.
With an electrode spacing of 19.1 mm, cell voltage is 4.7 at a current density of 6800 amps/m2.
Current efficiency is 93 per cent and energy consumption 1.32 kWh/kg of lead.
With the use of meshing saw tooth surfaces on the electrodes to facilitate the removal of chlorine
gas, spacing can be reduced to 12.7 mm, cell voltage to 2.5 and current efficiency can be raised to
98.7 per cent, giving an energy consumption of 0.66 kWh/kg of product lead.
A more complex design is the use of a stack of horizontal bipolar electrodes in which the lower
surface is the anode and the upper surface is the cathode. Only electrical connections are required for
the top and bottom electrodes. The problem with this system is that current can bypass around the
edges of the electrodes from top to bottom of the cell, and hence narrow gaps between the edges of the
electrodes and the walls of the cell are required. Sufficient room is necessary to provide for the flow of
lead to the base of the cell and chlorine gas to the top of the cell. Current bypass is reflected in a loss of
current efficiency. A cell using this principle was developed by Alcoa for the production of
aluminium from aluminium chloride, and has been applied to lead chloride, as shown in Figure 9.2.
Electrode spacing was 9.5 mm and inter-electrode voltage 2.8. Current efficiency was 95 per cent,
giving an energy consumption of 1.1 kWh/kg of lead.

FIG 9.2 - The Alcoa bipolar cell – designed for aluminium chloride.
Clearly electrode spacing is a critical parameter in achieving low energy use, but the design must
allow for ready separation of lead and chlorine to ensure high current efficiencies. There have been a
number of different designs proposed with this in mind, but it would seem that monopolar design is
favoured because of relative simplicity.
In general, current densities of between 1000 and 1500 amps/m2 are practical, cell voltage of 2.5 to
3.0 are achievable and current efficiencies of 95 per cent are attainable. The build-up of impurities in
the electrolyte bath is a significant problem in maintaining this performance, and an accumulation of
iron for instance can cause current efficiency to decline to 50 per cent. Similarly, copper can cause a
major decline in current efficiency.
Electrode life is unclear because of the lack of long-term operating experience. However, attack of
graphite anodes can be a significant problem if magnesium is present and erosion can result from the
addition of moisture with the lead chloride feed and the generation of oxygen at the anode.
US Bureau of Mines work indicated that only copper, silver and zinc (to a minor extent) appeared to
co-deposit with lead. Copper and silver could be removed by prior treatment of the melt with lead before
electrolysis. Elements less noble than lead can build up in the electrolyte, such as calcium, magnesium,
sodium, iron and zinc. These effects necessitate the feeding of relatively pure lead chloride as well as the
ability to bleed or purge the electrolyte periodically to maintain impurities at a low level. These aspects
of prolonged operation of a molten lead chloride cell have yet to be fully resolved.
Preparation of lead chloride feed

The essential lesson from past attempts to develop processes for the production of lead by molten
chloride electrolysis was that the electrolyte must be of high purity. Chlorination of lead concentrates
and feeding of the resulting lead chloride directly to an electrolytic cell was unsuccessful.

Consequently, the first stage of any process must be the preparation of high purity lead chloride. This
will inevitably require the preparation of an aqueous solution and separation of a high purity lead
chloride therefrom. Fortunately, this can be facilitated by crystallisation utilising the high temperature
coefficient of solubility for lead chloride.
Lead chloride can be prepared by direct chlorination of lead concentrates either as dry chlorination
in a suitable reactor such as a fluidised bed, or by wet chlorination in a suspension in water as part of a
leaching operation. Alternatively lead concentrates can be leached with a ferric chloride solution
according to Equation 9.7:
PbS + 2FeCl3 = PbCl2 + 2FeCl2 + So (9.7)
As indicated above, this reaction proceeds rapidly and efficiently and can be relatively selective with
lower extraction efficiency for zinc and copper sulfides. However, there may be concerns with low
extractions for silver and gold, which are key economic by-products for lead extraction. For this reason
an aggressive leach is preferred, which then necessitates comprehensive purification procedures.
Where ferric chloride is used for leaching and converted to ferrous iron, it can be regenerated by
reaction of the solution (after lead chloride removal) with chlorine from the electrolytic cell. The can
be done using a packed absorption tower irrigated with depleted solution in exchange with an upflow
of gas from the anode compartment of the cells.
Whichever method is used for preparation, a hot aqueous leach solution is the end point, from
which a pure lead chloride must be produced. Cementation with lead powder can be used to separate
and recover copper, silver, gold and bismuth as well as removing arsenic and antimony. Separation of
lead chloride by crystallisation can then be used, relying on the high temperature dependence of lead
solubility as shown in Table 9.2.
TABLE 9.2
Solubility of lead in chloride solutions.
Temperature (°C) PbCl2 concentration in water PbCl2 concentration in a FeCl2/NaCl solution

(g/L) (g/L)
20 9.9 23
60 18 49
95 31.7 98
100 33.4 110
The solubility of lead in brine solutions is much higher than in water alone, due to the formation of
strong chloro complexes. Commonly, sodium chloride concentrations of the order of 250 g/L are
used, together with iron concentrations for ferric iron leaching of the order of 25 g/L. This also applies
to the leaching of silver, which can be readily solubilised in brine solutions, whereas AgCl is quite
insoluble in water alone. Table 9.3 shows the equilibrium chloride concentrations at which particular
complexes form.
There is clearly benefit in using brine solutions with a high chloride concentration where
solubility differentials of the order of 50 g/L of lead can be obtained. Many process developments
have therefore proposed to use crystallisation simply by cooling the leach solution as a means of
obtaining pure lead chloride. The crystals must then be thoroughly washed and dried in preparation
for feeding to a fused salt electrolytic cell.

TABLE 9.3
Chloro complex formation (equilibrium chloride concentration for complex formation at 25°C).
Complex Total Cl concentration (g/L)

PbCl+ 2
PbCl3- 14
PbCl42- 140
AgCl32- 8
3-
AgCl4 263
Processes using these techniques are the US Bureau of Mines process (Wong, Haver and Sandburg,
1980), the UOP process (Stauter, Tolley and Um, 1978), and the St Joe Minerals Corporation
developments (Bounds, 1980). However, there has been insufficient long-term experience on a
commercial scale to know whether there are any significant issues with the transfer of particular
impurities with the lead chloride. Indications from pilot testing are that cathode lead of 99.99+ per cent
quality can be produced. A typical flow sheet is shown in Figure 9.3 representing the USBM process.
Lead Sulfide
Concentrate
NaCl / FeCl 3 solution
Make up
Leaching reagents
Bleed Stream
Treatment
Crystallisation
Leach residue
and sulfur
Filtration and To by-product
Washing recovery
Lead chloride
Drying Chlorination
Molten Salt
Electrolysis Chlorine
Molten lead
Casting
Product Lead
FIG 9.3 - Flow sheet for aqueous ferric chloride leaching – molten salt electrolysis (US Bureau of Mines).

PROCESSES BASED ON AQUEOUS ELECTROLYSIS
Chloride systems
Rather than use molten salt chloride electrolysis, it is possible to directly electrolyse an aqueous brine
solution of lead chloride. As indicated in the Background section above, the cathodic deposition of
lead from a chloride solution will be crystalline and dendritic, and needs to be continuously removed
from the cathode by scraping or shaking. The lead deposit will collect in the base of the cell and can be
continuously removed using a conveyor system such as a screw. Because the finely divided lead will
oxidise readily it needs to be compacted by briquetting or extruding through high pressure rolls before
feeding to the melting pan. If a lead chloride–brine solution is electrolysed, then chlorine will be
evolved at the anode and can be collected and used for leaching. An acidic brine solution is preferred
for high conductivity and cell voltages of around 2.5 to 3.0 are possible with current efficiencies for
lead deposition of 95 per cent.
The PLACID process, developed by Tecnicas Reunidas in Spain, has been applied to
electrowinning lead from lead carbonate derived from secondary sources, and uses an electrolyte of
lead chloride and sodium chloride only. In this case the cell has a diaphragm permeable only to
hydrogen ions and produces an acidic spent electrolyte (hydrochloric acid) used for leaching lead
carbonate. The anolyte is an acidic solution free of chloride so that oxygen is produced rather than
chlorine. The dendritic or sponge deposit of lead is shaken from the cathodes and collected by
conveyor belt. The lead is pressed to remove electrolyte and form platelets, which are fed into a
melting kettle. Energy consumption is reported as 0.9 kWh/kg of lead (Frias, Garcia and Diaz, 2000).
A schematic of the PLACID flow sheet is shown in Figure 9.4.
It is also possible to electrolyse a solution containing iron in the ferrous state in a compartmented–
diaphragm cell. Ferrous iron will not interfere with the cathode reactions but will be oxidised to ferric
iron in the anode compartment. To achieve this, feed solution enters the cathode compartment and
electrolyte passes through the diaphragm, constructed of an inert fabric, to the anode compartment
and exits the cell. The anolyte can then be reused for leaching. Any escape or return of ferric iron to
the cathode compartment will result in its reduction to ferrous iron in preference to lead deposition,
thus reducing process current efficiency for lead recovery.
In the case where leach solution is used for cell feed, purification of the solution by cementation
with lead powder is necessary, as well as the treatment of a bleed to prevent the build-up of other
impurities such as zinc, calcium and magnesium. It is also important that the iron present in feed
solution is fully in the ferrous state to maintain high current efficiency by avoiding the reduction of
ferric iron at the cathode. To ensure this, it is preferable to have a two-stage counter-current leach in
which excess sulfides are in contact with the final leach solution. Some excess ferrous iron (10 to
15 g/L) should also be maintained in the anolyte to impede the formation of chlorine at the anode.
Solution compositions are generally around 80 g/L Pb in feed solution, reducing to 20 g/L in spent
electrolyte, which allows the cell to operate at a temperature of around 40°C. Iron levels are around
40 - 50 g/L and sodium chloride at 250 g/L. Cell voltages will be high due to the resistance of the
diaphragm and extra spacing involved at 3.5 to 4.5 volts depending on design. Current efficiencies of
95 per cent can be achieved with current densities of 200 amps/m2. Electrodes can be stainless steel
for the cathode and graphite for the anode, although there are reported difficulties with graphite
attack. The alternative anode is titanium or ruthenium coated titanium. In the case of titanium, the use
of expanded metal against the back of the diaphragm to provide an internal channel for the anolyte is a
favoured approach, particularly if current densities are relatively low.

Oxide Lead
Feed
NaCl / HCl solution
Leaching
Lime
Sulfate
Removal
Leach residue
Gypsum
Cement to by-product
recovery
Purification
Oxygen
Water
Anode Cathode
H+
Cathode lead powder
Briquetting
Melting
& Casting
Product Lead
FIG 9.4 - Aqueous chloride electrolysis for lead (PLACID process).
The Minemet process follows these principles but also incorporates an additional purification
stage following cementation. This uses ion exchange with IMACTI-GT73 resin with good selectivity
for copper and silver to remove the last traces prior to lead electrowinning. The resin is stripped with
HCl and the strip solution is recycled back to first stage purification (Demarthe and Georgeaux,
1980). A schematic flow sheet is shown in Figure 9.5.
The INTEC process is another alternative chloride-based system proposed for the direct recovery
of lead from sulfide concentrates (Everett and Moyes, 1992). The process was primarily developed
for the processing of copper concentrates using the cupric/ cuprous ion couple for oxidation; however,
later developments used a halogen complex for oxidation and this is more suited to the application to
lead extraction where copper must be absent during electrodeposition of lead. The halogen complex
or ‘Halex’ is BrCl2, and is generated at the anode as an alternative to chlorine gas. It is quite soluble
and avoids the complexities and difficulties associated with chlorine handling. The electrolyte is
basically a brine solution containing around 250 g/L NaCl and 25 g/L NaBr together with lead. Lead is
leached from the sulfide concentrate using a multistage counter-current operation, in essence
according to Equation 9.8:
3PbS + 2BrCl2 = 3Pb2+ + 4Cl- + 2Br- + 3So (9.8)

PbS concentrate
Stage 1
Leach
Lead powder
Stage 1
Purification
Stage 2
Leach HCl Cementate to by-product
recovery
Stage 2
Purification
Leach residue
+ sulfur IX eluate
NaCl / FeCl 3 solution

Anode Cathode
Cathode lead
powder
Bleed stream
Briquetting
processing Melting
& Casting
Product Lead
FIG 9.5 - Aqueous ferric chloride leaching and electrolysis (Minemet process).
Any iron present in the leach solution is removed by precipitation as goethite (FeOOH). The
solution is then purified by cementation with lead powder to remove copper, silver, bismuth, arsenic
and antimony, leaving impurities such as zinc, which do not co-deposit with lead. The purified
solution is electrolysed in a diaphragm cell, which uses a coated copper cathode and a titanium mesh
anode coated with ruthenium and iridium oxides. An ion permeable membrane separates the cathode
and anode compartments. The cathode is fabricated from a dimpled copper sheet coated with an inert
adhesive sheet between the dimples, leaving numerous sites of high current density to promote
dendritic growth of the lead deposit. The crystalline lead falls from the cathode and is collected in the
base of the cell.
Halex is regenerated in the anode compartment according to Equation 9.9:
Br- + 2Cl- = BrCl2 + 3e (9.9)
Spent electrolyte can then be treated to remove impurities such as zinc or removed as a bleed
stream before recycle to the leaching stage.
The INTEC process follows similar principles to other aqueous chloride electrowinning systems,
but uses ‘Halex’ in place of chlorine gas, avoiding the difficulties of handling chlorine. Halex is a
strong oxidant and can attack many minerals including pyrite. Consequently, there is less selectivity

in the leaching step than from the use of ferric chloride, giving rise to an increased load of impurities.
It would appear that methods of handling impurity control and removal from the electrolyte are far
from resolved for application of this technology to the extraction of lead.
Aqueous versus molten salt electrolysis

The use of aqueous chloride electrolysis in comparison with molten salt systems has the disadvantage
of producing a powdered lead cathode deposit in comparison with molten lead. The production of
chlorine can be common to both systems but can be avoided in the aqueous system if iron leach
solutions are used as the electrolyte, or proton permeable membranes are used to allow for a separate
anolyte solution composition. No clear preference has emerged to date from the many process options
examined.
Fluosilicate systems
Electrolysis of lead fluosilicate solutions is well established for lead refining by the Betts process, as
detailed in Chapter 13. The principal advantage is the ability to produce a dense cathode deposit rather
than a powder deposit. The process has largely been examined for the treatment of secondary lead
materials, which are converted either into lead carbonate or PbO from mixed sulfate–oxide residues,
and are then leached in fluosilicic acid. The US Bureau of Mines developed an approach along these
lines as an extension of the Betts electrorefining process to electrowinning (Cole, Lee and Paulson,
1981). This approach was also developed and applied on a commercial scale by RSR Corporation in
the USA (Prengaman and McDonald, 1990).
The lead fluosilicate solution is electrolysed in open tank cells using lead starter sheet cathodes
and graphite anodes coated with PbO2. Two possible competing anode reactions can occur, as shown
by Equations 9.10 forming oxygen and Equation 9.11 forming PbO 2.
H2O = 2H+ + ½ O2 + 2e (9.10)
2H2O + Pb2+ = PbO2 + 4H+ + 2e (9.11)
If PbO2 forms it must be recovered from the anode and be recycled. It does not reduce effective
current efficiency for cathode lead, but creates a troublesome recovery and recycle operation, and
hence must be suppressed. As discussed above, various additives will suppress the formation of PbO2,
such as phosphoric acid developed by the USBM or sodium arsenate. The RSR process uses arsenic at
0.5 to 1.0 g/L.
Effectively H2SiF6 is formed at the anode and is recycled to the leaching stage, and in the RSR
process the leach solution contains 150 g/L Pb, and the recirculating electrolyte is held at 60 g/L Pb
with H2SiF6 at 63 g/L. Antimony can build up in the electrolyte to 2 g/L, after which it is no longer
extracted during leaching. Arsenic, antimony, bismuth or zinc in solution will not co-deposit with
lead, but copper will deposit and needs to be removed. In the RSR operation this is removed from the
melted cathode deposit by conventional drossing techniques rather than by leach solution
purification.
Additives such as glue and lignin sulfonate are needed to ensure smooth, dense cathode deposits.
Current densities up to 200 amps/m2 are practical, cell voltages are in the range of 2.6 to 3.0 and
operating temperatures around 35 to 40°C.

Where an anode producing oxygen is in contact with the fluosilicate electrolyte, graphite has been
found to deteriorate; however, this can be corrected either by coating the graphite with PbO2, as used
by RSR Corporation, or the alternative use of titanium also coated with PbO2, as proposed by the
USBM (Smith, Sandberg and Cole, 1979).
For processes aimed at direct leaching of lead sulfide concentrates the most practical application is
to make use of the ferric/ferrous iron couple. As with the chloride system, ferric fluosilicate can be
used as an effective leaching reagent to produce a solution of lead according to Equation 9.12:
Fe2(SiF6)3 + PbS = 2FeSiF6 + PbSiF6 + So (9.12)
The leaching rates are highly temperature dependent and are quite high at temperatures above
60°C. In contrast zinc sulfide leaching rates are far slower giving rise to the possibility of selective
leaching. However, this does not consider the extraction of valued by-products from lead concentrates
such as silver and copper.
The leach solution can be purified by cementation with lead powder and can then be electrolysed
to produce high purity lead at the cathode. Ferrous iron is oxidised at the anode of a compartmented
cell in the same way as for the chloride system above. The advantage of this reaction is that electrode
potentials are sufficiently low to avoid competing reactions, which either form oxygen or PbO2. This
will mean that ordinary graphite can be used with long life.
Fluoborate systems
Fluoborate systems are generally similar to fluosilicate, but it has not been widely used for lead
electrochemical processes due to its higher cost. However, fluoborate does have distinct advantages
over fluosilicate:
• solution conductivity is higher,
• smooth deposits of lead can be produced at much higher current densities,
• the vapour pressure of HF above a hot solution is an order of magnitude lower, and
• the fluoborate ion is more stable.
The use of fluoborate for lead electrowinning from both secondary and primary sources has been
developed by Engitec SpA in Italy and is known as the FLUOBOR process (Olper, 1998).
The FLUOBOR process uses the ferric/ferrous couple with oxidation of ferrous iron in the anode
compartment of a diaphragm cell. Oxygen and PbO2 formation are completely avoided and a simple
graphite anode can be used.
Primary lead sulfide concentrates are leached with ferric fluoborate solution in much the same
way as for ferric chloride detailed above. The solubility of lead fluoborate is much greater than the
solubility of lead chloride and the kinetics of the leaching reaction are faster. This gives more
possibility of selective leaching for lead than is possible with ferric chloride leaching, but again
selectivity to lead may not be beneficial for processing sulfide concentrates where by-product
values from silver in particular can be of major importance to venture economics. Leaching
conditions are a pH of less than one and a temperature of 50 to 90°C. The leaching reaction is shown
in Equation 9.13:
2Fe(BF4)3 + PbS = 2Fe(BF4)2 + Pb(BF4)2 + So (9.13)

Leach residue and elemental sulfur are separated by filtration and the clarified solution is treated
with lead powder to cement out impurity elements Cu, Ag, Sb, As, Se, Te and Bi. The purified
solution is then electrolysed in a diaphragm cell with a 316 stainless steel cathode and graphite anode.
Lead is deposited as a dense deposit, which is periodically stripped from the stainless steel cathode.
Solution flows through the diaphragm to the anode where ferrous iron is oxidised to ferric iron for
return to the leaching stage. Cathode current density is around 300 amps/m2 and cell voltage is about
two, giving an energy consumption of around 550 kWh/tonne of recovered lead.
In order to remove impurities such as iron and zinc, which will build up in the electrolyte, a bleed
stream is processed to remove these elements by a crystallisation procedure.
Elemental sulfur can be extracted from the leach residue using perchlorethylene as a solvent at
60°C and is crystallised from the solvent by cooling to 20°C. Otherwise, flotation techniques for
sulfur recovery followed by melting and filtration could be used.
The FLUOBOR process has been extended to the treatment of secondary materials or pastes from
lead–acid batteries, and to the refining of impure lead bullion. For refining, crude smelter bullion is
granulated and then leached using a ferric fluoborate solution in a rotating stainless steel drum.
Impurities with a higher electrochemical potential than lead are not dissolved and remain in the leach
residue so long as they are in contact with residual lead. Other impurities will dissolve but will
generally not be deposited on the cathode, except possibly for tin. However, ferric iron can oxidise
Sn2+ to Sn4+, which will precipitate as metastannic acid, H4SnO4, which can be removed by filtration
before electrolysis.
For the treatment of battery pastes, which are a mixture of PbSO4, PbO2, PbO and metallic lead, a
sulfidisation process has been proposed, converting all lead components into PbS, which can then be
subjected to ferric fluoborate leaching as above. Sodium sulfide can be used for this step but involves
a complex procedure for its recovery. Alternatively, a biological sulfate reduction process developed
by PAQUES Biosystems of the Netherlands has been applied (Olper et al, 2000).
REFERENCES
Ashcroft, E A, 1933. Chlorine smelting with chloride electrolysis, Trans IMM, 43:151-255.
Bounds, C O, 1980. Chloride based lead extraction – Possibly an economic solution to the environmental
restraints on lead smelting, in Proceedings Canadian Institute of Mining and Metallurgy (CIM) 82nd
Annual Meeting (Canadian Institute of Mining and Metallurgy (CIM): Montreal).
Cole, E R, Lee, A Y and Paulson, D L, 1981. Electrolytic method of recovery of lead from scrap batteries,
Research investigation no 8602 (US Bureau of Mines).
Demarthe, J M and Georgeaux, A, 1980. Hydrometallurgical treatment of lead concentrate, in Proceedings
Lead-Zinc-Tin ’80, pp 426-444 (The Minerals, Metals and Materials Society (TMS): Warrendale and
American Institute of Mining, Metallurgical and Petroleum Engineers (AIME): Littleton).
Everett, P K and Moyes, A J, 1992. The INTEC copper process, in Proceedings International Conference on
Extractive Metallurgy of Gold and Base Metals, pp 287-292 (The Australasian Institute of Mining and
Metallurgy: Melbourne).
Frias, C, Garcia, M and Diaz, G, 2000. New clean technologies to improve lead acid battery recycling, in
Proceedings Lead-Zinc 2000, pp 791-801 (The Minerals, Metals and Materials Society (TMS): Littleton).
Liddell, D M (ed), 1962. Chlorine metallurgical processes, in Handbook of Non-Ferrous Metallurgy, vol II,
pp 1151-1188 (McGraw-Hill Book Company: New York).
Olper, M, 1998. Fluoborate technology – A new challenging way for primary and secondary lead processing, in
Proceedings Lead and Zinc Processing Symposium, pp 185-198 (Metallurgical Society and Canadian
Institute of Mining and Metallurgy (CIM): Montreal).

Olper, M, Maccagni, M, Buisman, C J N and Schultz, C E, 2000. Electrowinning of lead battery paste with the
production of lead and elemental sulphur using bioprocess technologies, in Proceedings Lead-Zinc
Symposium, pp 803-813 (The Minerals, Metals and Materials Society (TMS): Warrendale).
Prengaman, R D and McDonald, H, 1990. RSR’s full scale plant to electrowin lead from battery scrap,
in Proceedings Lead-Zinc ’90, pp 1045-1056 (The Minerals, Metals and Materials Society (TMS):
Warrendale).
Smith, L L, Sandberg, K G and Cole, E R, 1979. Method of producing lead dioxide coated anode, US Patent
4,159,231, June 16.
Stauter, J C, Tolley, W R and Um, R T, 1978. The recovery of lead from sulphide concentrates using a
chlorination/brine leach/electrolysis process, in Proceedings ACS Meeting, Anaheim, March.
Wong, M M and Haver, F P, 1977. Fused salt electrolysis for the production of lead and zinc metals, in
Proceedings International Symposium on Molten Salt Electrolysis in Metal Production, pp 21-29
(Institution of Mining and Metallurgy (IMM): London).
Wong, M M, Haver, F P and Sandberg, K G, 1980. Ferric chloride leach – Electrolysis process for the production
of lead, in Proceedings Lead-Zinc ’80 Conference, pp 445-454 (The Minerals, Metals and Materials Society
(TMS): Warrendale and American Institute of Mining, Metallurgical and Petroleum Engineers (AIME):
Littleton).

PART C
SECONDARY SMELTING
This part of the text covers the preparation of secondary feed materials and the
smelting processes used for lead extraction. This predominantly covers the
treatment of scrap lead-acid batteries.
Chapter 10 Secondary Materials and Pretreatment

Chapter 11 Secondary Smelting Methods
CHAPTER 10
Secondary Materials and Pretreatment
INTRODUCTION
As indicated in Chapter 1, global lead consumption from secondary sources approached four million
tonnes per year in 2005, or 60 per cent of total world consumption. Around 20 per cent of world
consumption is for uses where recycling is difficult, such as for plastics stabilisers, for TV tube glass,
for shot and ammunition. Of the remainder, ten per cent is used for rolled or extruded alloys and cable
sheathing, which have long-term applications, and 70 per cent is used for batteries. Recyclable lead
therefore is predominantly from used automotive batteries, with some from reclaimed sheet, cable
sheathing and other metallic scrap. In addition there are various residues, drosses and flue dusts
containing lead.
Secondary residues are often handled by primary smelters as a supplement to concentrate feeds.
Secondary smelters accept metallic scrap, but are primarily oriented to the processing of scrap lead
acid batteries, which represent more than 85 to 90 per cent of secondary smelter feed.
Up to the 1970s the secondary industry was often small scale and localised in major population
centres for ease of collection of used automotive batteries. It was also oriented to the return of the lead
produced to the battery manufacturers. This was not difficult since most batteries used antimonial lead
alloy for the grid material and hence the secondary smelter could recover both antimonial lead and
soft lead, which could be suitably blended for return to the battery manufacturers. Since that time
there have been significant changes, as follows:
• Increased environmental regulations affecting the gas and fugitive dust emissions from the
smelter, as well as constraints on the wastes produced, such as smelter slags.
• Stricter occupational health regulations, which have impacted on handling methods and the
generation of dust and general exposure to lead in the workplace.
• Changes in the design of lead acid batteries, particularly the grid alloys for the purpose of
producing maintenance free batteries, such as sealed or valve regulated, recombinant batteries.
Alloys have changed from antimony lead to calcium-tin-lead with many proprietary minor
additives, and requiring much higher purity lead supplies.
• Changes in the non-metallic components of the battery such as the case and separator materials.
Polypropylene has virtually completely replaced hard rubber or ebonite casings, and has
significant recyclable value in itself.
These changes have increased the operating costs of secondary smelting operations and have
increased the need for some refining of secondary lead rather than simply blending for suitable
antimony contents. Separation of battery components is more important because of the value of
recovered plastic components, in particular polypropylene. Economies of scale have become
significant and secondary operations have become far more automated and capital intensive in order
to meet these changed requirements. As a result smelters have become part of major metal producing
corporations rather than small local enterprises.
There has also been a general trend to restrict the disposal of lead acid batteries in waste landfill,
mandating their collection and recycling. Many countries introduced schemes for battery recycling,
which included the levying of charges on new batteries to cover the costs of collection and recycling,

CHAPTER 10 – Secondary Materials and Pretreatment
or a deposit system to provide incentive for return of an old battery when it is replaced. This has led to
a significant increase in the availability of secondary feed and secondary lead production.
Originally smelting involved the processing of whole batteries, usually after draining of the
electrolyte, either in a reverberatory hearth furnace or in a blast furnace. However, differences in the
composition of grid lead, which is alloyed, and paste lead, which is high-grade lead, gave a significant
advantage to separation before smelting. Metallic lead also only needed to be melted without
consuming high-grade fuel such as coke. Problems with chlorine from the separators producing
volatile lead chloride, and the recoverable value of polypropylene from battery cases all contributed
to the benefits from separation of the battery into its various components and the separate handling of
each component as appropriate. Few operations now process whole batteries and breaking and
separation prior to smelting is the common approach.
LEAD-ACID BATTERY COMPOSITION

To understand the requirements for processing scrap lead-acid batteries, as the predominant
component of lead scrap, it is useful to review the operation of a battery and its construction. The
lead-acid battery uses a positive electrode or plate composed of PbO2 as the active material, and a
negative electrode or plate, composed of sponge lead as the active material. The electrolyte is dilute
sulfuric acid and upon discharge both active materials are converted into lead sulfate according to the
reactions shown in Equations 10.1 and 10.2. This explanation of the action of the battery is referred to
as the ‘double sulfate theory’. It may be a simplistic view, but broadly explains the essential principles
of the operation of the battery.
Positive plate PbO2 + SO42- + 4H+ + 2e = PbSO4 + 2H2O (10.1)
Negative plate Pb + SO42- = PbSO4 + 2e (10.2)
Reading Equations 10.1 and 10.2 from left to right is the battery discharge reaction, and from right
to left is the charging reaction. Clearly, as the battery discharges the concentration of sulfuric acid in
the electrolyte decreases and hence the density of the electrolyte will fall, which is used as a measure
of the charge condition.
The active materials are held within a lattice or grid made of lead metal to act as the current
conductor and into which the materials are pasted. Many different techniques are used for the
manufacture and preparation of battery plates, but will not be covered in this text. The active paste
material changes in volume as the above reactions take place and must be designed as a porous
structure to accommodate these changes over many charge and discharge cycles, without degradation
and spalling of material from the plates.
Positive and negative plates should be close to reduce the electrical path through the electrolyte,
but must avoid the possibility of contact, which causes an internal short circuit. Hence separators are
used as inert porous plates, usually constructed of PVC or microporous polyethylene.
The general construction of the lead-acid automotive or starting lighting ignition (SLI) battery
using the above principles is shown in Figure 10.1.
Grids need to be corrosion resistant and have reasonable strength and dimensional stability. Soft
lead is unsuitable and antimony was successfully used for many years as an alloying element for this
purpose. However, antimony tends to migrate into the negative active material and lowers the
hydrogen overvoltage on that material, increasing the generation of hydrogen during charging and the

1. Lead alloy grid 6. Negative electrode set for one cell

2. Separator - porous 7. Full electrode and separator assembly
insulating plate for one cell
3. Positive plate 8. Battery case
4. Separator 9. Positive terminal
5. Negative plate 10. Positive electrode set for one cell
FIG 10.1 - Construction of the automotive lead-acid battery.
associated decomposition of water and loss from the battery. In these circumstances the battery has
to be topped up with water from time to time, requiring ‘maintenance’. The presence of antimony is
also one of the main causes of self-discharge of the battery on standing. This led to the development
of lead calcium alloys to minimise grid corrosion and gassing, giving rise to the ‘maintenance free’
battery. With the ability to avoid water decomposition and gassing, the electrolyte can be
immobilised by the use of glass microfibre mats or by gelation with silica, giving rise to the sealed
battery.
Antimonial lead alloys used typically contain 4.5 to 6.0 per cent Sb, 0.1 to 0.4 per cent As, 0.2 to
0.5 per cent Sn and 0.02 to 0.06 per cent Cu. There are also a range of antimonial alloys containing up
to 4.5 per cent Cd.
Calcium lead alloys contain 0.05 to 0.08 per cent Ca, 0.1 to 2.0 per cent Sn and around 0.05 per
cent Ag.
Overall, the lead-acid automotive battery is close to 60 per cent lead and is typically made up of the
following components:
• sulfuric acid electrolyte, 24 per cent by weight (around 18 per cent H 2SO4);
• grids – metallic lead, 22 per cent by weight;
• top lead – connector posts, four per cent by weight;
• pastes, 38 per cent by weight;
• case – polypropylene, seven per cent by weight; and
• separators – five per cent by weight.
An average analysis of separated pastes from scrap batteries is shown in Table 10.1.
Separators are primarily PVC and contain around 21 per cent chlorine.

TABLE 10.1
Average battery paste analysis.
Lead sulfate PbSO4 50 - 60%

Lead dioxide PbO2 15 - 30%
Litharge PbO 5 - 10%
Metallic lead Pb 2 - 5%
Antimony Sb 0 - 0.5%
Carbon C 2 - 4%
Silica SiO2 0.5 - 1.0%
Moisture H2O 8 - 15%
Total lead content 69 - 75%
Based on the above average figures, if the components are separated and only the pastes need to be
processed in the smelting operation, the input tonnage to be processed is reduced to around 50 per cent
in comparison with whole battery smelting.
BATTERY BREAKING AND SEPARATION

A number of proprietary battery breaking systems are available, in particular those offered by MA
Industries and the CX System from Engitec–Tonolli. The sequence of operations for battery breaking
and separation is shown in Figure 10.2.
Primary breaking is either by hammer mill or by spiked rolls in combination with a knife shredder.
Batteries are handled by front end loader into a hopper with apron feeder discharging onto a conveyor
and into the primary breaker. Breakage releases the dilute sulfuric acid electrolyte and equipment
must be constructed of stainless steel and be fully enclosed to contain acid spray and fine particulates.
If crushing rolls are used the discharged material is wet screened to separate fines and electrolyte, and
the coarse material is passed under a magnet to remove any tramp steel and is then processed in the
knife shredder.
The material crushed to around -50 mm is passed over a vibrating screen with a flow of water to
wash out fine paste material. The screen underflow passes to a settler where the pastes are settled out
and the overflow is recirculated over the screen or discarded to either acid reclaim or to neutralisation
and disposal.
The primary screen oversize consists of grid metal, separator plastics and case plastics. It is fed to
a water filled tank where the polypropylene case material floats and is collected and washed. The
remainder of the material is extracted from the bottom of the tanks by drag or screw conveyor and is
passed to a hydrodynamic separator or elutriating column where an upward flow of water separates
out plastic material as overflow from metallic lead, which sinks to the base of the column and is
extracted by drag or screw conveyor.
Coarse materials are dewatered and washed on fine mesh screens and stockpiled for further
processing. Metallics may simply be melted in a pot or standard lead kettle or can be melted in a short
rotary furnace, with some collection of a litharge slag to separate antimony and arsenic and produce a
soft lead. Separator plastics are usually disposed of in landfill but polypropylene is thoroughly
washed, and extruded as pellets for sale to battery manufacturers for new case production.

Whole Batteries
Alternative Route
Roll Crusher Hammer Mill
Oversize
Wet Screen
Magnetics
Undersize
Shredder
Settler
Acid Discard
Oversize Wet Screen
Magnetics
Undersize
Float Separator
Polypropylene Acid discard
Elutriation Pastes
Separator
Separator plastics
Metallic Lead
FIG 10.2 - Generalised flow sheet of battery breaking and separation.
Battery pastes may be directly sent to smelting or can be further processed for desulfurisation prior
to smelting. In some cases the final separation of metallics and plastics from battery separators may
not be included and the mix is sent to the secondary smelter. The plastics can be used as fuel for
reduction in smelting but have the disadvantage of introducing chlorine and associated problems with
volatile chlorides in the smelter gas handling system, as well as causing the formation of noxious
compounds in exhaust gases such as dioxins.
Sulfuric acid reclamation

Sulfuric acid may be reclaimed for reuse in batteries by filtration of discard from the primary paste
collection settler, or it may be neutralised with lime and the resulting gypsum filtered off and discarded.

Because of the low cost of sulfuric acid and the difficulties of handling and storing as a dilute
solution (around 20 per cent), there is generally no justification for acid reclamation and reuse.
However, in situations where the battery recycling facility is part of a larger battery manufacturing
operation on the same site, then acid reclamation would be sensible. Also, if it is part of a primary
smelting operation with a sulfuric acid plant then the dilute recovered acid can be used to provide
make up water for acid production and hence can be recovered. The East Penn Manufacturing Co
Inc in Pennsylvania, USA as a major battery manufacturer with secondary operations has
developed an acid recycling facility in which filtered reclaimed acid is subjected to a solvent
extraction process to remove metal impurities – principally iron. Iron is reduced from a level of
around 15 mg/L to less than 1.5 mg/L by extraction into an organic solvent. It is electrolytically
reduced to the ferrous state and is stripped from the solvent using a low volume of more
concentrated sulfuric acid (Leiby, 1993).
PASTE DESULFURISATION
In the smelting of battery pastes the sulfur from lead sulfate is either captured in the slag as a matte or
reports to the smelter gases and must be removed before discharge to atmosphere by scrubbing. Many
secondary processes were designed to operate with soda-iron slags, which captured sulfur as Na2S or
FeS matte as the bulk of the smelter slag. Depending on performance of the operation some sulfur still
reported to smelter gas, but at the time was sufficiently low to permit discharge to atmosphere.
However, regulations have tightened and in some instances scrubbing is now necessary in addition to
the use of soda-iron slags.
A further complication is the stability of soda-iron slags in landfill dumps. FeS in wet acidic
conditions can oxidise to Fe2O3 and elemental S, releasing considerable heat, which can be sufficient
to raise the temperature and cause ignition of the sulfur and the remainder of the matte. This process
causes expansion and disintegration of the slag and exposes the material to leaching of heavy metal
components. Consequently the slag is treated as a hazardous material with associated high disposal
costs. As a result there has been a move towards the use of more conventional inert silica slags and the
elimination of sulfur from the secondary smelter feed by using a paste desulfurisation process.
Desulfurisation depends on the fact that lead carbonate has a much lower solubility than lead
sulfate. Hence lead sulfate can be converted to the carbonate by treatment with a solution of sodium or
ammonium carbonate. With the use of ammonium carbonate the reaction is shown in Equation 10.3.
The paste is agitated with a strong carbonate solution for one or two hours until the S content is
reduced from around five per cent to less than 0.5 per cent.
PbSO4 + (NH4)2CO3 = (NH4)2SO4 + PbCO3 (10.3)
The ammonium carbonate solution can be regenerated by first reacting the ammonium sulfate
solution with lime, as in Equation 10.4, to form gypsum, which is separated by filtration to leave an
ammonium hydroxide solution. This is then treated with CO2 by absorption in a packed tower to
reform ammonium carbonate solution as in Equation 10.5. CO2 can be generated from kiln gases from
the burning of limestone to produce the lime required for the first stage.
(NH4)2SO4 + Ca(OH)2 + 2H2O = CaSO4.2H2O + 2NH4OH (10.4)
2NH4OH + CO2 = (NH4)2CO3 + H2O (10.5)

With the use of sodium carbonate, the solution pH is higher and there is a tendency to produce a
basic carbonate (hydrocerrusite), according to Equation 10.6:
3PbSO4 + 2Na2CO3 + 2H2O = Pb3(CO3)2(OH)2 + 2Na2SO4 + H2SO4 (10.6)
With treatment at high pH or temperatures above 55°C there is a tendency for sodium to enter
the solid phase as NaPb2(CO3)2(OH), and if sodium carbonate is present in excess, the double salt
Na2CO3.2PbCO3 can form. These effects will incorporate sodium into the desulfurised paste, as can
the presence of NaCl in the solution, which is usually the case for industrial grade soda ash. Hence
one to two per cent Na is usually always present in paste desulfurised by this method. Conversion of
lead to carbonate is also lower at around 85 to 90 per cent and the sodium must be discarded in
smelter slag (Queneau et al, 1998; Stout, 1993).
An alternative to carbonates for desulfurisation is sodium hydroxide producing hydrated lead
oxide according to Equation 10.7:
PbSO4 + 2NaOH = Na2SO4 + PbO.nH2O + (1-n)H2O (10.7)
This results in a cleaner separation with no sodium present in the desulfurised paste (Reynolds,
Hudson and Olper, 1990).
The sodium sulfate solution resulting from past desulfurisation can be filtered, evaporated and
crystallised to produce sodium sulfate for sale. It is used in water treatment and for detergent
manufacture as the quality from this source is sufficiently free of metals for this purpose. In the case
where sodium carbonate is used the residual solution is usually neutralised with waste acid to remove
any residual carbonate before evaporation and crystallisation.
Alternatively it is possible to regenerate sodium hydroxide by reaction with lime to remove sulfate
as gypsum, according to Equation 10.8:
Na2SO4 + Ca(OH)2 + 2H2O = CaSO4.2H2O + 2NaOH (10.8)
Engitec have proposed the electrolysis of the sodium sulfate solution in a diaphragm cell to
regenerate sodium hydroxide at the cathode and sulfuric acid at the anode to give a battery grade
sulfuric acid as the anolyte.
Paste sulfate reduction
A novel approach in treating paste in order to provide feed for a paste lead electrowinning process is
proposed by Engitec, in which all lead containing salts are converted into PbS by using anaerobic
bacteria. This follows the successful commercial application of sulfate reducing bacteria to treat
smelter waste waters for the separation and recovery of heavy metals as sulfides. Reactions are as in
Equations 10.9 to 10.11:
PbSO4 + 4H2 = PbS + 4H2O (10.9)
PbO + H2SO4 + 4H2 = PbS + 5H2O (10.10)
PbO2 + H2SO4 + 5H2 = PbS + 6H2O (10.11)

The bacterial leaching step requires the injection of H2 and CO2, which can be produced by
cracking natural gas. The carbon dioxide is used for bacterial growth and the hydrogen as an electron
donor for the reduction reactions as above.
The lead sulfide is leached with ferric fluoborate solution to dissolve lead and produce elemental
sulfur. The resulting lead–ferrous fluoborate solution is electrolysed in a diaphragm cell to produce a
pure lead cathode and a ferric fluoborate solution at the anode for recycle to leaching. This process is
also applicable to primary lead production from lead sulfide concentrates and thus allows a high
degree of integration of secondary and primary lead smelting operations. In any event the conversion
of pastes into lead sulfide allows integration with most primary smelting operations (Olper et al,
2000).
PROCESSING OF SECONDARY RESIDUES

There are many lead containing residues from other metallurgical operations including flue dusts,
drosses and leach residues, often containing lead as lead sulfate and often containing a wide range of
other impurity elements. Large tonnages of such residues are available from the electrolytic
production of zinc as sulfate leach residue and from copper smelting as flue dusts. In general these
materials contain substantial quantities of gangue elements such as silica, lime and iron oxides, but
often contain substantial amounts of precious metals which represent the bulk of the value. Smelting
will produce much slag as well as a relatively impure bullion requiring extensive refining. This is
quite incompatible with normal secondary smelting, oriented to scrap battery processing, and hence
the treatment of such secondary residues is usually handled by primary smelters as an addition to
concentrate feeds.
Depending on the smelting process used there can be limits to the acceptable proportion of feed
represented by such residues. For the sinter plant–blast furnace combination the input of sulfate
residues is commonly limited to around 25 per cent of net new feed. The decomposition of lead sulfate
is endothermic and can limit the attainment of peak bed temperatures in the sinter plant, affecting the
quality of sinter produced, which is critical to blast furnace performance. This is discussed in detail in
Chapter 4. Many of the direct smelting processes covered in Chapter 7 are more able to cope with
residue feeds, particularly the Kivcet and Kaldo processes.
REFERENCES
Leiby, R A, 1993. Secondary lead smelting at East Penn Manufacturing Co Inc, in Proceedings EPD Congress
1993, pp 943-957.
production of lead and elemental sulfur using bioprocess technologies, in Proceedings Lead-Zinc 2000,
TMS Symposium, Pittsburg, pp 803-813 (The Minerals, Metals and Materials Society (TMS): Warrendale).
Queneau, P B, James, S E, Downey, J P and Livelli, G M, 1998. Recycling lead and zinc in the United States, in
Proceedings Zinc and Lead Processing – CIM Symposium, Calgary, pp 127-153.
Reynolds, R M, Hudson, E K and Olper, M, 1990. Advances in lead acid battery recycling: Engitec’s automated
CX Breaker system, in Proceedings Lead-Zinc ’90 Symposium, Anaheim, pp 1001-1022 (The Minerals,
Stout, M E, 1993. Secondary lead recovery from spent batteries, in Proceedings EPD Congress 1993,
pp 967-979.

CHAPTER 11
Secondary Smelting Methods
GENERAL
Secondary lead smelting is predominantly based on the treatment of scrap lead-acid batteries, as
detailed in Chapter 10. A wide range of smelting methods are used for the treatment of secondary
lead, originally based on traditional smelting methods such as the hearth and blast furnace, feeding
whole batteries, but are changing under stricter environmental controls to the use of prior separation
and specialised reduction in rotary furnaces or newer electrochemical techniques.
Processes are essentially classified by the type of equipment used, as follows:
• reverberatory furnace based processes, coupled with additional slag reduction equipment such as
the blast furnace;
• blast furnace;
• rotary kiln;
• short rotary furnace;
• submerged lance slag bath reactor;
• electric furnace; and
• electrochemical treatment methods.
In many operations a combination of two processes is used; the first for bulk smelting of total lead
containing scrap and the second for reduction of lead-rich slags produced in the first stage. Often
impurities can be concentrated into the first stage slag, reducing the quantity of lead requiring
refining. Figure 11.1 shows the more common combinations and interrelationships between the
primary and secondary smelting processes.
The primary smelting stage feed varies from whole drained batteries to disintegrated whole
batteries, mixed paste and metallics after separation of plastics, pastes only after separation of metallics
and plastics, and pastes after desulfurisation. Some processes are unsuited to different types of feeds.
The feed for the secondary smelting stage in a combination is the slag from the primary process.
Bullion from each stage may be acceptable for reuse in battery manufacture or it may require some
refining. Where slag recycle is shown in Figure 11.1 it is usually done on a separate campaign basis to
enrich an alloying element into a separate bullion stream. For example it is common to accumulate
first stage blast furnace slags for recycle through the furnace in a campaign. This serves to recover
extra lead as well as concentrate alloying elements such as antimony, which tend to preferentially
report to the slag.
REVERBERATORY FURNACE
The reverberatory furnace is possibly an extended use of the old hearth smelting process. It has
generally been replaced by other methods, but is still widely used in the USA.
The furnace is rectangular in shape with a shallow hearth and arched roof. The floor and roof slope
down to the firing end, and the opposite end contains a feeding port where the feed mix is
continuously or intermittently pushed into the furnace. A natural gas or oil burner flame extends to the

CHAPTER 11 – Secondary Smelting Methods
Whole Drained Batteries
Slag recycle
Battery Breaking Blast Furnace
Short Rotary
Furnace
Plastics Separation
Rotary Kiln
Stage 1
Slags for
secondary
Paste + Metallics smelting
Metallics Separation Top Lance Blast Furnace

Stage 2 Slag Bath Reactor
Kettle Melting
Reverberatory Electric Arc
Pastes
Furnace Furnace
Short Rotary
Furnace Slag recycle
Paste
Desulfurisation
Short Rotary
Furnace
Leaching &
Electrowinning
FIG 11.1 - Secondary smelting process options.
centre of the furnace and melts the charge, which flows into a pool on the hearth, settling as a lower
layer of lead bullion and an upper layer of slag. Slag continuously overflows, whereas bullion can be
tapped intermittently or continuously through an underflow weir and lead well. It is often the practice
to adjust the level of bullion on the hearth to maintain a relatively shallow slag layer, without causing
bullion to be lost with the slag.
Furnace sizes vary widely, with hearth areas from 2 to 70 m2. Construction commonly uses
chrome magnesite brick to the slag level and high alumina brick above. Suspended arch roofs are used
in the larger furnaces. A schematic of the reverberatory furnace is shown in Figure 11.2.
The charge consists of broken battery components premixed with coal or coke fines at about
five per cent by weight. The charge is fed by conveyor onto a mechanical stoker which pushes it into
the furnace. Initially the charge is dried, the metallic lead then melts followed by PbO, allowing the
reactions shown in Equations 11.1 to 11.6 to proceed. Because the battery pastes are closely mixed
with the grid metal in the charge, lead metal acts as a reducing agent to convert PbSO4 and PbO2 to
PbO. PbS is an intermediary which can be oxidised according to the ‘roast reaction’ – Equation 11.3
or reaction with PbO as in Equation 11.4. PbO is also reduced to lead metal by carbon as in
Equation 11.5.

Exhaust ports Exhaust gas

Arched Roof
Drying feed
Feed
Burner
Feed port Working ports Slag

Hearth Bullion
FIG 11.2 - Reverberatory furnace schematic.
Because the furnace conditions are not strongly reducing, a PbO-rich slag will be present and
antimony, arsenic and tin tend to be oxidised and remain in the slag as per Equation 11.6. The lead
bullion produced is thus relatively free of alloying components, although any copper, bismuth and
silver present in the feed mix is captured by the bullion.
Pb + PbO2 = 2PbO (11.1)
4Pb + PbSO4 = 4PbO + PbS (11.2)
PbS + PbSO4 = 2Pb + 2SO2 (11.3)
PbS + 2PbO = 3Pb + SO 2 (11.4)
2PbO + C = 2Pb + CO2 (11.5)
2Sb + 3PbO = 3Pb + Sb 2O3 (11.6)
Furnace gases are cooled either by direct water injection or by indirect heat exchange to below
200°C and are then cleaned in a bag filter. Collected dusts are recycled to the feed mix. Although most
secondary smelters using this technology in the past discharged filtered gas directly to atmosphere,
the SO2 content no longer makes this permissible in most locations. Hence gas scrubbing to remove
SO2 using lime or ammonia solutions is necessary for the application of this technology.
Slag production is roughly one tonne for every four tonnes of bullion produced and typical slags
contain around 75 per cent Pb and close to 90 per cent of the antimony in the feed material, with
bullion commonly reporting around 0.1 per cent Sb. The reverberatory furnace is not efficient for
reduction and the slag is normally treated in separate equipment with a higher reduction potential.
The blast furnace has commonly been used, but also the short rotary furnace and electric furnace are
used for this duty. The bullion produced from reduction of reverberatory slag is enriched in alloying
elements such as antimony and tin and requires refining or careful blending to produce suitable
alloys.
In some instances first run reverberatory slag can be re-run through the furnace on a campaign
basis. The slag is mixed with coal at around five per cent of feed and more than half the lead content

can be recovered as bullion. The resulting second run slag is enriched in impurity elements and
reduced in volume for separate treatment. However, this does leave an intermediate bullion stream
with somewhat higher impurity levels and will possibly need to be refined.
THE BLAST FURNACE

The blast furnace is used in two modes, one for the smelting of whole batteries and the second for the
reduction of reverberatory slags. A key feature of the blast furnace is its requirement for bulk feed to
maintain an open structure in the shaft so that gas flow is not impeded. As a result it is not able to
process fine material and application to separated battery paste reduction is impractical.
Secondary blast furnaces are much smaller than primary smelter furnaces and are often circular in
cross-section rather than rectangular as with larger furnaces. Furnace shaft diameter at the tuyeres
ranges from 0.7 to 1.5 m, and working height is from 2.5 to 3.8 m. Larger furnaces, mainly used for
whole battery smelting, tend to be of rectangular cross-section similar to the primary smelter units
(see Chapter 5).
Whole battery smelting

This is typified by the Varta process implemented by Varta Batterie AG at Hannover, Germany and as
used by Boliden-Bergsoe AB at Landskrona, Sweden. The batteries are drained and charged with
fluxes (lime, silica and shredded scrap iron), coke and an amount of recycle lump slag. The slag has a
melting point above 1000°C and maintains an open structure in the shaft until it nears the tuyere zone
with a temperature of around 1150°C.
Coke use is around 180 kg per tonne of crude lead bullion.
Larger furnaces of rectangular cross-section are generally required in this case and the Varta
furnace is 4 m2 in hearth area and 7 m high. The furnace used at Britannia Lead in the United Kingdom
(UK) was similar at 1.1 m wide by 4 m long at the tuyere level with eight tuyeres per side and 4.7 m
high (Koch and Niklas, 1989; Taylor and Moore, 1980).
Water is evaporated in the upper part of the shaft, followed by decomposition of the plastic
components as the temperature rises to 500°C. Lead also melts and reacts with PbO2 to form PbO.
This is reduced by CO to lead further down the shaft, and sulfates are reduced to PbS. A feature of the
Varta process is the use of metallic iron to react with PbS and form lead and FeS as a matte, thus
capturing the majority of the sulfur in feed.
The crucible at the base of the furnace contains lead bullion and a mixed slag–matte phase. Lead
bullion is usually tapped continuously via the lead well into a ladle, and slag may be tapped
intermittently into slag pots where the matte separates. The solidified slag and matte can be broken up
and mechanically separated. The lump slag is crushed to an appropriate size and part is returned to the
furnace. The matte phase contains excess iron and is represented as (FeS + 0.35Fe). It contains 25 to
26 per cent sulfur and six to nine per cent Pb as entrained metal. Matte provides the main outlet for
sulfur and is usually disposed of in landfill.
Furnace gases pass through a fuel fired afterburner to raise gas temperature to 1000°C in order to
combust organics distilled from decomposing plastics in the upper shaft. After burning the gases pass
through a drop-out chamber and are then cooled and filtered through a bag house before discharge to
atmosphere. Although most of the sulfur is captured as matte this will not be complete, and the advent
of tighter emission standards may make scrubbing of final gas necessary. The destruction of organics
by afterburning requires added fuel in addition to the CO content of the gas and is a significant
inefficiency in the energy requirements of this process.

Chlorine from PVC separators forms volatile lead chloride, which vaporises in the lower shaft and
condenses in the upper shaft, forming a recycle loop as well as wall accretions. Some lead chloride
reports to flue dusts, again causing accretions in the gas handling system, and collected dusts must be
leached for removal of chlorine before recycling to the furnace feed.
Another difficulty with the processing of whole batteries is the tendency of the cases to melt in the
upper part of the shaft to form a sticky mass bridging across and blocking the furnace.
The blast furnace is also a high energy consumer for various reasons, not the least being the
requirement to melt a high circulating load of slag. Furnace heat is supplied by the burning of coke,
which is a costly fuel. Together with the complications of consuming plastic materials, the bulk of
which can be a valuable by-product, and the environmental issues with disposal of lead-rich mattes,
these problems have rendered the blast furnace smelting of whole batteries an unattractive approach.
Blast furnace smelting of reverberatory slags

The furnaces used in this case are relatively small and commonly circular in cross-section. A
schematic of a typical small-scale furnace is shown in Figure 11.3. Construction of the shaft is water
jacketed mild steel, sitting on a brick crucible fitted with lead well and siphon. The top is sealed using
a cone seal through which the charge is periodically dropped. The furnace feed is crushed
reverberatory furnace slag and it is fuelled with coke at around ten per cent of the charge. Lime, silica
and shredded scrap iron are added as fluxes, making up about 20 per cent of the charge.
Feed
Charge Hopper
Cone seal
Gas Offtake
Water jacketed
shaft
Shaft
Dam
Tuyere
Bullion spout
Slag spout
Crucible
FIG 11.3 - Typical secondary blast furnace cross-section.

In some cases the bullion produced can be rich in antimony and to achieve high antimony recoveries
under these circumstances it is necessary to avoid speiss formation, and hence keep the iron input
relatively low. In turn this means that slags are lower in iron than normal primary smelter slags with
FeO:SiO2 ratios at 0.8:1 and CaO:SiO2 at 0.9:1. This compares with typical primary smelter slag ratios
of 1.3 and 0.7 respectively. The lead content of slag is typically between one and three per cent.
Where lower antimony slags are processed and recovery is not a critical issue, then more typical
lead blast furnace slags can be used. Where feed has a significant sulfur content, iron can be added to
capture the sulfur as a matte, and in this case relatively high iron slags can be produced with FeO:SiO2
ratios above 2.0 and CaO:SiO2 ratios below 0.5.
Blast furnace gases pass through an afterburner to convert CO to CO2, and are then cooled by
water injection and cleaned in a bag filter before discharge to atmosphere. Collected dusts are
recycled to the reverberatory furnace.
It is usual to operate the blast furnace on a campaign basis, stockpiling feed until sufficient has been
accumulated for a reasonable campaign run of from one to four weeks. It is also possible to re-run blast
furnace slags under different conditions, particularly if it is desired to concentrate antimony or other
alloying elements into a small quantity of final bullion. This mode of operation provides considerable
flexibility and allows the furnace to be cleaned between runs, minimising operational difficulties due to
accretion build-up and maximising the efficiency of the furnace (Pike, 1990).
THE ELECTRIC ARC FURNACE
The electric arc furnace has been applied as a replacement for the blast furnace by RSR Corporation
for the purpose of treatment of reverberatory furnace slags (Eby, 1990).
RSR recycle first run slags through the reverberatory furnaces to produce a second run slag
enriched in alloying elements such as antimony. The second run slag reports 35 to 50 per cent Pb, five
to ten per cent Sb, one to three per cent As and one to three per cent Sn and is fed to the electric arc
furnace mixed with coke fines at five to seven per cent, limestone at four to seven per cent and iron
turnings at zero to five per cent of the charge weight respectively.
Mixed feed is dried in a rotary dryer using furnace off gases and air to burn CO and is dropped
through a port in the furnace roof. Lead oxide is reduced by carbon to metal along with antimony and
tin oxides to produce a bullion containing these elements. A residual slag floats on the surface of the
bullion and is maintained at a minimum depth of at least 150 mm to provide a resistance path for the
electrodes. Any shallower depth has the danger of electrical shorting through the underlying bullion.
During operation slag depth will increase to 450 mm.
Slag temperature is relatively high and high iron levels are not required to maintain a fluid slag as
is the case in the blast furnace. Hence FeO:SiO2 ratios can be in the range 0.15 to 0.4, with CaO:SiO2
ratios around 1.0. This will avoid the formation of a speiss phase.
Sulfur in the charge will form a matte phase usually composed of CaS and FeS.
The lead content of slag is between 0.5 and two per cent and the total of lead, antimony, arsenic
and tin is generally less than 4.5 per cent, compared with six to 12 per cent for the blast furnace. The
slag is disposed of in landfill.
The RSR furnace is 4.8 m internal diameter by 4 m high and is fitted with three 355 mm diameter
graphite electrodes, rated at 4.0 MVA. Electrode consumption is around 7 kg/t of slag smelted.
Construction is a water-cooled steel shell lined with chrome magnesite brick, with a suspended domed
roof. Electrodes are sealed into the roof.

The furnace is operated by slowly adding feed to the furnace and building up a layer of solid
charge to a set level. Feed is then stopped and power is increased to fully melt the charge, and at
completion the slag is tapped and run down to the minimum level. During the above cycle of about
eight hours from one slag tap to another, bullion is also periodically tapped. Energy consumption
per cycle is 12 000 to 14 000 kWh. Lead production per cycle is understood to be of the order of
30 tonnes.
ROTARY FURNACE SMELTING

Two broad types of rotary furnace are used – the rotary kiln and the short rotary furnace. Rotary kilns
are characterised by large length to diameter ratios of the order of 10 to 15:1, whereas for the short
rotary furnace the length to diameter ratio rarely exceeds 1.5:1.
One important aspect of the operation of these furnaces is the slag regime used. Traditionally, a
high sodium slag has been used since it had the characteristics of a relatively low melting point and
low viscosity, allowing for good separation of slag and bullion. It also provided a means of capturing
sulfur into the slag rather than reporting to the smelter gas and the need for costly gas scrubbing.
However, there are significant costs in the use of soda ash and there are environmental problems with
the disposal of soda slags (see below). As a result of these issues the lime–iron–silica slags used in
primary smelting have become more favoured.
Slag regimes
The use of soda slags is primarily a means of capturing sulfur from the smelting operation and the slag
is essentially a sulfide or matte – usually a mixture of FeS and Na2S. The normal fluxes used are
shredded iron scrap as cast iron chips or steel turnings and soda ash (sodium carbonate). Small
amounts of lime and/or silica might be added depending on the composition of feed material, but is
generally not needed with pure battery feeds.
For the smelting of battery pastes the reactions given by Equations 11.7 to 11.14 take place:
PbO + CO = Pb + CO2 (11.7)
CO2 + C = 2CO (11.8)
PbSO4 + 4CO = PbS + 4CO2 (11.9)
PbS + CO + Na2CO3 = Pb + Na2S + 2CO2 (11.10)
PbS + Fe = FeS + Pb (11.11)
PbO2 + Pb = 2PbO (11.12)
PbO2 + 2CO = 2CO2 + Pb (11.13)
The gas phase mainly contains CO and CO2, but some SO2 can be present due to limited reaction
according to Equation 11.14 – ‘the roast reaction’:
PbS + PbSO4 = 2Pb + SO2 (11.14)

It should be noted that CO2 generated from sodium carbonate will react according to
Equation 11.8 and thus will lead to increased fuel consumption. For this reason and because of the
cost of soda ash, the balance between the addition of iron and soda ash should favour a greater
proportion of iron.
The slag resulting from the above is basically Na2S and FeS with a small amount of PbO and
possibly CaO and SiO2. A phase diagram for the Na-Fe-S system is given in Figure 11.4 and shows
that between 25 and 75 per cent FeS the melting point is relatively low. The lowest melting point
eutectic is 640°C at 36 per cent FeS and the highest for a liquid slag is 760°C at 60 per cent FeS.
1200
1000
Liquid
Temperature °C
3 Na 2 S.4FeS
800 5Na 2 S .2FeS 760°C
(730°)
695°C
650°C 640°C
600
400
0 20 40 60 80 100
Na2S Composition % FeS
FIG 11.4 - Na-Fe-S system phase diagram.
A high FeS content in the matte tends to increase the lead content and reduce lead recovery to
bullion by reducing the reaction given by Equation 11.11. The equilibrium constant (k) for
Equation 11.11 is given by Equation 11.15:
Log k = -1610/T + 2.388 (11.15)
where:
T is the temperature in K
At 1000°C, k = 13.3, so that the activity of PbS in the matte is the activity of FeS divided by 13.3.
A high FeS content of the matte also has more tendency to precipitate Fe or magnetite (Fe3O4) at
lower reduction potentials. These are solid phases at normal operating temperatures and will raise the
viscosity of the matte or slag mix, tending to increase the loss of lead as entrained metal. An optimum
Na2S:FeS ratio in matte is regarded as 1:1.86.
If significant slag forming components are present, such as in residue smelting, a separate slag
phase will form in equilibrium with the matte. The Na2O activity coefficient in slag is low compared

with matte and will cause sodium to transfer from the matte to the slag until activities are equal. The
sodium composition of slag will thus be higher than matte and the sodium contained in slag is
essentially wasted as a means of capturing sulfur. Consequently, for cases where a significant amount
of slag is produced the aim should be for a low Na2S:FeS ratio in the matte of little more than 1:4. A
reasonable level of sodium is needed to maintain low slag viscosity and high levels unnecessarily
consume soda ash as a costly reagent. Some Na2S will also dissolve in slag and an optimum level of
sodium in slag is regarded as 25 per cent as (Na 2S + Na2O).
An iron–soda matte–slag mix tends to be emulsified and is difficult to separate (Queneau, Cregar
and Mickey, 1989).
Although soda slags provide a ready means of capturing sulfur and provide a low viscosity slag/
matte at relatively low temperature for the efficient separation from bullion, there are significant
associated problems, which may be listed as follows:
• Soda ash is a costly reagent.
• Soda slags are very aggressive to chrome magnesite brickwork and to steel if exposure occurs.
• Soda slags are hygroscopic and can expand and break down in landfill. Under these conditions the
FeS can be oxidised to Fe2O3 and So, generating heat and raising the temperature sufficiently to
ignite the sulfur and the remaining sulfides.
• The slags contain water soluble heavy metal compounds, which can be leached in landfill
situations, particularly when breakdown occurs as above.
Because of the above, disposal of soda slags are classified as hazardous wastes with significant
disposal difficulties and are unacceptable in many locations, hence there has been significant
incentive to change to a more conventional silicate slag regime as used in primary smelting (see
Chapter 5). This will require an increase in operating temperature to 1150 to 1200oC, which can be
assisted by the use of oxygen enrichment. A matte can still be generated using metallic iron fluxing,
but sulfur has more potential in this case to report to the gas phase. The solubility of sulfur in the silica
slag is also limited, and in general the sulfur should be less than one per cent in the feed material. This
will essentially require desulfurisation of the battery pastes prior to smelting with the use of silica slag.
Target silica slags are generally of the olivine structure with melting points in the range of 1100 to
1200°C and composition as follows:
• ten to 15 per cent CaO
• 40 per cent SiO2
• 45 to 50 per cent FeO
Fluxing materials required are silica, shredded iron scrap and lime, with coal as the reductant.
The rotary kiln

It is possible to process whole batteries in the rotary kiln, but more often it is used to smelt lead-
bearing components after separation of plastic materials. Thus the rotary kiln can perform similar
functions to the blast furnace but with a higher degree of flexibility due to the ability to handle fine
material, and it is free of many of the problems associated with the blast furnace. The primary
disadvantage is the relatively short life of refractories.
Kilns are constructed as a steel shell fitted with two or three outer rings as tyres, which sit on
trunnion rollers. The kiln is inclined at between two and four per cent. A large ring gear attached to

and encircling the outside of the kiln is driven by a pinion gear, which in turn is driven by an electric
motor. Rotational speed is usually variable from around 0.3 to 1.5 rev/min depending on kiln
diameter, but usually the nominal design speed represents a peripheral speed of 10 m/min. The kiln is
lined with high alumina brick at the feed end and chrome magnesite brick in the reaction zones and
discharge end. This brickwork overlays a full backing of insulating firebrick. The discharge end is
narrowed to form a dam for the collection of molten lead and slag.
Figure 11.5 shows a schematic of a smelting kiln installation.
Stack
After Burner Bag Filter

Drop-out Chamber
Battery Scrap Coke Soda Ash

Feed
Dusts
Iron
Screw conveyor
Burner
Kiln
Slag
Bullion
FIG 11.5 - Rotary kiln – secondary smelter.
Feed is composed of battery materials, other lead-bearing residues and scrap, fine coke or coal,
and fluxes. The fluxes used depend on the type of slag and can be soda ash (sodium carbonate) and
shredded iron scrap for the production of soda slags or limestone, silica and iron for the production of
silica slags. Separate bins and weighfeeders for each component are used to continuously blend the
feed, which is fed by conveyor into the kiln.
The kiln is fired at the discharge end with a natural gas or oil burner and the flame is directed at the
surface of the slag pool, since its main use is control of the viscosity of the slag to ensure good
separation of lead bullion. The burner is used for initial heating on start-up, but the oxidation of coal
and the exothermic heat of reduction of PbO are sufficient to maintain the operating temperature of
the kiln. Gases leaving the feed end are cooled and filtered in a bag house before discharge to
atmosphere. Dusts collected in the flues and bag house are recycled to the kiln feed.
Slag continuously overflows the dam at the discharge end and is collected in slag pots where it
solidifies and can be crushed for campaign reprocessing if required or for disposal. Bullion is
intermittently tapped through a tap hole by stopping the kiln, opening the tap hole and rotating the kiln
so that the tap hole is at the bottom. Lead is collected via a chute into a ladle.
Rotary kiln smelters are operated at the Harz-Metall plant at Goslar, Germany and at the
Pedricktown plant of NL Industries in New Jersey, USA. The Harz-Metall kiln of 3.1 m internal
diameter by 40 m long had an average capacity of between 130 and 300 t/d of lead bullion depending
on the nature of the feed material processed. Performance details are reported as in Table 11.1 on the
basis of the production of a soda slag.

TABLE 11.1
Performance data for the rotary kiln smelting process (Schenker, 1990).
Feed material Metallics Oxides Refinery drosses Lead residues Cl rich flue dusts
Feed rate (t/d) 350 270 400 200 240
Lead bullion output (t/d) 300 195 300 130 150
Number of tappings per day 12 8 12 5-6 6
Iron chips flux (kg/t feed) 70 160 160 160 120
Soda ash flux (kg/t feed) 40 90 90 90 320
Reduction coal (kg/t feed) 40 70 70 70 100
Slag make (kg/t lead) 210 350 340 460 960
Fuel gas used (kWh/t lead) 500 890 690 990 860
The composition of rotary kiln slag varied depending on the compounds to be eliminated in the
slag, which are principally S, SiO2 and CaSO4, and is within the range shown in Table 11.2.
TABLE 11.2
Composition of rotary kiln slag.
FeO Na2O S SiO2 CaO C Pb + Sb

25 - 45% 13 - 27% 10 - 15% 4 - 8% 1 - 2.5% 2 - 6% 3 - 5%
In one variant of the rotary kiln by the ‘Oliforno process’ operated by Accumulatoren – Fabrik,
Oerliken, Switzerland, the kiln is used to incinerate whole batteries to produce a molten slag and lead
bullion, which are simply granulated together on discharge from the kiln. The kiln is designed with a
relatively steep incline to allow molten lead to drain rapidly and not be held up in the kiln and possibly
be oxidised.
The mixed granulated material is then processed in a short rotary furnace with coal or coke for
reduction to lead bullion.
The plastic components of the battery provide the bulk of the fuel for the kiln, but the problems of
handling chloride rich dusts and sulfur in kiln gases remain.
Short rotary furnaces
These furnaces are the workhorses of the secondary smelting industry. They have similarities with the
reverberatory furnace, but are operated on a batch basis, providing considerable flexibility in being
able to adjust the fluxing regime. The thorough mixing action greatly enhances its ability to conduct
reduction reactions, as well as allowing optimum reaction time for drossing. The rotary furnace is
used on a campaign basis to process separated battery components, such as melting the metallic lead
fraction and separately reducing pastes. It can be used for controlled oxidation of bullion for drossing
out impurities such as arsenic and antimony, as well as reduction of oxide drosses to concentrate
impurities such as antimony.
The construction of the short rotary furnace is relatively simple. It consists of a drum fitted with
two steel ring tyres resting on trunnion rollers and driven through a ring gear. Diameters range from
2 to 5 m with lengths from 2.5 to 7 m, and usually have a burner fitted in one end with the gas exit flue

located above the burner at the same end. The charging door is fitted in the other end as well as the
tapping port, with access for both charging equipment and tapping ladles. A schematic of a typical
installation is shown in Figure 11.6.
Stack
Mixed Feed After-burner &

Quench chamber
Charge Hopper
Ventilation Air
Drop-out Chamber Bag Filter
Charge Burner Dusts recycled
Slag Pots Rotary Furnace
Bullion Holding Pot
FIG 11.6 - Schematic of a short rotary furnace installation.
Furnace lining is usually chrome magnesite brick and the life of the refractories is relatively short.
Most installations have more than one furnace to allow for downtime for re-bricking.
The most common furnace size is 3.5 m diameter by 5 m long with an effective working volume of
7 m3. Maximum rotational speed is 1 rev/min. Burner capacity is of the order of 2.5 MW and furnace
gas volume 10 000 Nm3/h. This volume may double with afterburning and dilution prior to gas
cleaning. Ventilation air covering the furnace surrounds and ancillary operations can total up to
50 000 Nm3/h for such a furnace installation.
Operation is on a batch basis and components are commonly premixed with coal and fluxes before
feeding. The furnace is fed by means of a retractable conveyor through the charging door and loaded
by front end loader, or more commonly by a ‘spoon’ hopper fitted to the front of a fork-lift truck,
which is pushed into the furnace and rotated through 180 degrees to dump the contents.
After completion of charging the furnace is intermittently rotated to turn over the material for
drying, which takes about two to three hours. When drying is complete the furnace is rotated
continuously under maximum burner operation. On completion of meltdown a second charge is
added followed by a second drying and melting cycle. A third charge can sometimes be added.
Following final meltdown the furnace is run at operating temperature for a set time of around two
hours and is then ready for tapping. Temperature is raised prior to tapping to facilitate the separation
of slag and bullion. The tap hole is opened and the furnace rotated to first tap slag and matte, followed
by bullion into separate ladles.
Furnace gases usually pass through an afterburner, followed by a drop-out chamber, a cooler and
bag house before discharge to atmosphere. Bag house areas used are typically 100 m2 per m3/s of gas
passing.

Collected dusts are recycled to feed mixing. Dusts produced from smelting battery pastes can be
up to ten per cent of the bullion production, but this can be reduced by more than 50 per cent if the feed
is crudely pelletised in a drum or disc pelletiser.
Short rotary furnaces have been used for processing whole batteries as well as mixed components
and separated pastes and metallics. The furnace has been widely used for processing pastes with the
production of soda slags. A typical sulfur balance for a short rotary furnace is given in Table 11.3.
TABLE 11.3
Sulfur distribution in a rotary furnace with soda slags.
Output stream S deportment

Slag 80%
Bullion 7%
Dusts 11%
Gases 2%
The problems associated with soda slags detailed above have led to a shift to desulfurisation of
pastes and the reduction of desulfurised pastes with the production of lime silica slags. This has
necessitated furnace operation at higher temperature and the use of oxygen enrichment of the gas
burner.
It is preferable to separately process pastes and metallics because of the different impurity or
alloying elements present. Metallic components are simply melted in the furnace, but may be oxidised
to some extent to separate calcium, antimony, arsenic and tin into a small volume of PbO-rich slag.
That slag can be accumulated and separately treated by addition of coke or coal at the end of the cycle
to produce an impure bullion, which can be sent to a refinery. In past practice the main impurity was
antimony and the resulting lead–antimony alloy could simply be used for the production of specific
antimonial lead alloys. Currently there is a much larger range of alloying elements for battery grids,
particularly calcium and tin. Calcium will be oxidised readily and report to the final slag, whereas tin
will report to the impure bullion with antimony and will need to separated by standard refining
procedures.
Paste materials are separately processed with the addition of coke fines and fluxes as detailed
above, and generally produce a high-grade lead bullion.
Table 11.4 illustrates performance of a short rotary furnace of 3.5 m diameter for various feeds and
with the production of a soda slag.
TABLE 11.4
Performance data for a typical short rotary furnace (Schenker, 1990).
Feed materials Whole batteries Metallics Oxides (pastes) Refinery drosses

Feed rate (t/d) 90 130 60 100
Lead bullion production (t/d) 70 110 45 80
Reduction coal (kg/t feed) 40 80 120
Slag (kg/t lead) 150 - 200 60 750 50
Gas use (kWh/ t lead) 410 170 870 470
Cycle time (hours) 10.5 12 7 4.5
(Three loads) (Four loads)

TOP BLOWN ROTARY CONVERTER (TBRC)

The TBRC is represented by the Kaldo process, developed and operated by Boliden in Sweden and
detailed in Chapter 7. This process is suitable for both primary and secondary smelting and can accept
whole batteries if required. The Kaldo system at the Ronnskar smelter has adequate facilities for the
capture of sulfur and paste desulfurisation is unnecessary.
TOP LANCE SLAG BATH REACTORS
Two proprietary designs are available as the Isasmelt process and the Ausmelt process, both
following developments of the CSIRO in Australia for both primary and secondary lead smelting and
as detailed for primary lead smelting in Chapter 7. The Isasmelt was first adapted for secondary
smelting at the Britannia Lead smelter at Northfleet, England in 1991, followed by a unit at the Metal
Reclamation Industries’ secondary smelter in Malaysia in 2000 with a capacity of 50 000 t/a of lead.
In this case batteries are fully separated and the metallics are separately melted by campaign through
the Isasmelt or using rotary furnaces. Desulfurised pastes containing around one per cent sulfur are
processed in the Isasmelt furnace on a batch–semi-continuous basis.
Pastes are added continuously together with coal, and lead bullion is regularly tapped until the slag
volume builds up to a preset level, which takes around 36 hours. Slag composition at this point is
between 55 and 65 per cent PbO. Bath temperature is slowly raised during this time from 900 to
1000°C to maintain slag fluidity as impurities build up. Bullion is relatively pure at over 99.9 per cent
Pb and impurities such as arsenic, antimony and tin accumulate in the slag. Paste addition is stopped at
this time and slag is tapped into a short rotary furnace for reduction with coal to form an impure
antimonial lead and a final silica slag containing less than 0.5 per cent lead. It is possible to continue
slag reduction with coal and flux additions in the Isasmelt reactor at an increased temperature of
1200°C, but this practice has not been as efficient as the use of a separate slag reduction stage in the
rotary furnace. The total cycle is 40 hours including 36 hours of continuous paste feeding and two
hours of fluxing and slag reduction. Lead production and the lead balance during that time is given as
(Brew, Fountain and Pritchard, 1991):
• 175 tonnes of lead in paste feed,
• 170 tonnes of soft lead bullion,
• five tonnes of alloyed impure lead,
• 0.03 tonnes of lead in final slag, and
• ten tonnes of lead recycled in flue dusts.
The advantages of this approach are the use of silica slags low in residual lead, and high thermal
efficiency.
The Ausmelt plant at the Metalleurop Nordenham smelter in Germany is designed to process both
primary and secondary feeds and is detailed in Chapter 7.
ELECTROWINNING PROCESSES
To address the problems associated with slags, environmental emissions and occupational health
issues from secondary smelting operations, a number of hydrometallurgical processes involving the
electrowinning of lead from battery pastes have been developed. One or two only have been operated

on a small commercial scale, but without any significant acceptance for new or expanded secondary
smelting operations. Despite this the technologies appear to adequately address the issues and are
mostly founded on well established principles used in electrolytic lead refining. The processes also
closely relate to technology developed for primary hydrometallurgical extraction, as covered in
Chapter 9.
In this case batteries are fully separated, metallic components are simply melted and drosses
from that operation together with desulfurised battery pastes are subjected to hydrometallurgical
extraction of lead followed by electrowinning from the leach solution. As detailed in Chapter 9,
solutions used for lead electrolytes are fluosilicates as used in the Betts refining process,
fluoborates and chlorides.
After desulfurisation, battery paste material contains PbO, Pb(OH)2, PbCO3, PbO2 and some fine
metallic Pb. A common problem with hydrometallurgical extraction is that both metallic lead and
PbO2 are not soluble in the leaching solutions. A common approach is to make use of the reaction
shown in Equation 11.16, by the addition of lead powder as required under acidic conditions.
Pb + PbO2 = 2PbO (11.16)
The fine metallic lead contained in the paste material will contribute to this reaction and will in
turn be dissolved.
As shown in Chapter 10 – Table 10.1 ‘Average battery paste analysis’, lead will be distributed in
battery paste as follows:
• sulfates converted to soluble salts 51 to 64 per cent of contained lead
• PbO – soluble eight to 11 per cent of contained lead
• PbO2 – insoluble 24 to 32 per cent of contained lead
• Pb – insoluble four to six per cent of contained lead
Based on this analysis, the amount of powdered lead required to reduce PbO2 is an equivalent
amount to the lead as PbO2 less the amount of free metallic lead already present, that is 20 to 26 per
cent of the contained lead in the paste material. This could be regarded as the required amount of
cathode lead recovered which needs to be recycled to the leaching stage, and is a significant amount.
An alternative proposed for the RSR process is the use of carbon or organics present to reduce
PbO2 during drying, in which the paste is heated to 290°C. The low temperature operation will avoid
problems of lead fuming and is sufficient to achieve reduction. In line with the above composition,
carbon equivalent to 1.2 to 1.5 per cent of the lead content would be required to achieve reduction of
PbO2.
Another option with the RSR process is the use of SO2 during paste desulfurisation leaching with
sodium carbonate; however, this will generate additional sulfate at around 50 per cent more than
generated from the removal of the lead sulfate content alone.
In the Engitec process, based on a fluoboric acid electrolyte, hydrogen peroxide is used according
to Equation 11.17 during leaching with HBF 4.
PbO2 + H2O2 + 2HBF4 = Pb(BF4)2 + 2H2O + O2 (11.17)
Residual H2O2 in solution is useful in this case in preventing the formation of PbO2 at the anode
during electrolysis.

The other significant issue for hydrometallurgical electrowinning processes is the formation of
PbO2 at the anode. As discussed in Chapter 9 (Equations 9.10 and 9.11), competing reactions at the
anode result in the formation of oxygen or PbO2. PbO2 deposition is unwanted since the aim is to
recover all lead as metal by deposition on the cathode. Various techniques have been developed to
prevent the deposition of PbO2, such as the presence of phosphorus in solution as developed for the
US Bureau of Mines process and the presence of arsenic in solution as used in the RSR process (see
below). In the proposed Ginatta electrowinning process the addition of cobalt to the electrolyte at
around 200 mg/L is used to reduce the oxygen overvoltage, thus promoting oxygen evolution and
reducing any formation of PbO2. It is also claimed that the use of cobalt prevents the degradation of
graphite and enables it to be used without PbO2 coatings, or the use of titanium anodes (Ginatta, 1984).
Figure 11.7 gives a generalised flow sheet for the electrowinning processes with various options
for handling PbO2 shown as dotted lines.
Separated Battery Pastes
Optional SO2 addition to

reduce PbO2
Paste
Desufurisation
Optional C addition to
reduce PbO2
Drying
Optional lead powder
recycle for PbO 2 reduction
Optional reagents to
reduce or facilitate
the reduction of PbO2
Leaching
Reagents for deposit levelling
and suppression of PbO2
formation
Filtration
Electrolysis
Cathode lead
FIG 11.7 - Generalised flow sheet for electrowinning lead from battery pastes.
The US Bureau of Mines process

This process was developed in the 1980s to address environmental problems associated with secondary
lead smelting at that time. It extended the Betts electrorefining technology using fluosilicate electrolytes
to process desulfurised battery pastes and produce a dense cathode deposit of pure lead metal.

Desulfurised paste is leached with fluosilicic acid as spent electrolyte to dissolve lead, as in
Equation 11.18:
PbO + H2SiF6 = PbSiF6 + H2O (11.18)
Leaching time is around one hour at 50°C and can give a solution of up to 150 g/L Pb. Metallic
lead powder is added to the leach to reduce PbO2, as discussed above. After filtration the solution is
fed to the electrolytic cells, maintaining an electrolyte composition of the order of 70 g/L Pb and
90 g/L H2SiF6. Lower levels of lead in solution will cause the cathode deposit to lose density and
become spongy. The solution contains animal glue at 0.05 g/L and lignin sulfonate at 4 g/L as grain
refiners to aid the production of a smooth and level cathode deposit. Lead starting sheets are used for
the cathode.
Initially graphite anodes were used but with oxygen evolution they were attacked and deteriorated
rapidly. Hence titanium anodes coated with PbO2 were ultimately selected. To prevent the formation
of PbO2 the USBM process uses the presence of phosphorus in solution at around 1 to 2 g/L, which is
added as phosphoric acid (H3PO4 at 3.1 to 6.3 g/L). 1.5 g/L P in solution will correspond with one per
cent lead deposition on the anode as PbO2, whereas at 0.5 g/L the lead deposition on the anode will be
closer to 20 per cent. Phosphoric acid may be lost in the leaching step and needs to be continuously
added to the electrolyte.
Current densities proposed are 170 amps/m2 of cathode area in line with electrorefining practice (see
Chapter 13), and current efficiencies are 95 to 97 per cent. Cell voltages are around 2.9 volts, giving
energy consumption of 0.78 kWh per kilogram of lead recovered (Cole, Lee and Paulson, 1985).
The RSR process

As described above, the preferred method of preparation of desulfurised battery pastes is low
temperature drying to decompose PbO2, and it has been found that sufficient organic materials are
present to provide carbon for the reduction reaction.
The dried paste is leached in spent electrolyte to dissolve lead in accordance with Equation 11.18.
Lead concentration is raised to around 150 g/L or up to 200 g/L but must maintain a free fluosilicic
acid concentration of at least 50 g/L to prevent hydrolysis and precipitation of lead compounds. Lead
recovery to the leach solution is about 95 per cent and the leach residue containing 30 per cent lead
and two to three per cent sulfur can be recycled to the desulfurisation step, or part discarded after
conversion to a slag in an electric furnace.
The electrowinning electrolyte is maintained at around 60 g/L lead by recirculation and contains
glue and lignin sulfonate for deposit levelling. Each cell contains 50 anodes and 51 cathodes of 2 m2.
Cathodes are starter sheets fabricated from lead sheet. Anodes are graphite but are prepared by
electroplating a smooth coating of PbO2 over a non-conducting inert mesh material. Deposition of the
PbO2 is continued until the mesh material is completely covered, and this technique provides a
reinforced conductive coating that is coherent and is not subject to breakage or spalling (Prengaman
and McDonald, 1980).
The formation of PbO2 on the anode during normal electrolysis is prevented by the addition of
arsenic to the electrolyte at a level of 0.5 to 1.0 g/L. Boric acid is also added to the electrolyte to
prevent the decomposition of fluosilicate and the release of HF vapour from the cells.
Any copper in the electrolyte will deposit with lead, but arsenic, antimony and bismuth will
remain in the electrolyte. It has been noted that antimony builds up to a maximum of around 2 g/L in

the electrolyte and then is no longer extracted during leaching. High purity lead is deposited at better
than 99.9 per cent and any minor impurities in the cathode lead, such as copper, can be removed by
conventional refining approaches after melting in preparation for ingot casting. Purification of the
electrolyte by lead powder addition could possibly be used to avoid this (Prengaman and McDonald,
1990).
The Engitec process

The Engitec process for battery paste processing is based on the use of a fluoborate electrolyte.
Desulfurised pastes are leached in spent electrolyte with the addition of H2O2 to decompose PbO2 and
produce a solution of up to 200 g/L Pb. After filtration the leach solution is added to a circulating
electrolyte to maintain lead at around 100 g/L and 100 g/L of free HBF4. Glue and lignin sulfonate are
used for cathode deposit levelling, and electrolyte temperature is held at 35°C.
Stainless steel cathode sheets are used, from which the lead deposit can be readily stripped. The
cathode current density is around 330 amps/m2 and cycle time 48 hours between stripping operations.
Cathode purity is in excess of 99.99 per cent.
The anodes have been specially developed by Engitec and consist of a composite wire of copper
with an outer layer of tantalum on which PbO2 has been deposited to lower the oxygen overpotential.
Each anode consists of a grid of wires held in a frame and operates at a high current density of around
1500 amps/m2 of anode surface. The high current density and the presence of residual H2O2 from the
conversion of PbO2 in the leaching step prevent the formation of PbO 2 at the anode.
Energy use is reported to be around 0.9 kWh/kg of cathode lead (Reynolds, Hudson and Olper,
1990).
Subsequent to the development of the above process for battery paste processing, Engitec have
extended their fluoborate technology to the extraction of lead from sulfides by leaching with ferric
fluoborate solution, followed by electrowinning in a diaphragm cell to recover cathode lead and
re-oxidise ferrous iron in solution back to the ferric state for recycle to the leaching stage. This is
detailed in Chapter 9 – ‘Fluoborate Systems’. Although this involves the use of a diaphragm
electrolytic cell with increased voltage drop through the diaphragm, the anode potential for ferrous
iron oxidation is much lower than for oxygen evolution and there is no possibility of PbO2 deposition
on the anode. As a result standard graphite anodes can be used. Application of this approach to battery
scrap processing has been proposed by conversion of pastes into lead sulfide by means of a biological
sulfate reduction process, which effectively follows the reactions given by Equations 11.19 to 11.21
(Olper et al, 2000):
PbSO4 + 4H2 = PbS + 4H2O (11.19)
PbO + 4H2 + H2SO4 = PbS + 5H2O (11.20)
PbO2 + 5H2 + H2SO4 = PbS + 6H2O (11.21)
Lead sulfide so produced together with metallic lead from battery grids can then both be leached
with ferric fluoborate according to Equations 11.22 and 11.23, allowing a common system for
handling all battery components, and producing high quality refined lead.
PbS + 2Fe(BF4)3 = Pb(BF4)2 + 2Fe(BF4)2 + So (11.22)

Pb + 2Fe(BF4)3 = Pb(BF4)2 + 2Fe(BF4)2 (11.23)
The Ginatta process

The Ginatta process also uses a fluorborate electrolyte and is based on the leaching of battery pastes
which have been desulfurised with ammonium carbonate. The electrowinning process is licensed to
MA Industries, who promote it in conjunction with their battery breaking technology (Ginatta, 1984).
In the leaching stage PbO2 is reduced by lead metal, as in Equation 11.16, but this is promoted
by the use of a ‘redox pair’ such as Fe3+/Fe2+ in the solution in small amounts, as shown by
Equations 11.24 and 11.25:
Pb + 2Fe3+ = Pb2+ + 2Fe2+ (11.24)
PbO2 + 2Fe2+ + 4H+ = Pb2+ + 2Fe3+ + 2H2 (11.25)
In any event it is most likely the reaction given by Equation 11.16 proceeds in this way during acid
leaching, whether by iron or another ‘redox pair’.
Some scrap metallic lead may need to be added to the leaching stage to allow for complete
conversion of PbO2. The leach solution contains 100 g/L lead and the spent electrolyte 40 g/L.
As mentioned above, cobalt at 200 mg/L is used to promote oxygen formation at the anode and
prevent the deposition of PbO2. This also enables the use of ordinary uncoated graphite for the anodes
with minimal degradation.
Triton x-100 and phenolphthalein are used as levelling agents and are said to enable the use of
higher cathode current densities at 400 amps/m 2.
The PLACID process

The PLACID process uses a chloride system with a hydrochloric acid leach of direct battery pastes
without prior desulfurisation. Details are given in Chapter 9 – ‘Processes Based on Aqueous
Electrolysis – Chloride Systems’ and a flow sheet is shown in Figure 9.4. Lead powder is used during
the leaching stage to reduce PbO2, constituting a significant circulating load. Sulfate is removed from
the leach solution by precipitation of gypsum with lime.
The disadvantage of the use of a chloride system is the production of lead powder or sponge at the
cathode rather than a dense deposit as with fluosilicate and fluoborate electrolytes. In this case such an
output would facilitate recycle to the leaching stage, but the bulk of the cathode deposit must be
compressed by briquetting or roll extrusion prior to melting to minimise oxidation.
REFINING OF SECONDARY LEAD

Much of the secondary lead bullion produced, particularly from paste materials, will be suitable for
direct recycle for battery manufacture, whereas bullion derived from battery grid materials or from
general scrap metal will contain a range of impurities which may need to be removed. In some
smelting options these impurity elements can be concentrated into first run slags and then into bullion
produced from the reduction of those slags in the secondary smelting stage. This can significantly
reduce the volume of lead to be refined.
The most common impurities are antimony, tin and copper, with some arsenic, zinc, cadmium and
iron. Bismuth and silver are rarely significant impurities.

The refining method used is usually a simplified thermal refining process following the
procedures applied for primary lead refining as detailed in Chapter 12. Copper is first removed by
sulfur drossing in a pan or kettle, which will also remove any nickel present. It may be difficult to
reach low copper levels with low tin and silver contents, but this can be overcome by the addition of
pyrite with sulfur. Following this, a simplified Harris process can be applied by treating the bullion
with sodium hydroxide and sodium nitrate. This will remove antimony and tin in particular, but also
traces of arsenic, zinc and cadmium. It is possible to recover antimony and tin from refining drosses if
this is required using methods outlined in Chapter 12.
REFERENCES
Brew, R B M, Fountain, C R and Pritchard, J, 1991. Isasmelt for secondary lead smelting, in Proceedings
Lead-Zinc ’90 Tenth International Lead Conference, Nice, pp 170-181 (Lead Development Association:
London).
Cole, E R, Lee, A Y and Paulson, D L, 1985. Electrolytic method of recovering lead from scrap batteries,
Journal of Metals, 37(2):79-83.
Eby, D, 1990. Electric furnace smelting at RSR Corporation, in Proceedings Lead-Zinc ’90 Symposium,
Anaheim, pp 825-839 (The Minerals, Metals and Materials Society (TMS): Warrendale).
Ginatta, M V, 1984. US Patent 4 451 340, May 29.
Koch, M and Niklas, H, 1989. Processing of lead-acid-battery scrap: The Varta process, in Proceedings Minerals,
Metals and Materials Society (TMS) Symposium on Productivity and Technology in the Metallurgical
Industries, Cologne, September, pp 495-500 (The Minerals, Metals and Materials Society (TMS):
Warrendale).
production of lead and elemental sulphur using bioprocess technologies, in Proceedings Lead-Zinc 2000
Symposium, Pittsburg, pp 803-813 (The Minerals, Metals and Materials Society (TMS): Warrendale).
Pike, K N, 1990. Secondary lead blast furnace smelting at East Penn Manufacturing Co Inc, in Proceedings
Lead-Zinc ’90 Symposium, Anaheim, pp 955-969 (The Minerals, Metals and Materials Society (TMS):
Warrendale).
Prengaman, R D and McDonald, H B, 1980. US Patent 4 236 978, December 2.
Prengaman, R D and McDonald, H B, 1990. RSR’s full scale plant to electrowin lead from battery scrap, in
Proceedings Lead-Zinc ’90 Symposium, Anaheim, pp 1045-1056 (The Minerals, Metals and Materials
Society (TMS): Warrendale).
Queneau, P B, Cregar, D E and Mickey, D K, 1989. Optimizing matte and slag composition in rotary furnace
smelting of leady residues, in Proceedings Primary and Secondary Lead Processing Symposium, Halifax,
pp 145-178 (Canadian Institute of Mining and Metallurgy (CIM): Montreal).
Reynolds, R M, Hudson, E K and Olper, M, 1990. Advances in lead acid battery recycling: Engitec’s automated
CX Breaker system, in Proceedings Lead-Zinc ’90 Symposium, Anaheim, pp 1001-1022 (The Minerals,
Schenker, G, 1990. Lead recycling from battery scrap and other raw materials in Metaleurop’s lead smelting
plant in Oker, in Proceedings Lead-Zinc ’90, pp 979-999 (The Minerals, Metals and Materials Society
(TMS): Warrendale).
Taylor, J D and Moore, P J, 1980. Secondary lead smelting at Britannia Lead Company Ltd, in Proceedings
Lead-Zinc-Tin ’80 Symposium, pp 1003-1022.

PART D
REFINING OF LEAD BULLION
This part of the text covers refining methods used for the removal of a range of
impurity elements from crude lead bullion produced by smelting operations. It
also covers the recovery of valuable by-product metals such as silver.
Chapter 12 Thermal Refining of Primary Lead Bullion

Chapter 13 Electrolytic Refining of Lead
Chapter 14 Alloying and Casting
CHAPTER 12
Thermal Refining of Primary Lead Bullion
Primary lead bullion is an efficient solvent for a range of metallic elements during smelting operations
and these elements need to be removed in order to produce pure lead metal. Impurities generally
impart hardness to the metal, particularly arsenic and antimony, and lead is softened as these
impurities are removed. Hence in the past, pure lead was referred to as ‘soft lead’ and early refining
techniques, particularly for removal of arsenic and antimony, were called softening.
Removal of impurities or refining is mainly carried out by thermal refining methods, which are
commonly conducted by batch processing in open pots or ‘kettles’. Impurities are generally
removed individually or in groups in a series of steps. The usual refining steps are made in the
following order:
• copper removal or copper drossing (in two stages);
• arsenic, tin and antimony removal or ‘softening’;
• silver and other precious metal separation;
• removal of zinc (added for silver recovery);
• bismuth removal; and
• caustic refining to remove a range of minor residual elements.
Figure 12.1 illustrates a generalised flow sheet of the thermal refining sequence.
In some cases special removal steps are added, such as tellurium removal, where these elements
are present in significant amounts in the ores treated. Also, particular smelters may have less than the
full range of separation stages depending on the impurities present and the smelter’s source of lead
concentrates; for instance bismuth removal can often be omitted. However, in all cases copper
drossing and caustic refining are required.
Some of the steps in the refining process can be conducted continuously, but this is not common
practice and the associated plant is only justified for large lead refineries over say 120 000 t/a of lead
production. Batch processing can be highly flexible and is more easily controlled to final product
specifications. Because of the high density of lead one batch is commonly around 200 tonnes and the
number of batches required per day is quite limited.
A significant part of any refinery can be the various processes required to treat drosses and
residues produced from each of the separate refining steps for the purpose of recovering by-products,
recovering lead for recycle, or rendering the material suitable for disposal. Such processes include the
conversion of copper dross into a marketable form for copper recovery, the production of silver and
gold, the recovery of zinc for recycle, the recovery of antimony to produce antimonial lead alloy and
the conversion of arsenic into a stable material suitable for disposal.
The alternative approach for lead refining is the electrolytic refining process, which is covered in
Chapter 13, but this must be preceded by copper removal and usually by some softening. It also
requires a final caustic refining stage and is not a full replacement of thermal refining.

CHAPTER 12 – Thermal Refining of Primary Lead Bullion
Hot Lead Bullion
Lead concentrate
Iron
Copper Drossing Copper dross
Melting
Sulfur Lead
Arsenic speiss
Sulfur Drossing
Dross to smelter
Copper matte
to copper smelter
Harris Process Sod. Hydroxide

Oxygen Oxygen Softening
or air Alternative Sod. Nitrate
Carbon
Iron Slag
Slag
Reduction Hydromet.
Lime
Rotary Furnace Zinc Slag Treatment
Sod. Antimonate
Calcium Stannate
Arsenic speiss
Calcium Arsenate
Desilvering
Antimonial Lead Alloy Zinc crusts
Liquation
Vacuum Dezincing Lead return

‘Triple Alloy’ Ag/Zn/Pb
Zinc return Vacuum

Distllation
Calcium + Magnesium
Cupellation PbO slag

Kroll Betterton
to smelter
Bismuth Removal
Silver dore
Drosses
Electrolytic Anode slimes

Sod. Hydroxide
Refining
Ca /Mg slag Melting
Gold
Bi /Pb
Sod, Hydroxide Caustic Refining recovery
alloy Refined Silver
+ sod. nitrate
Air Oxidation Gold

Slag to smelter
PbO slag Refined Lead to casting

to smelter
Bismuth metal
FIG 12.1 - Thermal lead refining sequence.

METHODS AND EQUIPMENT

Most refining is carried out in a batch mode and techniques are generally based on the addition of
reagents to molten lead to form a separate solid or molten phase, which separates from the lead and
floats to the surface as a dross, crust or slag to be removed by scraping or skimming.
The principal equipment used is the open top pan or kettle holding between 100 and 300 tonnes of
molten lead. Figure 12.2 shows a cross-section of a typical refining kettle of 3.4 m diameter, but
diameters vary from 2.5 to 4 m. The upper cylindrical part of a 3.4 m diameter 200 tonne kettle is around
1.5 m long, and 10 mm of depth represents one tonne of lead. Steel thickness is 30 mm and unalloyed
steel is used (ASTM -A284-55T). The kettle sits within a brick furnace fired by natural gas or oil and
with provision for air cooling. The level of the operating floor of the refinery is usually one metre below
the rim of the kettle so that the furnace is located and accessed from a lower floor or basement.
Support Plate
Working Floor
Vent Flue 1.7 m
Cooling Air
Injection
Cooling Air
Gas Burner
Furnace Walls
FIG 12.2 - Typical refining kettle.
An agitator fitted in a removable frame can be placed on the top of the kettle and is handled by an
overhead crane. Similarly a submersible centrifugal pump can be fitted for transfer of molten lead
from one kettle to another. The kettle is also fitted with a ventilation hood to capture emitted fumes,
and this also needs to be removable to allow access for placement of other equipment. Ventilation
requirements range between 800 and 1200 Nm 3/h per m2 of kettle surface area.
Drosses are removed by skimming from the surface either manually using a perforated spoon
ladle, or by a crane-operated scoop, or by mechanical equipment such as a backhoe, pneumatic grabs,
or using proprietary skimming equipment based on drag or screw conveyors such as are manufactured
by Worthwick.
The refining kettles need to be serviced by an overhead gantry crane to lift covers, pumps,
agitators and skimming devices at various stages of the batch cycle.
COPPER REMOVAL OR COPPER DROSSING

The copper content of primary bullion depends on the composition of the concentrates treated and can
be up to six per cent, but more commonly between one and three per cent. Copper needs to be removed
to less than 0.01 per cent in this stage and is achieved by cooling the bullion to reduce the solubility of
copper as well as by final treatment with sulfur to precipitate copper sulfide (Cu2S). It may be
considered a two-stage process of first cooling bullion from around 1000°C to around 400°C to

produce a ‘copper dross’, and then a sulfur addition at close to the freezing point or ‘sulfur drossing’
stage. Sulfur drossing was also known as the Colcord or Hulst process.
The cooling of hot impure bullion initially precipitates a PbS-Cu2S matte using the dissolved
sulfur, or a mix of matte and solid alpha copper. As sulfur is depleted, copper may be precipitated as
an arsenide (Cu3As) or as metallic copper (Davey, 1963). As the bullion cools the nature of the
precipitated material will change as the copper and sulfur contents of the bullion are depleted.
Thereafter, solid Cu2S and PbS may be precipitated at certain Cu:S ratios in the bullion. The
composition and texture of the materials rejected from solution are very sensitive to the composition
of the smelter bullion treated.
Figure 12.3 shows the lead corner of the equilibrium phase diagram for the Pb-Cu-S system and
indicates that on cooling some PbS will form as well as Cu2S.
FIG 12.3 - Pb-Cu-S system – lead corner (Davey, Jensen and Seguit, 1980).
The copper to sulfur ratio is important and with bullions low in sulfur content, such as from the
Imperial Smelting Furnace, copper dross has a high content of metallic copper. The precipitated
copper compounds are less dense than lead and float to the surface as a voluminous dross and are
skimmed off. A significant amount of lead is entrained in the dross and further processing is useful to
separate and recycle the entrained lead and yield a copper matte suitable for sale to a copper smelter.
The second stage or sulfur drossing stage merely adds excess sulfur in elemental form to ensure
complete precipitation of copper as Cu2S, and can reduce the level of copper in bullion to less than
0.005 per cent.
Figure 12.3 suggests that the copper level in lead cannot be reduced below the equilibrium
solubility of around 0.06 per cent by sulfur addition (or down to 0.02 per cent if arsenic or antimony
are present), whereas in practice it is possible to go an order of magnitude below this to 0.001 to
0.005 per cent copper. It has been found that these levels cannot be reached in the absence of silver or
tin, which act as promoters of the decoppering reactions. A percentage of 0.002 silver is required to
achieve copper levels of around 0.001 per cent (Davey and Happ, 1971). It has also been found that
continued stirring of the dross with decoppered bullion can cause the copper to revert and redissolve
into the bullion. The explanation for this phenomenon lies in the fact that the reactions are controlled
by kinetics and not thermodynamic equilibrium.

The solid products of reaction float to the surface and are removed from the body of the molten
metal. Reaction 12.1 below is slow, particularly in the presence of silver or tin, whereas Reactions 12.2
and 12.3 are very fast. Similarly, reactions between metallic lead and copper sulfides (Reaction 12.4)
are slow and equilibrium is slow to establish (Davey, 2000). However, reversion will occur if stirring
is continued for long enough after the bullion has reached levels of around 0.002 per cent Cu.
Pb + S = PbS (12.1)
Cu + S = CuS (12.2)
Cu + CuS = Cu2S (12.3)
Pb + Cu2S = PbS + 2Cu (in bullion) (12.4)
Pyrite (FeS2) can be added as a source of sulfur, usually as a supplement together with elemental
sulfur, and can enable effective decopperising without the presence of silver or tin.
Batch copper drossing methods

Usually two or four kettles are required for batch processing, one or two for each stage. One may be
filling or emptying while the other is carrying out the drossing operation.
It is common practice to transfer bullion from the smelter to the refining operation in ten to
20 tonne ladles. A number of these can be in use and can provide a buffer storage as well as being used
to allow the bullion to cool to around 600°C before transfer to the refining kettles. It is common for a
crust to form on the ladles as the lead cools and this crust can consist of a mix of ‘tin dross’ (zinc, tin
and iron spinels), frozen matte and copper speiss, in some cases with a concentration of nickel if this is
present in smelter feed. In fact this can be used as a preliminary purification stage.
The kettles are cooled by blowing air around the outer surface of the kettle, within the combustion
furnace. Water coils can also be used and in some cases direct water addition to the surface of the lead
is practised, but has the considerable risk of causing an explosion by water entrapment in frozen lead.
The molten lead is agitated while cooling takes place and coke breeze or sawdust is usually added to
the surface of the lead to aid the formation of a dry friable dross that can be easily removed. There is a
misconception that drying out the dross with such methods avoids entrainment of a large amount of
lead, but the reality is that the additives or stirring merely encourage surface oxidation of the dross
with its entrained metallics, creating the impression of ‘drying’. Typically the dross will contain 40 to
60 per cent metallic lead. Lead is cooled to 380 to 400°C in the first stage and copper is reduced to
between 0.1 to 0.5 per cent. Batch time may be of the order of eight to 24 hours.
The first stage also removes a portion of the arsenic, tin and antimony as Cu3As, Cu3Sn and
Cu2Sb, in the form of speiss, or as separately precipitated metallides. Arsenic removal may be more
than 50 per cent depending on relative levels of copper, arsenic and sulfur, but antimony is
significantly less due to the preferential formation of arsenides rather than antimonides.
In the second ‘sulfur drossing’ stage, the lead is cooled to close to the bullion’s freezing point of
about 320°C. Operators can sense the freezing point by watching for the formation of frozen lead rims
on the edge of the kettle. Once the bullion is cooled, elemental sulfur is stirred into the lead bullion by
addition into the agitator vortex. Additional water or air cooling may be applied to counter the heat
release from sulfide formation, since best results are obtained at the lowest temperatures. The
solubility of sulfur at this temperature is around 0.7 per cent and this will react with residual copper to

form CuS initially; the CuS then rapidly reacts with further copper in bullion to form Cu2S, which is
kept in suspension during stirring. Sawdust is commonly added to the surface of the lead when the
drossing is complete to kill the reversion reaction by coating the Cu2S particles with oxide and
produce a dry manageable dross. The sulfur dross so produced is low in copper and can contain high
levels of PbS as well as Cu2S. It is removed by scraping from the surface of the molten lead after
raising the temperature to about 360°C and is commonly recycled to the smelting operation or the
sinter plant.
Sulfur use is between one and two kilograms per tonne of lead, but it is also a common practice to
use pyrite in addition to elemental sulfur for copper precipitation, although this degrades the final
matte produced with iron.
Batch times for sulfur drossing are generally less than four hours and final copper levels in lead
can be as low as 0.002 per cent. The drossing reactions are very fast (five to ten minutes), so most of
the time involved is with cooling the batch and then later dross removal. Any copper not removed at
this stage will be extracted during desilverising with the zinc-silver alloy, although this is not
desirable as it complicates the recovery of silver.
Final dross grades produced can range from ten up to 50 per cent copper. Copper dross from the
complete drossing operation will also contain much of the tin present in primary bullion and virtually
all of the iron, tellurium and indium. If it is desired to separately recover these metals, particularly tin,
then the first stage can be controlled to remove predominantly copper and the second stage can be
delayed until after softening by the Harris process which will extract these metals as well as antimony
and arsenic. This is practised at the Hoboken smelter, in which copper is removed to 0.15 per cent in
the first stage prior to the Harris process and then the remaining copper is removed by sulfur drossing
to less than 0.02 before desilverising. It is important to reduce copper to low levels prior to the
desilverising operation.
The presence of silver and tin in bullion is beneficial to the sulfur drossing operation, possibly due
to a change in surface tension of the bullion at the molten sulfur/lead interface, suppressing PbS
formation.
Continuous copper drossing

Continuous copper drossing was developed and installed by the Port Pirie smelter in 1962. The
process uses a gas fired reverberatory furnace and uses the concept of mixing cold lead at 360°C with
incoming hot bullion to cause copper precipitation within the mixing zone. This avoids the need for
cooling through heat transfer surfaces, and the problem of adherence of copper precipitates to the
cooling surfaces, building up accretions and blocking the furnace. The copper dross produced floats
to the top of the lead where it is heated by gas burners, and melts to form a molten matte that is
maintained at about 1150°C. The matte can be tapped from the furnace substantially free of metallic
lead and usually contains above 50 per cent copper.
A cross-section of the Port Pirie continuous copper drossing furnace (CDF) is shown in
Figure 12.4 (Fern and Shaw, 1983).
Feed bullion enters at around 950°C at one end and displaces an equivalent volume of cold lead
from the furnace outlet at the side of the furnace. Bullion at around 380°C is pumped from the far end
through a circulation launder where it is cooled to 360°C by means of immersed water-cooled plates.
It is then returned to a separated compartment at the base of the furnace from where it flows upwards
to mix with the incoming hot bullion. The furnace operates with a number of layers increasing in
temperature from the bottom to the top surface.

Bullion Feed
Tap Hole
Slag
Vent Flue
Gas Burner
Matte
Bullion
Bullion Circulation
Bullion discharge Return Bullion Outlet
Outlet Inlet
Bullion Circulation
Bullion Feed Pump Tank
Pump Tank Tapping Spout
Cooling Plates
Burner
Product Bullion
Launder Circulation Launder
FIG 12.4 - Continuous copper drossing unit (Port Pirie).
A thin slag layer is maintained over the matte to provide protection from the furnace atmosphere.
This can be formed by the addition of silica to form lead silicate, but also contains zinc, iron and tin
extracted from the bullion. The latter elements can render the slag viscous and unworkable although
this effect can be compensated by increasing the PbO formation and by silica addition. Because of the
interference of silica on subsequent treatment of matte, Port Pirie converted to a slag based on the
PbO-As2O3-Sb2O3 system by adding some ‘softener slag’ as the sole flux.
Experience with the CDF has shown that accretions can form on the furnace side walls at the
mixing zone level, but this is manageable if the copper to sulfur ratio is below a critical value of 3:1.
At this ratio a matte of 48 to 50 per cent Cu, 34 to 36 per cent Pb and 16 per cent S can be produced.
The stoichiometric ratio of Cu:S is 3.96:1, so the critical ratio represents an excess of around 30 per
cent sulfur above stoichiometric requirements. Sulfur can be added to supplement the level in primary
bullion and is added into a vortex developed in the return of circulating lead from the cooling launder
back into the furnace (Wiltshire, Miller and Bauer, 1989).
Bullion from the CDF contains of the order of 0.06 per cent copper and must be further removed
by sulfur drossing. This is also carried out continuously at the Port Pirie smelter using a continuous
sulfur drossing unit (CSD) and lowers the copper content of lead to less than 0.005 per cent. This unit
consists of two stirred pots in series followed by a third unstirred pot fitted with a scraper to remove
the dross formed, as shown in Figure 12.5. The first pot is fitted with cooling coils and is for cooling
only, although sawdust as a conditioner is added to the surface of the lead. The second pot is fitted
with cooling coils and sulfur is continuously added from a feeder into the agitator vortex. Dross is
continuously removed from the third pot in the series and bullion flows under a weir to exit the
system. Dross collected from the CSD is high in lead and can be recycled to the smelting operation.

Sulfur Feeder Dross Granulator
Stirred Pans
Feed Launder Product Launder
Sawdust Dross Scraper

Feeder Cooling coils
FIG 12.5 - Schematic of continuous sulfur drossing unit (Port Pirie).
Treatment of copper dross

The composition of copper drosses (or mattes) covers a wide range depending on other impurities
present and the efficiency of the methods used, but typically the copper content is in the range of 30 to
45 per cent. Sulfur may be 15 to 20 per cent and lead in the range of 20 to 50 per cent.
The dross can be upgraded by melting with separation into a copper matte, a speiss and metallic lead
for recycle. This operation can be conducted in a range of different furnaces, including a shaft furnace
(campaigned through a blast furnace), a reverberatory furnace, a top submerged lance furnace and an
electric furnace or a rotary furnace. The addition of lead sulfide concentrate during melting can convert
any metallic copper present into sulfide matte and form additional metallic lead. Iron turnings can also
be added to bind arsenic as a speiss. Bullion is separated from the mix of slags from the melting furnace
during tapping and the slag mix is cast into pans and allowed to settle and solidify. It separates into three
layers of slag, matte and speiss and is broken up and mechanically separated into the three phases.
The matte can be sold to a copper smelter or can be converted to blister copper; however, returns
are generally poor due to impurity penalties for elements such as lead and arsenic. The lead recovered
from melting operations is relatively high in copper, which represents a significant circulating load on
the copper drossing operations.
There are many variations to these operations depending on the available outlets by way of copper
smelting operations, and the nature of the feed they can accept.
At the Port Pirie smelter, copper matte from the continuous drossing furnace was initially sold to
copper smelters, but at a poor return. Subsequently plant was installed to extract the copper as cathode
copper and could be justified by the available tonnage of copper recovered. This involved grinding the
matte and leaching using a sulfuric acid-sodium chloride solution at a temperature of around 85 to
90°C. The leach residue is predominantly lead sulfate and sulfur and is returned to the sinter plant.
The leach solution is subjected to solvent extraction using highly selective LIX reagents to remove
copper and the raffinate is recycled to leaching or partly to a bleed to control soluble impurities.
Loaded solvent is carefully cleaned of entrained aqueous solution to minimise chloride carryover to
the cell house, and is stripped using spent electrolyte (dilute sulfuric acid solution) and fed to the
electrowinning tank-house for deposition of cathode copper. Antimonial lead anodes and stainless
steel cathodes are used for electrolysis (Lal and McNichol, 1987).
Copper dross treatment using sodium metal (the Glover process)

Crude copper dross generally contains a substantial amount of entrained lead metal and PbS as well as
Cu2S. As above, standard practice is to melt the dross to release entrained lead and leave a mixed

copper lead matte. Another means of upgrading developed at the Glover smelter is the treatment of the
copper dross in a separate small kettle with sodium metal. The sodium is first dissolved in a small
batch of lead bullion to which the dross is added. Sodium reacts with the PbS to form Na2S and
metallic lead. Sodium sulfide has a low melting point and produces a fluid matte at a kettle
temperature of around 650°C, and the matte is upgraded to around 30 per cent copper and depleted in
lead to about three per cent. The matte can be skimmed from the surface and solidified. It is much
more acceptable as a saleable product to copper smelters, justifying the cost of the sodium.
This concept can be extended to the direct application of sodium metal to the copper drossing kettles
where the addition of sodium redistributes the sulfides and arsenides and enhances dross fluidity to
facilitate separation of matte from lead bullion. A separate speiss phase also tends to form but requires
the addition of sodium at least equivalent to 100 per cent of the stoichiometric amount corresponding
with sulfur in excess of Cu2S. The reactions with sodium form Na2S, Na3As and Na3Sb in that order.
This can be a useful means of arsenic and antimony separation if present in only small amounts.
Removal of minor amounts of copper

Where high purity concentrates are processed and only minor amounts of copper have to be removed,
one method used at the Naoshima smelter in Japan is to add aluminium to form the intermetallic
compound CuAl2. Aluminium is added as a 40 per cent alloy with zinc because of its low melting
point at 560°C compared with aluminium at 660°C. Zinc is removed from the lead later either in the
dezincing process or by caustic soda treatment. This method produces a dry powdery dross, which is
easily handled and can reduce copper levels to less than one gram per tonne (Moriya, 1989).
SOFTENING FOR ARSENIC, ANTIMONY AND TIN REMOVAL

Arsenic and antimony levels in primary bullion are generally in the range of 0.2 to two per cent for
each element, but antimony is commonly higher than arsenic. The amount of tin present varies widely
but rarely exceeds 0.1 per cent. Two techniques are generally used for separation of these elements:
• oxygen softening, and
• caustic extraction or the Harris process.
Softening relies on the fact that arsenic, antimony and tin are oxidised preferentially to lead and if
an oxide slag is produced it will extract and concentrate these metals as well as any zinc present.
If antimony levels are less than 0.5 per cent these operations can be eliminated at this stage of the
refining operation and reliance placed on final caustic refining.
Oxygen softening
In this case oxygen or air or mixtures thereof are blown into molten lead at temperatures in the usual
range of 500 to 800°C, to form a PbO-rich slag. Arsenic, antimony and tin are oxidised preferentially
to lead and are concentrated in the slag. Arsenic is most efficiently removed by this approach (98 per
cent extraction), followed by antimony (90 per cent extraction) and then tin. It is likely that PbO is
initially formed by oxidation followed by reaction with the impurities to form various arsenites
(nPbO.As2O3), antimonites (nPbO.Sb2O3) and stannates (nPbO.SnO2), where n is 1, 3 or 5. A liquid
slag, as a solution of impurities dissolved in PbO, can contain varying amounts of impurities,
depending on the final target level of impurities in softened bullion; the lower the target the lower the
level of impurities in the slag.

The softening process may be conducted continuously or by batch, and both kettles and
reverberatory furnaces are used. Originally reverberatory furnaces were used as a continuous process
with compressed air injection into the molten lead through air-cooled lances. In more recent forms of
the process, oxygen-enriched air is blown into lead bullion in a kettle through two or three lances.
Provided the temperature is high enough the slag formed can be sufficiently fluid to be continuously
tapped and run over a chilled plate to solidify. The slag may be displaced from the kettle by the
progressive addition of lead bullion to the kettle. With high levels of impurities, or if a high-grade slag
is desired to work up to antimonial lead, two stages in series may be used.
Generally the process is autogenous as the heat generation from oxidation will maintain the
temperature with little fuel input. However, this is influenced by the grade of oxygen or air
enrichment used as well as the operating temperature selected. Batch times also vary widely within
the range of eight to 20 hours and depend on the temperature used, the initial level of impurities and
the degree of oxygen enrichment of injected air. High rates are achieved with pure oxygen injection,
but there is an economic balance due to efficiency of use.
A fluid PbO-rich slag is produced at temperatures of 700 to 800°C, but lower temperature
oxidation may produce a solid dross. Lower temperatures can be used in the presence of a solvent melt
such as NaOH or NaCl to improve selectivity and reduce the amount of lead oxidised.
Final levels of antimony in bullion are the control indicator for the softening process and are
commonly around 0.05 per cent, but can be as low as 0.01 per cent with two softening stages.
Treatment of softener slags

There are various approaches to the handling of softener slags. Usually they are reduced with coke
fines or char in a short rotary furnace to produce an antimonial lead and an arsenic-rich slag from
which arsenic can be extracted by leaching with caustic soda. Arsenic is then precipitated as arsenic
trioxide for sale or by lime to form calcium arsenite for disposal. Alternatively the addition of iron
turnings to the rotary furnace will produce a speiss containing around 40 per cent arsenic for disposal
as well as an antimonial lead metal. The antimonial lead is usually cast into ingots for later use in
producing lead alloys. The antimony content of the alloy can range up to 30 per cent.
The Harris process

The Harris process removes arsenic, antimony and tin by oxidation with sodium nitrate and reaction
with sodium hydroxide to form sodium arsenite, sodium antimonite and sodium stannate, which form
a molten salt solution in excess sodium hydroxide. Sodium chloride can be added to extend the
solvent (Paschen and Winterhagen, 1968).
The overall reactions are given in Equations 12.5 to 12.7:
2As + 2NaNO3 + 4NaOH = 2Na3AsO4 + N2 + 2H2O (12.5)
2Sb + 2NaNO3 + 4NaOH = 2Na3SbO4 + N2 + 2H2O (12.6)
5Sn + 4NaNO3 + 6NaOH = 5Na2SnO3 + 2N2 + 3H2O (12.7)
Arsenic will react with sodium nitrate alone according to Equation 12.8:
2As + 6NaNO3 = 2Na3AsO4 + 3N2 + 5O2 (12.8)

Lead will also react with sodium nitrate as in Equation 12.9:
5Pb + 2NaNO3 = 4PbO + Na2PbO2 + N2 (12.9)
The ease of oxidation is greatest for arsenic and decreases in order – tin, antimony and lead. Full
oxidation of antimony does not occur until all the arsenic and tin are oxidised and extensive oxidation
of lead does not occur until all the antimony is oxidised.
The process reactions are diffusion controlled and require good agitation and dispersion of the
molten salt phase into the molten lead through a vortex induced by the mixer impeller. An alternative
method (as used by the Hoboken smelter) is to pump bullion at high rates into a cylindrical vessel
mounted over the kettle, with sodium nitrate added from a feeder into the cylinder. A temperature above
450°C is required and a residence time of the order of 12 hours to remove impurities to acceptable
levels, represented by a recorded antimony level of less than 0.0005 per cent. This is significantly better
than for oxygen softening, but the process has a higher cost in terms of reagents used and the extended
residence time required. Standard kettles are used and the process is conducted on a batch basis.
A guide to reagent consumption for the individual impurities, expressed as kilogram per kilogram
of impurity, is shown in Table 12.1 (Zaitsev and Margulis, 1985).
TABLE 12.1
Reagent use for the Harris process (kilogram of reagent per kilogram of impurity).
Reagent Arsenic Tin Antimony

NaOH 2.9 1.8 1.5
NaNO3 1.0 0.6 0.6
NaCl 1.0 0.6 0.5
The caustic slag contains arsenic, tin and antimony as sodium salts as indicated above. Of these,
only sodium arsenite is partly soluble whereas the rest are in suspension, and sufficient NaOH must be
used to maintain a reasonably fluid slag.
Treatment of caustic slags from the Harris process

The slags are tapped from the kettle, granulated, and then subjected to separation by hydrometallurgical
methods. The initial step is leaching with water, which will readily extract excess sodium hydroxide
and sodium chloride leaving a residue of the salts of arsenic antimony and tin. The solubility of these
salts is illustrated in Figure 12.6, with tin the most soluble, followed by arsenic and with antimony
relatively insoluble.
The leach slurry is usually cycloned to separate metallic lead granules, which are entrained in the
slag during separation from the surface of the molten lead in the refining kettle.
Figure 12.6 shows that if the concentration of NaOH in the initial leach is above 30 to 35 per cent,
then all salts are insoluble and are retained in the leach residue. Sodium stannate is hydrated under
these conditions to form Na2SnO3.3H2O. The excess sodium hydroxide-sodium chloride solution is
evaporated to recover the reagents for recycle.
A dilute water leach of the residue will extract tin and arsenic and leave antimony as insoluble
sodium antimonite. This residue will also contain any tellurium, indium and selenium contained in the
bullion and if these elements are present in recoverable amounts then a two-stage Harris process can
be employed (see below).

18
16
14
Concentration (% by mass)
12
10
Sn
8 As
Sb
6
-2
0 5 10 15 20 25 30 35 40
NaOH concentration %
FIG 12.6 - Solubility of impurity elements in caustic solution.
The leach solution containing arsenic and tin is treated with a controlled addition of lime (CaO) to
firstly precipitate tin as calcium stannate (CaSnO3.3H2O), and then by further lime addition after
dilution to a NaOH concentration of less than 80 g/L to precipitate arsenic as calcium arsenite
(Ca3(AsO4)2). In some instances calcium carbonate is used for tin precipitation followed by lime
addition, firstly to remove carbonate as calcium carbonate and then to precipitate arsenic. This
approach may give a cleaner separation of tin if required.
Following precipitation of arsenic, the residual solution can be evaporated to recover sodium
hydroxide for recycle to bullion treatment.
Two-stage Harris process

The two-stage process uses the fact that arsenic and tin are more easily separated from bullion than
antimony. In the first stage kettle, sufficient sodium nitrate and sodium hydroxide are added to
separate all the arsenic and tin, leaving most of the antimony to be removed in the second stage with
excess reagent. The slags from the two stages are separately treated by the same hydrometallurgical
routine as above, but in the case of the first stage slag, the initial leach residue or ‘black’ antimony
cake concentrates the minor elements tellurium, indium and selenium. These can be separately
recovered by treatment of the leach residue. The initial leach residue from the second stage slag is
relatively pure sodium antimonite.
Leach solutions may be combined for recovery of arsenic and tin by calcium precipitation. A
generalised process flow sheet for the treatment of Harris process slag is shown in Figure 12.7.
The two-stage approach is used at the Hoboken lead smelter in Belgium. In that case the ‘black’
antimony residue is acid leached to separate indium and tellurium leaving a lead-antimony residue.
Tellurium is precipitated from solution using sulfur dioxide followed by indium precipitation as a
hydroxide. The indium hydroxide is re-dissolved in acid and cemented from the resulting solution as
indium metal by the addition of zinc dust (DeKeyser and Jespers, 1981).

Second Stage First Stage

Harris Slag Harris Slag
NaOH Leach NaOH Leach
Wet Cyclone Lead particles

Wet Cyclone Lead to remelt
to remelt
Filter Filter
Solution
Water
Water Leach Water Leach
Filter Filter
As + Sn solution CaO
Tin Precipitation
‘White’ sod. antimonate ‘Black’ sod. antimonate

48% Sb Sb + (Se, In, Te)
Filter To further processing
CaO Calcium Stannate

40 - 42% Sn
Arsenic
Precipitation
Filter
Calcium Arsenate
15 - 25% As
Evaporation
NaOH (+NaCl) recycle

to the Harris Process
FIG 12.7 - Process flow sheet for treatment of Harris process slags.

Separation of tellurium
If tellurium is present in significant amounts it can be removed by an initial treatment of lead bullion
with a small amount of sodium hydroxide at around 420°C. Tellurium rapidly reacts according to
Equations 12.10 and 12.11. Although tellurium is far more reactive than arsenic, tin or antimony, the
resulting slag will contain some of these elements.
3Te + 6NaOH = 2Na2Te + Na2TeO3 + 3H2O (12.10)
xTe + Na2Te = Na2Te(x+1) (12.11)
When the slag is leached in water the soluble sodium polytelluride can be oxidised with air to
precipitate metallic tellurium as in Equation 12.12:
Na2Te(x+1) + H2O + ½ O2 = 2NaOH + (x+1)Te (12.12)
Sulfur dioxide can also be used to precipitate tellurium metal from sodium polytelluride solution.
A Russian approach uses the addition of sodium metal to produce a high melting point intermetallic
compound Na2Te, which can be collected in a caustic slag and skimmed from the surface of the
molten lead. This material can contain up to 25 per cent Te.
REMOVAL OF SILVER AND OTHER PRECIOUS METALS

Prior to the development of procedures to remove silver it was necessary to cupel all the lead bullion
to oxidise the total lead content to PbO, leaving a silver doré. The PbO-rich slag was then reduced
back to metallic lead free of silver. This was of course practical and economical only for lead bullion
with a relatively high silver content.
The Pattinson process

In 1839 a refining process for silver removal was developed by H L Pattinson in England. This
process used the fact that lead and silver form a eutectic at around two per cent silver with a melting
point of 305°C compared with the melting point of lead at 327°C. The lead corner of the lead-silver
phase diagram is shown in Figure 12.8.
For any lead bullion containing less than two per cent silver, freezing will first produce crystals of
pure lead, leaving silver dissolved in the residual lead melt. A typical operation used a series of small
pans or kettles (say nine). Bullion was fed to the middle pan and was allowed to cool so that relatively
pure lead crystallised from the melt. The crystals were skimmed from the pan using a perforated ladle
and were transferred to the pan on the right, whereas the remaining liquid was transferred to the pan
on the left. This process was repeated for each pan in the series ending with the pan on the extreme
right containing lead almost free of silver and the pan on the extreme left containing lead significantly
enriched in silver at say 30 times the input silver content or up to one per cent. The enriched lead was
then cupelled to yield a silver doré and a litharge slag, but considerably less lead has to processed in
this way compared with the old system of full cupellation.
An improvement to this approach was developed by Luce-Rozan in Marseilles in which dry steam
was injected into the molten lead while cold water was sprayed onto the surface. The steam blast kept the
temperature much more uniform and the enriched alloy approached closer to the eutectic composition of
two per cent silver. Generally only two pans were required for this variant of the process.

420
400
Liquid
380
Temperature
360
Solid Silver
340 + Liquid
320
Solid Lead
+ Liquid
300
0 2 4 6 8
Per cent Silver
Solid Lead
Solid Silver + Eutectic
+ Eutectic
FIG 12.8 - Lead-silver binary phase diagram.
The Pattinson process was replaced around 1880 by the Parkes process, which used zinc to extract
silver, and is now obsolete.
The Parkes process

The precious metals, particularly silver and gold, are removed by the Parkes process, which uses the
ability to form high melting point intermetallic compounds with zinc of the form AgZnm. The
technique was developed by Parkes in Birmingham in 1852, and made practical by Balbach in New
Jersey with a procedure for treatment of the zinc crusts in 1872. The process has not been supplanted
since that time. Gold has a greater affinity to react with zinc than silver and is thus readily separated
with silver, which is the predominant precious metal associated with the production of lead.
Removal of silver using zinc must follow copper removal and ‘softening’. Copper forms
intermetallic compounds with zinc, as does arsenic and tellurium. The presence of antimony and tin
also affects the performance of the desilverising operation, in particular separation of the silver-zinc
alloy phase.
As shown in the zinc-silver phase diagram in Figure 12.9, there are five identified solid phases.
The extremes α and η are solids solutions and there are three intermetallic compounds; β, γ and ε. In
practice the addition of molten zinc to lead bullion followed by cooling will result in the formation of
these intermetallics as solid precipitates, which are mainly of the ε form but also contain η towards the

end of the process. The process also relies on the fact that above 420°C zinc and lead form two
separate liquid phases with a range of compositions and merge into a single liquid phase above 798°C,
as shown in the zinc-lead phase diagram in Figure 12.10. There are thus no solid phases of zinc and
lead to interfere with the separation of solid phase zinc-silver intermetallic compounds.
Temp.
o
C
900
Liquid Phase
800
700
600
500
400
300
200
100
0 10 20 30 40 50 60 70 80 90 100
Ag Zn content % by mass Zn
FIG 12.9 - Zinc-silver phase diagram.
Temp.
o
C Vapour Phase
900
One Liquid Phase
800
700
Two Liquid Phases
600
500
417
400
318
300
200
0 10 20 30 40 50 60 70 80 90
Zn Lead % by mass Pb
FIG 12.10 - Zinc-lead phase diagram.

Generally the Parkes process is conducted as a two-stage batch process using standard lead kettles
or pans. In the first stage, recycled zinc crusts from the second stage are added and dissolved into hot
lead coming forward from arsenic and antimony separation at around 600°C. The lead is then cooled
to 480°C to allow solid phases to form and float to the surface as a crust. This requires the zinc content
at the start to be above the saturation level at 480°C, which is around two per cent. The crust is
skimmed from the surface of the molten lead and typically contains 60 to 70 per cent lead as entrained
metal, 25 to 30 per cent zinc and up to five to seven per cent silver, as well as up to one per cent copper
and some arsenic and antimony. It is important to avoid oxidation of the crust at this stage, to ease
downstream handling and to increase zinc recovery.
The residual lead from the first stage may contain 0.01 to 0.03 per cent silver and is subjected to an
addition of around 10 to 12 kg of zinc per tonne of lead bullion. The temperature is initially raised to
dissolve the zinc, and is then lowered to close to the freezing point or 320°C. After a suitable time the
surface crust is skimmed off and is recycled to the first stage. The silver content of the lead at this point
is generally reduced to less than 5 g/t (0.0005 per cent), but the residual dissolved zinc content is 0.5 to
0.7 per cent.
In the case where large amounts of silver are contained in lead bullion, a three-stage Parkes
process can be used, such as the case at the Torreon Smelter in Mexico, which has an input silver
content of 1.4 per cent and uses around 18 kg of zinc per tonne of bullion. Using this technique some
selectivity between silver and gold can be obtained, since gold is concentrated in the first crusts.
Davey desilverising procedure

The Davey desilverising method consists of a two-stage counter current system using one kettle and
has been applied at the Noyelles Godault refinery in France. The kettle is fitted with a floating shallow
annular trough, fabricated from mild steel, which is filled with water during the cooling cycle to leave
a solid crust at the surface of the kettle.
The sequence starts with fresh bullion from softening being pumped into a kettle containing solid
crusts retained from the second stage. Ingot lead from the liquation of silver crusts is also added at this
point. When filled, the temperature of the kettle is raised to around 470°C with agitation to dissolve
the retained crust and ingot lead. Agitation is then stopped and the kettle is allowed to settle and zinc
silver crystals to collect at the surface. The crystals are then scooped off the surface of the lead and are
transferred to a liquation kettle for melting under a CaCl2-NaCl covering flux. A 28 per cent
silver-lead alloy is produced and a lower lead layer for recycling.
After removal of the zinc-silver crystals, fresh zinc is added to the kettle with additions calculated
according to the silver and copper content of the incoming lead from softening, as given in
Equation 12.13:
% Zn added = 0.634 + 1.676 × (Ag%) + 1.0 × (Cu% - 0.02%) (12.13)
After completion of zinc addition the cooling tray is placed on the bath and water is continually
added to maintain a level in the tray. The lead is gently stirred to promote heat transfer and when the
kettle temperature has fallen to 320°C the cooling tray is removed, leaving a bridging solidified
crust at the surface. The liquid lead in the base of the kettle is then pumped out as desilvered lead
and the above sequence repeated. Cycle time is around 13.5 hours with four hours for stage 1, two
hours for zinc addition, 6.5 hours for cooling and one hour for desilvered lead transfer.
This procedure is most suited to mid-range silver contents of softened lead at around 0.3 per cent.

Continuous desilverising
For many years the Port Pirie smelter operated a continuous desilverising kettle, developed by
G K Williams in 1932.
This process uses a tall cylindrical cast iron vessel 3.05 m diameter × 7.05 m tall. Molten lead
bullion at 600 to 650°C flows into the top and through a layer of molten zinc 1 m deep and held at
530 to 580°C, where it becomes saturated with zinc at that temperature. It then flows down through
the kettle and is progressively cooled to 320°C, close to its freezing point at the base. Silver-zinc alloy
precipitates and floats up to the surface and is incorporated into the zinc layer. Depleted lead flows
back up through a central siphon to overflow at the top, and is reheated in the process. The zinc layer
becomes enriched in silver and its melting point rises. It is periodically ladled off before precipitation
of solid phases begins to occur, and fresh zinc is added. The alloy contains ten to 15 per cent silver,
60 per cent zinc and around 25 per cent lead, and 0.5 per cent copper. This composition is significantly
higher in zinc and lower in lead than crusts from the batch Parkes process. Figure 12.11 gives a
diagram of the Williams desilverising kettle.
FIG 12.11 - Continuous desilverising kettle at Port Pirie (Dawson, 1980).
Zinc is aggressively corrosive to the cast iron kettle and the top section in contact with the zinc
alloy layer is lined with chrome magnesite brick. However, lower sections serve as heat transfer
surfaces in contact with bullion and corrosion is significant, especially with the two upper castings.
Consequently the life of the kettles is only of the order of two years. This imposes a significant cost
penalty and adverse economics have caused the Port Pirie operation to replace this elegant approach
with the more conventional batch system, using standard kettles.
Treatment of silver-zinc alloy

The silver-zinc crusts contain substantial quantities of entrained lead, depending on the efficiency of
the skimming procedure. Hence the first processing step generally involves the removal of excess free

lead by melting and liquation, or in some cases by pressing the hot crusts to squeeze out excess molten
lead using a Howard press. The operation of the Howard press is illustrated in Figure 12.12.
Compressed air
Crust flows into press

Pressed crust
Molten lead return to kettle
Crust
Molten lead
FIG 12.12 - Schematic of the operation of the Howard press.
For liquation, the crusts are melted in a crucible or induction furnace at around 650°C using a salt
flux cover to minimise crust oxidation. The upper silver-zinc layer (or ‘triple alloy’) is poured off and
cast into bars, and the lower lead layer is returned to the main refinery stream ahead of the desilvering
operation. Drosses separated from this melting operation are usually returned to the smelter, but can
contain significant amounts of silver and thus represent a circulating load. Typical performance is
shown in Table 12.2.
TABLE 12.2
Typical performance of silver separation stages.
Stream Silver Zinc Lead Copper
Parkes crust 10% 20% 65%
Triple alloy – after liquation 30% 65% 3%
Impure silver (retort bullion) – after distillation 80% 5% 10%
Doré – after cupellation 99+% 0.2%
The silver-zinc alloy is further separated by removal of the zinc by distillation to leave a residual
impure silver. Distillation was originally conducted using the Faber Du Faur process in silicon carbide
retorts fitted with an air-cooled zinc condenser. The retorts were located within a gas-fired furnace.
Coke breeze or charcoal were usually added to the charge to prevent oxidation as well as calcium borate
to aid in the prevention of ‘Blue Powder’ formation in the zinc condenser. This process required high
temperature operation at around 1250°C and high fuel costs as well as a high cost in retort replacement.
The retorting technique has largely been replaced by the use of an electrically heated vacuum
furnace, also fitted with a zinc condenser. There are a number of different devices for this purpose
with heating by induction, by electrical resistance through a slag layer or by radiant heating bars as in
the Leferrer furnace. The sealed electrical induction furnace under vacuum with an attached zinc
condenser appears to be the most favoured approach – the vacuum induction retort. Operating costs
are much lower using this technique and zinc separation is much higher and above 90 per cent.

Furnaces are constructed using an induction heated crucible of graphite or silicon carbide,
contained within a refractory lined vacuum vessel. The zinc condenser may be external, in the
vacuum train, or may be contained within the lid of the containment vessel. Seals are by rubber O
rings in water-cooled flanges and the ability to maintain vacuum is a critical aspect of efficient
operation. Target operating pressure is around 80 mbar absolute. The final temperature of the retort
bullion (impure silver) formed within the retort at the end of a batch is in the range of 1100 to
1200°C. The detection of the end point of the batch distillation is also an important aspect of
operation and usually is determined by the vacuum pressure and the temperature of the residual
metal. Typical performance is shown in Table 12.2.
The distilled zinc product is recycled to the desilverising stage and the retort bullion is treated by
cupellation, in which air or oxygen is blown into the molten metal to oxidise the lead and residual zinc
to form a slag and leave a molten silver doré containing gold and some copper. Cupellation was
traditionally conducted in a hearth within a reverberatory furnace with lance injection of air or
oxygen-enriched air. However, reactors such as a bottom blown converter, top blown rotary converter
or top submerged lance reactor (Ausmelt or Isasmelt) are now more commonly used, with much
higher efficiency. Again the operations are batch and can have batch times of the order of eight hours.
Sodium nitrate may be added to assist oxidation of some impurities. The bottom blown converter has
the advantage of direct injection of oxygen into the bullion layer, allowing a much deeper litharge slag
layer to minimise the entrainment of metal. Oxygen use efficiency also approaches 100 per cent
(Barrett and Knight, 1989).
Lead-rich slag from the cupellation stage is returned to the lead smelter, and the silver doré is
prepared by casting into anode plates for electrolytic refining or is granulated for ‘parting’.
Electrolytic silver refining

The most common approach for the production of high purity silver is electrolytic refining. Anodes of
silver doré are electrolysed using a silver nitrate electrolyte and pure silver is deposited on stainless
steel cathodes. Silver deposits on the cathode in a dendritic crystalline form, which readily separates
from the cathode by scraping and collects in the bottom of the cell. The anode is separated by a cloth
membrane and retains the anode slimes. The slimes contain gold, platinum and palladium and are
further processed to recover these metals.
The electrolyte is neutral and can contain up to 250 g/L of silver nitrate. Copper tends to build up
in the electrolyte and is controlled by a bleed to maintain a level below 40 g/L. The bleed solution is
treated with zinc dust to precipitate a silver cement which is returned to cupellation. Make-up silver
nitrate is produced by the digestion of doré in nitric acid.
The cathode deposit of silver crystals is washed and filtered and then melted in a graphite crucible
and cast into 23 kg (1000 troy ounce) bars.
The cells used are commonly the Balbach-Thum cell design, which uses a single anode within an
upper diaphragm compartment and a single horizontal cathode sheet on the base of the cell. The cell is
constructed from PVC. Silver deposits in dendritic form and needs to be periodically scraped from the
cathode to prevent short circuiting. It is then removed from the cell. Anode current densities used are
in the range of 450 to 650 amps/m2, and for a cell with anode area of around 0.25 m2 the theoretical
production is around 0.5 kg/h of silver per cell (Mantel, 1960).
The Moebius cell uses a more conventional and compact cell design with vertical electrodes. The
anodes are enclosed in cloth bags and the cathodes are equipped with vertical mechanical scrapers to
continuously remove the silver deposit, which drops to the bottom of the cell.

Maintenance of a consistent and uniform electrolyte composition by recirculation is important

for the achievement of optimum cathode purity and product silver of better than 99.999 per cent can
be obtained.
The anode slime containing all the gold and any platinum and palladium is first treated with
sulfuric acid to extract residual silver and copper, and is then melted and cast into crude gold bar or
into anode plates for electrolytic refining, depending on the presence of the other precious metals. The
Wohlwill process is commonly used for electrolytic refining. It uses an electrolyte of ten per cent HCl
and seven to eight per cent Au and rolled gold cathodes. Current densities are high at 1000 amps/m2.
The electrolyte is periodically withdrawn and treated with SO2 to precipitate gold which is recycled,
and then with NH4Cl to precipitate platinum as (NH4)2PtCl6, leaving palladium in solution which can
be subsequently precipitated with HNO3.
Silver parting
Separation of silver and gold by parting involves dissolving silver from the doré using hot
concentrated sulfuric acid or nitric acid, leaving gold as the residue. The residual gold is simply
melted and cast into bars or may be further refined by chlorination. For effective dissolution of silver
the silver to gold ratio must be greater than 2:1, otherwise the silver will not dissolve. Ferrous sulfate
is added to the clarified silver solution to reduce silver ions and precipitate metallic silver, which is
filtered from the solution, melted and cast into ingot.
For dorés rich in gold that cannot be extracted by acid leaching, the doré is melted and chlorine is
injected. A silver chloride slag will be formed leaving pure gold. The silver chloride slag includes
traces of other metals, but some metal chlorides such as zinc, bismuth and arsenic will be volatilised.
SEPARATION OF THALLIUM
Normally thallium, like mercury, is effectively removed by volatilisation in the sintering process. For
direct smelting processes there may not be sufficient volatilisation with direct capture into the lead
bullion, and a direct method of separation may be required, as is the case at the Trail smelter with the
introduction of the Kivcet process. In this case thallium is removed by the addition of zinc chloride to
molten bullion, displacing thallium as a thallium chloride dross, and leaving zinc in the bullion for
later removal.
SEPARATION OF ZINC FROM LEAD

Metallic zinc is added for desilverising and leaves around 0.5 to 0.7 per cent residual zinc in the lead.
The most common method of residual zinc removal is by vacuum distillation, although methods
involving oxidation into a slag are available. Batch vacuum distillation of zinc from lead was
developed by the St Joseph Lead Company at Herculeneum, Missouri in the 1940s using a bell placed
in a standard kettle as in Figure 12.13b (Isbell, 1949).
Vacuum distillation utilises the widening differences in vapour pressure between zinc and lead at
lower temperatures, as shown in Table 12.3. The rate of mass transfer is also increased at reduced total
pressure.
Batch operation in a kettle of standard size is the most common approach. In one form of the
equipment, the kettle is covered with a lid containing a condenser as a flat water-cooled plate and
sealed onto the rim of the kettle by the use of rubber seals set in a water-cooled flange (Figure 12.13a).

TABLE 12.3
Vapour pressures of zinc and lead.
Temperature (°C) 600 700 800 900

Zinc vapour pressure (mm Hg) 11.2 59.4 231.3 714.2
Lead vapour pressure (mm Hg) 0.00035 0.0051 0.045 0.27
Vapour pressure ratios (Zn/Pb) 31 540 11 625 5160 2631
Condenser surface Condenser surface

Lead flow
Seal Vacuum
Feed launder Lead feed

Vacuum
Agitator
Vacuum
Lead exit seal pot
A. Batch Equipment B. Batch Equipment C. Continuous Equipment
FIG 12.13 - Schematic of vacuum dezincing equipment. (A) Standard kettle developed by Britannia Refined
Metals. (B) Equipment design to avoid seals. (C) Continuous equipment developed at the Port Pirie smelter.
The lid is placed on the kettle and a relatively high vacuum is applied at around 0.05 mbar. The lead is
agitated and zinc distils over from the lead to collect as a solid crystalline material on the cold
condenser surface. Batch time is of the order of eight hours at an operating temperature of 600°C. At
completion the vacuum is released, the lid is lifted and the zinc deposit is removed by hammering and
scraping. The recovered zinc is recycled to the desilverising stage.
An alternative device, shown in Figure 12.13b, uses an inverted open cylinder or ‘bell’ with a
condenser surface at the top as in Figure 12.13a. This is immersed into the kettle to form a hydraulic
seal with the lead rising up into the cylinder as the vacuum is applied. No seals are required but access
for zinc removal from the condenser plate is more difficult. A ‘mud’ slurry can be applied to the
condenser surface to facilitate condensed zinc removal.
Continuous dezincing equipment uses a vacuum vessel in which lead is fed to a peripheral weir to
overflow as a film down the walls to the bottom of the vessel from where it is withdrawn through a
barometric leg seal. The condenser consists of a central water-cooled projection from the lid in the
form of a truncated cone. The lid sits on the rim of the vessel and is sealed by a rubber ring located in a
water-cooled flange. Zinc collects as a crystalline solid deposit on the surface of the condenser. The
process is periodically interrupted for about ten minutes every eight to 12 hours to remove the
condenser and replace it with a cleaned unit. Zinc is removed by hammering and scraping as with the
other forms of dezincing equipment. The equipment is illustrated in Figure 12.13c (Davey and
Williams, 1956).
These processes generally remove in excess of 90 per cent of the zinc content of the lead, down to
a level of less than 0.05 per cent.

Zinc can also be removed by oxidation with air or oxygen and captured in a sodium hydroxide
slag. However, this approach is not efficient or selective for zinc removal but is useful as a final
cleaning stage.
In a similar approach chlorine injection into molten lead will preferentially react with zinc to form
a molten zinc chloride slag, which may be separated by skimming from the surface of the lead. The
handling of chlorine gas in open kettles has inherent hazards and this approach has not often been used
on a large scale, although there is one application at the Trepca smelter in Serbia, where a slag
containing 92 to 95 per cent ZnCl2 is produced. The major disadvantage is that metallic zinc is not
recovered for recycle to the desilverising step.
SEPARATION OF BISMUTH
Because of its adverse effect on the electrochemical and corrosion properties of lead in particular
situations (notably the lead-acid battery), the specification for lead of 99.99 per cent quality requires
bismuth to be below 0.005 per cent. In many applications this is not critical and levels up to
0.03 per cent can be acceptable. Bismuth is also chemically so close to lead that its separation is
difficult. However, depending on the source of lead concentrates, a suitable level can often be
achieved without separate removal, but it can also be present in many ores and in that case, a separate
removal stage is required. Separation relies on the formation of high melting point intermetallic
compounds with calcium and magnesium – Ca3Bi2 with a melting point of 1350°C and Mg3Bi2 with a
melting point of 823°C, as well as the ternary CaMg2Bi2. This technique is known as the
Kroll-Betterton process.
In their initial work Kroll and Betterton found that separation of bismuth was poor with the use of
calcium or magnesium alone, but they later discovered the presence of both metals dissolved in lead
provided synergy and greatly improved separation. As well as forming individual intermetallics, the
ternary compound is also formed, which may be expressed as a combination of the two separate
compounds – Ca3Bi2.2Mg3Bi2 (or 3CaMg2Bi2) (Betterton and Lebdeff, 1936).
In practice the mass ratio of magnesium to calcium used is between 2:1 and 4:1, and depends on
the relative cost of the reagent metals. The process is promoted by the addition of antimony, which
can also form intermetallic compounds as a replacement for bismuth, and is necessary to achieve low
levels of residual bismuth. It is suggested that the antimony compound is isomorphous with the
bismuth compound and a solution of the two causes a lowering of the activity of the bismuth complex
(Moodie, 1976).
The concentrations of the metals in lead at its melting point (327°C) have been given by the
solubility product of the ternary compound according to Equation 12.14 (Davey, 1979):
Log10([Ca][Mg]2[Bi]2) = -7.37 (12.14)
where the concentration of each metal is expressed in weight per cent.

The effect of antimony on the above solubility product has not been defined; however, bismuth
can be removed to less than 0.005 per cent by this process.
In practice calcium and magnesium need to be dissolved into the lead bullion as a first step and this
encounters significant problems due to the ready oxidation of the reagents at operating temperature,
and due to the low density relative to lead which causes them to float to the surface of the lead.
Magnesium is also prone to burn when exposed to air at kettle temperatures. Hence the metals are
handled in ingot form and are usually placed in a wire cage, immersed into the molten lead in a

standard refining kettle, with circulation of lead by pump or stirrer over the alloying metals to aid
dissolution. It is also important that the surface disturbance of the lead bath is minimal to avoid
oxidation – particularly of the calcium content. Even so, oxidation of 15 per cent of the calcium input
and ten per cent of the magnesium input is to be expected. Additions of calcium plus magnesium are
generally in the range of 2 - 5 kg/t of lead. Batch temperatures begin at 450 to 500°C for dissolution of
the reagents, and are reduced to close to 330°C at the end of the batch. Batch times range between ten
and 20 hours.
Depending on the bismuth content, two batch stages can be used with antimony additions into the
second stage. Such additions are typically 0.4 kg per kilogram of bismuth and are usually less than
1 kg/t of lead. It is also possible to dissolve the calcium and magnesium in a small part of the lead
stream with addition of that alloy mix to the main debismuthising kettle. In this case better control of
potential oxidation can be achieved using an enclosed kettle for dissolution either purged with
nitrogen or with the surface covered with a layer of charcoal. Calcium-magnesium alloys at either
70 per cent Mg at 30 per cent Ca or 65 per cent Mg at 35 per cent Ca are also available for this
application, and can be added without the wire cage and with reduced oxidation loss.
The bismuth dross formed is removed from the surface of the lead on completion of the batch.
Drosses normally contain between three and ten per cent Bi, and commonly around six per cent.
Calcium plus magnesium total around two per cent and the remainder is lead. Drosses can be
upgraded by pressing or centrifuging to remove entrained lead.
Bismuth dross is treated by melting at 500 to 600°C with the addition of sodium hydroxide and
sodium nitrate. Calcium, magnesium and antimony are oxidised and removed in a caustic slag,
leaving a bismuth lead alloy with around six to ten per cent bismuth. With upgrading of the dross this
can be raised to around 15 to 25 per cent. The bismuth lead alloy can be further processed to bismuth
metal using a similar series of procedures as used above for lead refining and removing the bulk of the
lead as a litharge slag.
The Kroll Betterton process is relatively expensive due to the cost of calcium and magnesium and
the fact that they cannot be recovered. There is some flexibility in the relative amounts of calcium and
magnesium used, providing some opportunity for cost optimisation.
FINAL CAUSTIC REFINING

The final stage in most refining operations is treatment with sodium hydroxide, often also with the
addition of sodium nitrate as an oxidising agent. This stage particularly removes remaining amounts of
zinc and antimony, but also removes residual calcium and magnesium from the bismuth removal stage.
Sodium nitrate tends to oxidise lead to PbO according to Equation 12.15:
5Pb + 2 NaNO3 = 5PbO + Na2O + N2 (12.15)
PbO then oxidises the various impurity elements as in Equation 12.16:
Zn + PbO = ZnO + Pb (12.16)
Arsenic and antimony are also removed in accordance with the principles of the Harris process as
detailed above, and this is particularly applicable if oxygen softening has been used, where higher
residual levels of arsenic and antimony remain than from application of the Harris process.

Caustic refining is conducted in a standard refining kettle at a temperature of 450 to 580°C with a
batch time in the range of six to 12 hours. Reagents are in flake or powder form and are mixed into the
molten lead by addition to the vortex created by the agitator. Reagent use varies depending on the
impurity load, but is generally less than 2 kg/t of lead and sodium nitrate use is usually less than half
the amount of sodium hydroxide. The oxides are absorbed into the caustic slag layer as a dross, which
can be skimmed from the surface of the melt. At this point the resulting lead will be fully refined and
can be cast into ingots.
REFINING OF SECONDARY LEAD

The impurities contained in secondary lead bullion are generally confined to copper, tin, calcium,
antimony and arsenic, and the full range of refining is not required. Copper is generally quite low
and can be controlled by simple sulfur drossing in a kettle. All other impurities can be removed by
‘softening’, usually using a simplified Harris process by treatment with sodium hydroxide and
sodium nitrate, or by oxygen injection, depending on the amounts involved.
SUMMARY OF COMMON IMPURITIES, THEIR CONTROL

AND RECOVERY
Molten lead is a particularly good solvent for many base metals present during smelting unless they
can be readily oxidised under lead smelting conditions and report to slag. Alternatively the presence
of a matte phase during smelting can also capture many impurities as well as precious metals.
Otherwise the impurities present in lead bullion need to be progressively removed, as described
above. The following provides a brief summary reference for the common impurities encountered in
extractive lead metallurgy.
Antimony
Antimony present in smelter feed reports primarily to bullion, with smaller amounts in slag, and in
any matte or speiss formed. It is the major impurity in secondary lead where it is sourced from
antimonial lead alloys used in lead-acid batteries.
Antimony is oxidised preferentially to lead, and hence is removed by oxidation with air or oxygen
in the ‘softening’ process or by sodium nitrate used with sodium hydroxide in the Harris process. The
litharge slag from ‘softening’ can be reduced to form an antimonial lead alloy, and the caustic slag
from the Harris process can be treated to produce sodium antimonate.
Arsenic
Arsenic present in smelter feed reports to lead bullion as well as slag and matte, and can also form a
separate speiss phase containing up to 30 per cent, depending on the relative amounts present. It can
also report in significant amounts to smelter fumes.
Bullion commonly contains up to two per cent arsenic. Arsenic is preferentially oxidised in the
softening or Harris processes, but more readily than antimony. Consequently when softener slag is
reduced to form an antimonial lead alloy, arsenic can be retained in the residual slag from where it can
be extracted by leaching and precipitation as arsenic trioxide or as calcium arsenite. Alternatively it
can be extracted from caustic slags from the Harris process by leaching and precipitation with lime as
calcium arsenite, which can contain around 20 per cent As.

Bismuth
Being chemically similar to lead, bismuth reports readily to bullion during smelting and is difficult to
separate. It is usually removed by precipitation from molten lead as a high melting point intermetallic
compound with calcium and magnesium using the Kroll Betterton process. Treatment of the bismuth
dross with sodium nitrate and sodium hydroxide yields a bismuth-lead alloy from which lead can be
removed by selective oxidation and further caustic treatment to give a refined bismuth.
Bismuth is retained in anode slimes from the electrolytic lead refining process and can be
recovered using similar caustic treatment procedures after recovery of silver.
Cadmium
Cadmium is normally volatilised during sintering and smelting and reports to fumes from those
processes. Otherwise some may report to smelter slag, similar to zinc.
Calcium
During smelting, calcium reports exclusively to slag, but is subsequently introduced into lead bullion
as calcium metal additions during removal of bismuth by the Kroll Betterton process. The residual
calcium is readily removed by oxidation in the final caustic refining step with the addition of sodium
hydroxide and sodium nitrate.
Copper
During smelting copper predominantly reports to lead bullion, although it will preferentially report to
any matte phase formed during smelting. Copper is commonly present at up to three per cent in
primary lead bullion. It has a low solubility in lead close to its freezing point, but most importantly
readily forms Cu2S with any sulfur present at low solubility. Consequently copper is removed by
cooling smelter bullion and by the addition of sulfur or pyrite to form a matte. This is usually the first
step in the lead refining sequence and can remove copper to levels below 0.002 per cent.
Copper may be recovered by treatment of the copper drosses or matte in a conventional copper
smelting operation and can be a significant by-product for primary lead smelting operations.
Gold
Gold follows silver during smelting and in the refining operations. Following cupellation, which
separates residual lead from precious metals, silver is recovered by electrolytic refining, leaving a
crude gold residue containing any platinum group metal present. The crude gold is melted, cast into
anodes and electrolytically refined.
Indium
Indium tends to be distributed between smelter fumes, slag and lead bullion. It is separated during the
softening process or in caustic slags from the Harris process. If present in significant amounts indium
is recovered with tellurium from the first stage Harris process slags by acid leaching to yield a solution
of tellurium and indium from which indium is precipitated as a hydroxide.

Iron
Iron predominantly reports to smelter slags and any matte formed. The content of iron in bullion is not
significant, and any present is removed as matte during copper drossing.
Magnesium
Similar to calcium, magnesium is not present in primary smelter bullion, but is added as magnesium
metal in the removal of bismuth by the Kroll Betterton process. The residual magnesium is readily
removed by oxidation in the final caustic refining step with the addition of sodium hydroxide and
sodium nitrate.
Mercury
Mercury is efficiently separated by volatilisation during sintering or direct smelting, reporting to the
SO2 rich gas stream. It will contaminate sulfuric acid produced from the gas stream, and usually needs
to be removed during wet scrubbing prior to gas drying and acid production.
Nickel
During smelting any nickel present in concentrates will be distributed to both slag and bullion, but
will report to a greater extent to any matte or speiss formed on cooling of the bullion. Nickel present in
bullion is readily removed with copper during sulfur drossing.
Platinum group metals (PGMs)

PGMs follow silver and remain as the final residues following gold refining.
Selenium
Selenium is normally separated by volatilisation during sintering or smelting operations and
predominantly reports to fumes. Any present in lead bullion can be separated in caustic slags from the
Harris process, but is relatively minor and of no real consequence.
Silver
Silver normally reports to lead bullion during smelting but will also report to any matte formed. It is
the most valuable by-product metal contained in primary lead bullion and efficient recovery is of key
importance.
Silver is normally separated from lead bullion following copper removal and softening, using zinc
addition to form a high melting point silver zinc alloy (the Parkes process). Zinc is recovered from the
alloy by melting and vacuum distillation, leaving a lead-silver mixture from which lead is removed by
oxidation or ‘cupellation’. The resulting silver doré is electrolytically refined to recover pure silver
cathode and leave an anode residue of gold plus any PGMs present.
Tellurium
Tellurium primarily reports to lead bullion during smelting. It follows arsenic, antimony and tin into
softener slags or caustic slag formed in the Harris process. It will concentrate in the first stage Harris

slag and can be extracted by a water leach followed by precipitation as tellurium metal from the leach
solution by oxygen or by SO 2.
Thallium
Thallium is normally separated by volatilisation in the sintering operation, but in direct smelting of
lead concentrates can be at relatively high levels in bullion. It can be removed by the addition of zinc
chloride to form a thallium chloride dross, leaving zinc in the bullion for subsequent removal.
Tin
Tin tends to follow arsenic and antimony and is removed from lead bullion in softener slags or caustic
slag from the Harris process. It is the most soluble of the three metals in caustic slags and can be
selectively leached with water and precipitated from the resulting solution by the addition of lime to
form calcium stannate containing around 40 per cent Sn.
Zinc
During smelting zinc reports to slag, although it can also be present in any matte formed at up to eight
per cent. It is only present in trace amounts in lead bullion. However it is added in excess in the Parkes
process for the separation of silver, but is subsequently removed by vacuum distillation and residual
traces by the final caustic refining stage. Treatment of lead bullion with sodium hydroxide and with
oxidation by oxygen or sodium nitrate will efficiently remove zinc into a caustic slag.
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smelter, in Proceedings Primary and Secondary Lead Processing Symposium, pp 71-86 (Canadian Institute
of Mining and Metallurgy (CIM): Montreal).
Paschen, P and Winterhagen, H, 1968. Die raffination von blei mit atznatron, Erzmetall, 21:14-20.
Wiltshire, P G, Miller, M J and Bauer, J C, 1989. Improved decoppering of lead bullion at Port Pirie, in
Proceedings Non-Ferrous Smelting Symposium – 100 Years of Lead Smelting and Refining at Port Pirie,
pp 65-70 (The Australasian Institute of Mining and Metallurgy: Melbourne).
Zaitsev, V Y and Margulis, E V, 1985. The metallurgy of zinc and lead, Metallurgiya, p 96.

CHAPTER 13
Electrolytic Refining of Lead
Electrolytic refining involves electrochemically dissolving lead from an impure anode and depositing
lead free of impurities onto a lead cathode. The impurities predominantly remain at the anode as a
residue or anode slime, from which valuable by-product metals can be recovered.
The electrolytic process for the refining of lead is based on the use of a fluosilicate electrolyte and
was developed by Betts in 1902. At that time the electrolytic refining method was the only technique
available for the efficient handling of lead bullion produced from high bismuth concentrates, until
development of the Kroll-Betterton process. Although it is ideally an alternative to multistage thermal
refining, it does not fully replace all steps, and copper and tin removal by thermal methods is generally
required as well as final caustic refining.
For electrolytic refining, an electrolyte is required that has a reasonable lead solubility, is stable,
has a high electrical conductivity and will yield a smooth compact deposit of lead. Various organic
acids have good lead solubility and conductivity but tend to be unstable. It was found during the
early development of the process that fluosilicic acid, fluoboric acid and sulfamic acid were most
suitable and fluosilicic acid was the least costly. Sulfamic acid systems were also used, but showed
instability at high current densities. Consequently, most electrolytic refining operations are based
on a fluosilicate electrolyte.
PROCESS PRINCIPLES
The chemical processes involved are simply the dissolution of the lead anode according to
Equation 13.1 to produce lead ions in solution, and the discharge of lead ions and the deposition of
metallic lead at the cathode according to Equation 13.2:
Anode Pb0 = Pb2+ + 2e (13.1)
Cathode Pb2+ + 2e = Pb0 (13.2)
The above reactions are the reverse of each other and the reversible electrode potential under
standard conditions (E0) is -0.13 volts. For non-standard conditions the electrode potential is given by
Equation 13.3:
RT
E = E0 × ln(a) (13.3)
nF
where:
E0 is the electrode potential under standard conditions
R is the universal gas constant (8.314 joules K-1mole-1)
T is the temperature in K
a is the ionic activity of the metal ion in solution = molar concentration × mean ion activity
coefficient (which is dependent on solution composition and the ionic strength of the solution)
F is Faraday constant = 96 500 coulombs per mole
n is the number of electrons involved per mole

CHAPTER 13 – Electrolytic Refining of Lead
E0 values are given for various metals at 25°C relative to the standard hydrogen electrode in
Table 13.1.
TABLE 13.1
Standard electrode potentials (relative to the H + electrode at 25°C).
0
Electrode reaction E volts
2+ 0
Au / Au +1.42
-
Cl2 / Cl +1.36
Hg2+ / Hg0 +0.85
Ag+ / Ag0 +0.80
Fe3+ / Fe2+ +0.77
5+ 3+
Sb / Sb +0.75
SeO32- / Se0 +0.74
Te4+ / Te0 +0.63
As5+ / As3+ +0.58
-
O2 / OH +0.40
Cu2+ / Cu0 +0.34
As3+ / As0 +0.30
Bi3+ / Bi0 +0.20
3+ 0
Sb / Sb +0.10
H+ / H0 0
Pb2+ / Pb0 -0.13
Sn2+ / Sn0 -0.14
Ni2+ / Ni0 -0.25
2+ 0
Co / Co -0.28
In3+ / In0 -0.34
Cd2+ / Cd0 -0.41
Fe2+ / Fe0 -0.44
Ga3+ / Ga0 -0.56
2+ 0
Zn / Zn -0.76
Mn2+ / Mn0 -1.10
Al3+ / Al0 -1.66
Mg+ / Mg0 -2.39
In the practical situation electrodes depart from equilibrium and for the electrode process to proceed
at a practical rate, a higher potential than the equilibrium value is needed to overcome the energy loss in
activating ions taking part in the reaction and in transporting ions to the electrode surface.
The actual observed electrode potential for an operating cell is then:
Ea = E + ηa + c (13.4)
where:
E is the reversible potential as defined above
ηa is the activation overpotential (or chemical polarisation)
c
is the concentration overpotential (or concentration polarisation)

The activation overpotential may be collectively made up of three broad processes:

1. the energy required to decompose complex ions in solution,
2. the energy barrier to be overcome to discharge the ion, and
3. the energy required to arrange the metal on the electrode surface in a particular crystalline state.
The concentration overpotential normally has little impact until high currents are reached and
depends on boundary layer effects, either fluid surface film effects or the build up of a slime layer,
eventually limiting the current to a level determined by ionic diffusion.
For electrorefining the standard potential of lead at each electrode will be the same and the
equilibrium voltage (at zero current) between the two lead electrodes is therefore zero. In practice it is
desired to transfer lead from the anode to the cathode and a current will flow, giving a potential drop
across the solution path between the two electrodes as well as overpotentials at each electrode. This
will define the starting voltage for a refining cell.
As the anode lead is dissolved the residual impurities will form a slime layer. This will impede the
flow of lead ions and hence the concentration overpotential will rise and the anode potential will
increase at a given current. Hence the cell voltage will progressively increase as the anodes are
consumed. Removal of the slime layer can be used to reduce the cell voltage. Cell voltages can vary
from 0.45 volts for new anodes up to 0.6 volts for old anodes and a typical cycle range is shown in
Table 13.2.
TABLE 13.2
Refining cell voltage range over cycle.
Voltage drop due to: Start Finish

Cathode contact 0.07 0.04
Cathode sheet resistance 0.04 0.02
Electrolyte resistance 0.35 0.35
Anode slime resistance 0 0.15
Anode sheet resistance 0.01 0.01
Anode contact resistance 0.01 0.02
Total 0.48 0.59
Theoretically, elements with electrode potentials lower than lead in the electrochemical series will
also dissolve at the anode, and from Table 13.1 this includes tin, nickel, iron, cadmium and zinc. All
the elements with higher electrode potentials, including antimony, arsenic, bismuth, silver and gold,
selenium and tellurium will remain at the anode and will not transfer to solution as long as lead is
present. However, as refining proceeds the potential drop across the slime layer will increase and
potential at the outer surface can reach a critical level for the dissolution of some impurities. Bismuth
is the most critical for refining performance and it is generally acknowledged that the critical anodic
overpotential above which bismuth starts to dissolve rapidly is 200 mV.
Only elements with electrode potentials higher than lead will co-deposit with lead at the cathode.
Hence, those elements that dissolve with lead from the anode are theoretically not able to deposit at
the cathode and will remain and build up in solution. Ideally this automatically allows only the
predominant metal to transfer from the anode to the cathode, but does require treatment of the
electrolyte to remove those impurities which tend to accumulate. However, departure from
equilibrium caused by high transfer currents and different electrode overpotentials for dissolution and
deposition can broaden the range of elements that can be co-dissolved at the anode and co-deposited

at the cathode. This consideration impacts on tin in particular with an electrode potential so close to
lead, and also antimony to some extent, although it is largely insoluble in the electrolyte. Hydrogen
will not form at the cathode because of its relatively high activation overpotential. If an element is
insoluble in the electrolyte then its activity in solution is very low and the deposition potential in
accordance with Equation 13.3 can be reduced below that of lead so that it cannot co-deposit on the
cathode. This applies in the case of iron and to some extent antimony.
The capacity of the system is governed by the rate of transfer of lead ions from the anode to the
cathode, which is expressed by Faraday’s Law:
ItM
m= (13.5)
nF
where:
m is the mass deposited in grams
I is the current passed in amps
t is the time of passage of the current in seconds
M is the molecular weight of the material deposited
n is the number of electrons involved per mole
F is the Faraday constant = 96 500 coulombs per mole
From the above expression, and for the deposition of 1 kg of lead, 258.7 amp hours (It) are
theoretically required. The efficiency with which electric current is used for the dissolution and
deposition of lead is an important parameter and can differ slightly for the anode and the cathode. If the
anode current efficiency is higher, then more lead will dissolve than will deposit on the cathode and the
lead concentration of the electrolyte will tend to rise, and vice versa. This can be controlled by the lead
content of the anode, which is generally around 98.5 per cent Pb for balance, but it can also be controlled
by adding or removing lead salts from the electrolyte. Generally the cathode current efficiency is
slightly lower than the anode current efficiency, but is usually between 93 and 98 per cent.
PRACTICAL OPERATIONS
A generalised flow sheet of lead refining using the Betts process is shown in Figure 13.1 and details of
various operations are given in Table 13.3.
Electrolytic cells
Cells used are open topped rectangular tanks constructed of concrete and lined with PVC. Cell
dimensions are dictated by the size of the electrodes, and in particular the anode dimensions. Anodes are
generally in the range of 200 to 300 kg starting weight with thicknesses of around 30 mm. Immersed
depth is commonly about 1.3 times the electrode width, hence the following is typical:
• Total anode length 1120 mm Range 950 to 1250 mm
• Immersed depth 1020 mm 850 to 1150 mm
• Width 780 mm 570 to 980 mm
• Thickness 30 mm 25 to 35 mm
• Immersed surface area 1.59 m 2
0.97 to 2.2 m2
• Weight 300 kg 190 to 400 kg

Hot Smelter Bullion
Copper Drossing
Copper Dross
Sulfur
Sulfur Drossing
Sulfur Dross to Smelter
Oxygen Softening
Softener Slag
Crude Lead
Anode Casting
Cathode Starter Sheets

Anodes
Electrolytic Cells Anode slimes
Cathode lead
Washing
Melting and
Caustic Refining
Carbon
Slag to smelter
Melting and
Starter Sheet Reduction As/Sb Fume
Ingot Casting
Preparation
Alloy of Pb, Pb/Sb Slag
Ag, Bi, Cu
Refined Lead
Converter Stage 1
As/Sb Fume
Oxygen
Coal
Sb/Cu/Bi Slag
Converter Stage 2
Sulfur
Rotary Furnace Silver Dore Oxygen

Reduction
Electrolytic
Copper Matte Refining
PB/Bi Alloy for Gold Refining

Further Refining
Refined Silver
Refined Gold
FIG 13.1 - Flow sheet for electrolytic lead refining (Betts process).

232

TABLE 13.3
Electrolytic lead refining operations by the Betts process (Gonzalez-Dominguez, Peters and Dreisenger, 1991; Siegmund, 2000).
Operation Takehara Chigirishima Harima Kamiok Shenyang Teck Cominco La Oroya Onsan
(Japan) (Japan) (Japan) (Japan) (China) (Canada) (Peru) (Korea)
Electrolyte – Pb (g/L) 236 - 270 75 90 - 100 75 74 170 - 180 75 90 - 110
– Free H2SiF6 52 - 61 110 - 115 75 38 - 58 85 - 95 60 65 - 75
Additives – Lignin sulfonate (g/t) 1000 180 300 - 450 275 500
Glue (g/t) 600 200 - 300 500 1000
Other (g/t) 210 - Aloes 550 Beta
naphthol
Electrolyte temperature (°C) 28 - 43 35 - 38 40 - 43 35 - 45 32 - 45 38 - 42 40 35 - 38
2
Current density – A/m cathode 120 - 140 147 185 135 154 - 172 178 - 192 156 145 - 170
Cell voltage 0.5 - 0.6 0.47 0.55 0.55 0.46 0.45 - 0.5 0.5 - 0.6 0.5 - 0.7
Electrolytic energy (kWh/t) 156 143 165 125 120 143 175
Anodes – Sb % 0.98 1.25 0.5 1.0 0.68 1.3 1.8 0.8
Bi % 0.50 0.25 0.13 0.3 0.40 1.5 0.25
As % 0.01 0.05 0.10 0.26 0.15 0.02
Cu % 0.02 0.03 0.10 0.10 0.073 0.004 0.01 <0.05
Sn % 0.02 0.05 0.10 0.044 0.01
Size – Length × height × 1150 × 1000 × 32 1200 × 800 × 24 970 × 740 × 35 1140 × 990 × 20 920 × 620 × 23 880 × 670 × 30 940 × 690 × 25 1250 × 800 × 25
thickness (mm)
Weight (kg) 410 250 280 250 140 200 150 270
Anode spacing (mm) 100 110 110 95 100 100 100
Life (days) 4-5 7 8 6 2.5 6 4 6
Scrap (%) 30 26.5 45 20 - 25 40 49 38

Anode slime (as % of anode wt) 2.4 - 3.6 2.9 1.3 1.4 1.1 - 1.4 4 4 1.2
Cathode starting thickness (mm) 0.6 - 1.0 0.8 1.0 0.7 0.8 - 1.0 0.5 0.6 0.8
Cathode life (days) 4 7 5 2.5 6 4 6
Number cathodes per cell 43 29 44 33 25 41
Cathodes are 20 mm greater in dimensions than the anode and are usually 0.7 to 1.0 mm thick as
starting sheets, growing to between 12 and 23 mm (120 or 220 kg respectively) depending on the
cycle time in comparison with the anode.
The number of anodes per cell is commonly around 28, but there are some larger installations with
over 40 anodes per cell. Cathodes total one more than the number of anodes and are located at the ends
of the cell and between each anode. Electrodes are handled by overhead gantry crane and are lifted
from the cell at the end of their nominated life.
Centre line anode spacing is commonly 100 mm, resulting in a gap between new anode and
cathode surfaces of 34.5 mm with a 1 mm thick cathode starting sheet. The cathode thickness will
increase, but the anode thickness will not decrease to the same extent due to the residual slime layer.
Hence the gap will decrease with time. If the gap is too small there is an increasing risk of short
circuiting between the two electrodes.
Anode head-bars rest on a busbar along one side of the cell and cathode head-bars rest on a busbar
on the opposite side. Cells may be placed side by side, in which case the anode busbar for one cell
serves as the cathode busbar for the adjacent cell. This means that cells are electrically connected in
series with connections to the DC power supply only at the end of each cell bank.
Cathode current densities used generally range between 140 and 190 amps/m2. For a typical
electrode immersed surface area of 1.66 m2 from the above typical dimensions, the current flow per
cathode is up to 320 amps and for a cell with 28 anodes is 8960 amps. This current will transport
around 1.18 kg/h of lead per cathode, requiring 180 hours (7.5 days) to deposit a full load of 210 kg.
Anode life is typically six to eight days and cathode life may be the same or half the anode life. In the
case where the cathode life is half the anode life it is often the practice to lift both electrodes from the
cells, but to scrub half life anodes to remove anode slimes and return them to the cell for the remaining
half life. This practice will reduce the anode potential and the average cell voltage and there must be a
balance between the energy cost savings and the extra costs of handling and possibly providing extra
cathode starting sheets.
With a theoretical 258.7 amp hours per kilogram of lead and a current efficiency of 95 per cent the
actual current required is 272.3 amp hours per kilogram. For an average cell voltage of 0.5 over the
anode cycle life the energy use is 136.2 DC watt hours per kg (or DC kilowatt hour per tonne of lead).
With busbar and conversion losses of the order of ten per cent the AC energy consumption is close to
150 AC kWh per tonne of refined lead, which is a relatively low cost item.
Anodes
Anodes are cast from smelter bullion after copper separation and partial softening if needed, either in
flat open moulds on a casting wheel as a measured amount, or into closed ‘book moulds’. One critical
aspect of the performance of the anode is that it should dissolve at a uniform rate and this can be
influenced by the microstructure and uniformity of the anode as well as by the impurity content. In
this regard the casting method and the cooling rate are most important, and the use of book moulds
is preferable in achieving better control and uniformity of the surface structure. With an open mould
as in wheel cast anodes, the upper and lower surfaces are quite different in terms of crystal structure,
oxidation and flatness.
The other key issue with lead anodes is the nature of the anode slime deposit. It is desirable that
this adheres firmly to the anode and does not separate and fall to the bottom of the cell. If it separates
it can cause a short circuit between the electrodes. It can then also react differently with the
electrolyte, since various impurities, which would otherwise be in electrical contact with lead and

remain in the slimes, could dissolve in the electrolyte and co-deposit with lead, thus reducing the
purity of the cathode product. It is also important that the slime deposit adhering to the anode is
reasonably porous to allow access by the electrolyte and the diffusion of lead away from the anode.
A dense deposit will block the anode dissolution reaction in the extreme, but will raise the cell
voltage to a point that may cause impurities in the outer layers of the deposit to dissolve. This effect
will be aggravated by increased cell temperatures.
Key factors affecting slime adherence are the microstructure of the anode and the presence of
certain impurity elements. The microstructure determines the distribution of impurity containing
phases at the grain boundaries, which can form a residual honeycomb structure in the slime layer
after the lead has been dissolved, and is influenced by the cooling rate of the anode during casting.
Apart from microstructure, certain impurity elements significantly affect the adherence of the slime
layer, in particular bismuth and antimony, and to some extent arsenic and silver (Tanaka, 1977).
Bismuth has considerable effect but is not controllable and would not be purposely added.
Antimony is the key controllable element and is adjusted to achieve a suitable slimes deposit.
Generally, if antimony is much above 1.5 per cent, the slimes become dense and blocking, and if
below 0.5 per cent the slime layer will not adhere.
Copper will give rise to a dense slime deposit and will cause uneven dissolution of the lead and
levels generally should be below 0.1 per cent or 0.05 per cent. Given these constraints it is normally
necessary to remove copper from smelting bullion using the decopperising techniques outlined in
thermal refining – Chapter 12. Since copper is often a major impurity in crude lead bullion, prior
removal can also significantly reduce the amount of anode slimes which have to be treated.
As indicated above, tin is one impurity with an electrode potential close to lead that will dissolve
and co-deposit on the cathode. Hence it can be necessary to remove tin before casting anodes,
although smaller amounts can be removed from cathode lead in the final caustic drossing stage. As
outlined under thermal refining (see Chapter 12), tin is removed together with arsenic and antimony
in the softening process and depending on the levels of tin in smelter bullion as well as antimony,
some degree of softening will probably also be required. This step may leave less antimony than is
desired for control of the slime deposit and it can be necessary to also add antimony to the bullion
before anode casting.
Given the above requirements for control of anode composition it is therefore often necessary to
subject smelter bullion to decopperising and softening prior to electrolytic refining and the casting
of anodes.
Anodes are lifted from the cells at the end of their nominated life, which may be between six and
eight days. The slime deposit is removed by brushing using steel brushes and the residual ‘scrap’
lead is recycled back to anode casting. Residual lead consists of that part of the anode above
solution line as well as the remaining sheet below the solution line, which is needed to structurally
hold the slime deposit. The amount of unrefined lead recycled in this way is about 25 to 40 per cent of
input lead.
As indicated above, anodes may be lifted at half their nominal life, cleaned and returned to prevent
irregular dissolution and to reduce cell voltage.
As the anode is dissolved and the slime layer increases, it is noted above that the voltage increases
for a given cell current and there is a tendency for increased dissolution of unwanted impurities
and contamination of the lead cathode. This effect is shown by the fact that the impurity level,
exemplified by the bismuth content of refined lead, increases as the anode scrap ratio falls, as shown
in Figure 13.2. This clearly illustrates that there are limits to the extent of recovery of lead from each
anode and the life of the anode.

14
12
Bi content of refined lead (ppm)
10
0
25 30 35 40 45
Scrap ratio (%)
FIG 13.2 - Effect of anode scrap ratio on Bi content (Kubota et al, 1995).
Cathodes
The standard approach has been to use thin lead starter sheets for the cathode and to melt the total
cathode after removal from the cell. The alternative approach is to use stainless steel cathodes and
strip the deposited lead from the starting cathode. The latter has been applied more recently in
secondary lead refining using fluoroborate electrolytes (Olper, 1998). There must be a balance
between the requirements for producing starter sheets and equipment required for cathode stripping.
Lead sheet for production of starting sheets is usually produced using a water-cooled cast iron
drum partly immersed in a bath of molten lead and rotating such that lead solidifies in a thin layer on
the surface of the drum and is peeled off the top as a continuous sheet. Thickness of the sheet is
controlled to between 0.8 and 1 mm by the temperature of the bath and the depth of immersion, as well
as the speed of rotation and flow of coolant inside the drum. Cathode starting sheets are cut from the
continuous sheet and are attached to a copper head bar by wrapping around and riveting. The cathode
starter sheet is straightened in a press before being loaded into the cells. Weight is generally around
10 kg. The lack of rigidity of the starting sheet is a significant factor in limiting the size of the electrodes.
Lead has a tendency to form dendritic deposits and any such formations will bridge across from
cathode to anode causing an electrical short circuit. It is therefore important to ensure that the deposit
is dense and smooth and this is achieved partly by the selection of the electrolyte, but also by the
addition of smoothing agents such as animal glue or various lignin sulfonates, aloes, or other organic
agents. Beta naphthol can sometimes also be added. Use of these types of reagents is approximately
1 kg/t of lead in total.
When cathodes are lifted from the cells the head bars are removed for reuse and the lead cathodes
are washed, then melted in a standard refining kettle.
Electrolyte
The electrolyte is a solution of lead fluosilicate and free fluosilicic acid. The lead concentration is
normally in the range of 75 to 120 g/L and the free fluosilicic acid 65 to 100 g/L. The total equivalent
fluosilicic acid is close to twice the free acid amount.

Electrolyte temperature is normally in the range of 36 to 48°C, and little control by way of heating
or cooling is needed. At high operating temperatures fluosilicic acid has a significant vapour pressure
due to its decomposition, according to Equation 13.6. Both HF and SiF4 are toxic and need to be
removed by adequate ventilation of the cell house.
H2SiF6 = 2HFv + SiF4v (13.6)
The lead content of the electrolyte may rise or fall depending on the relative current efficiencies of
the anode and cathode reactions and can be controlled by precipitating lead as sulfate from a bleed
stream or by passing the electrolyte over a column of granulated lead (or adding PbO) to increase the
level. Generally the anode current efficiency is higher than the cathode efficiency by up to 0.5 per cent
and lead will tend to build up and must be reduced from time to time. Cominco have proposed a
control by simply passing a bleed stream through an electrowinning cell using graphite anodes, and
see this as preferable to lead sulfate precipitation. With electrowinning, PbO2 tends to deposit at the
anode, but can be suppressed by the addition of 75 mg/L of arsenic to the electrolyte as sodium
arsenate. However, anode life is very poor at around three months (Gonzalez-Dominguez, Kirby and
Heim, 1995).
Minor impurities can be controlled by a bleed of electrolyte and often the bleed resulting from
entrainment in anode slimes is sufficient for this purpose. As indicated above, elements that will
dissolve are mainly tin, nickel, iron, cadmium and zinc. Tin should be removed prior to anode
casting if it is significant, otherwise if present in small amounts the electrolyte can be passed
through a column of granulated lead for removal by cementation. This is suitable for controlling the
bismuth concentration in electrolyte to less than 25 mg/L, which is equivalent to around 10 ppm in
cathode lead.
Arsenic and antimony are virtually insoluble in the electrolyte and remain in the slimes. Zinc
and cadmium are present in very small amounts and will not co-deposit with lead, but can be
controlled by a small bleed of electrolyte. Iron normally does not dissolve from the anode to any
appreciable extent due to its presence in crude lead bullion as a sulfide or matte rather than metallic
iron. Nickel is generally not present in sufficient quantities in lead bullion for there to be a concern
with accumulation in the electrolyte. As a result of the above, electrolyte purification requirements
are minimal.
Typical installation performance
Based on the above details, the characteristics and performance of a typical Betts electrolytic refining
installation can be described as in Table 13.4.
CURRENT MODULATION
In order to maintain the overpotential at the slime layer surface, and consequently the total potential
drop across the slime layer below a critical value, it is possible to commence an anode cycle at high
current density and progressively reduce through the life cycle as the slime layer builds. This will
enable cell productivity to be raised, but does add major complications in current control to individual
cells, since cells will generally be operating on a range of anode life cycles as not all anodes are lifted
at the one time. Consequently, current modulation is not normally practised.

TABLE 13.4
Betts process characteristics and performance.
Individual weight 270 kg

Number per cell 28
Anodes Total starting anode load 7560 kg
Immersed area 1.59 m2
Life Six days or 144 hours
Starter weight 10 kg
Number per cell 29
Cathodes Immersed area 1.66 m2
2
Current density 190 amps/m
Current efficiency 95%
Current supply 8831 amps
Cell voltage – average 0.5 volts
Lead transfer rate 32.43 kg/h
Total cell Lead transfer per anode cycle 4670 kg
Slime produced 150 kg
Residual anode 2740 kg
Scrap ratio 36% of anode weight
Refined lead production 100 000 t/a (285 t/d)
Number of cells required 366 operating (370)
Total series cell voltage drop 183 V
Total installation Contacts and busbar voltage drop 20 V
DC supply voltage 203 volts
DC power input 1793 kW
DC energy per tonne of lead 151 kWh/tonne
PERIODIC CURRENT REVERSAL
Short circuiting between anode and cathode by dendritic growth of cathode lead can be a significant
problem and requires constant cell voltage monitoring to detect short circuits from this source as well
as from the deformation of electrodes. The practice of periodic current reversal (PCR) has been used
to assist in smoothing the cathode deposit and minimising dendritic growth. Consequently, the
number of short circuits can be significantly reduced. The effect of the reverse current is to dissolve
the deposited lead and this is concentrated at high points or dendrites, thus smoothing the deposit.
The ratio of forward to reverse current is around 100:1, with a cycle time of less than one minute. It
is also found that the free acid level in the slimes layer is greater under this practice, reducing the
voltage drop through the slime layer and giving a lower cell voltage. This effect on energy
consumption is greater than the impact of current reversal, so that the overall energy consumption is
slightly reduced at normal current densities. Electrical switching facilities have been a complication
in the past and this practice has rarely been applied, but the application of thyristoformers can allow
the technique to be applied more easily.

BIPOLAR ELECTRODE CELLS
In a bipolar system only the end electrodes in each cell are connected to the electrical supply. Each
electrode plate in the cell between the end electrodes will become an anode on one side and a cathode
on the other. Current can bypass around the edges of the electrodes to flow directly through the
electrolyte to the end electrodes and represents an energy efficiency loss. This can be minimised by
fitting the electrodes close to the sides and baffles in the bottom of the cell. The concept is to fill the
cell with cast lead anodes, which dissolve only on the one side, and pure cathode lead is deposited on
the other side. The electrodes are lifted from the cell at the end of a cycle and the freshly deposited lead
is separated from the residual anode.
The advantages of the system may be as follows:
• Starter sheets are not required.
• Larger electrodes are possible with stronger electrodes rather than using thin starter sheets, which
are easily bent.
• There are no electrical contacts for every electrode – only the two end electrodes per cell. This
reduces cell voltage to a minor extent and can allow higher current densities.
• Since all electrodes are lifted at the end of a cycle, mechanical handling is simpler.
• It is more practical to cover the cells to contain vapour emissions.
Cominco developed a bipolar cell using 4 m2 electrodes, each weighing around 700 kg and
operating between 200 and 265 amps/m2, with spacing of 70 mm. At the higher than normal current
density, periodic current reversal (PCR) and the application of smoothing agents were necessary to
minimise dendritic growth. PCR operated on 18 cycles per minute, with current reversal for 150 ms
per cycle. Current efficiency was 90 per cent and cell voltage 2.6.
Voltage was programmed to reduce during the operating cycle to maintain the voltage drop
through the slime layer at less than 200 mV.
Cathode lead was stripped from the residual anode by flexing the electrode in a press to break the
bond between the two and allow them to fall apart.
FINAL REFINING OF CATHODE LEAD
Melted cathode lead is usually subjected to treatment with sodium hydroxide and some oxidation with
air or oxygen in the melting kettle to remove traces of antimony and tin before casting into ingots. The
product is particularly high grade and can achieve 99.999+ per cent lead content. Drosses from final
refining can be treated with softener slags and slime treatment slags in a short rotary furnace or in a
blast furnace campaign to recover antimonial lead, which can be used for alloying and for control of
the antimony content of anodes.
ANODE SLIMES TREATMENT
The composition of anode slimes will be highly variable but typical ranges are shown in Table 13.5.
Selenium and tellurium can sometimes be present in recoverable amounts. Treatment of the slimes
is primarily for the purpose of recovering the precious metals silver and gold, but also to recover lead
and antimony for recycle.

TABLE 13.5
Typical anode slime composition ranges.
Element Range
Antimony 40 - 50%
Silver 5 - 25%
Bismuth 4 - 15%
Lead 10 - 25%
Gold 100 - 300 g/t
Copper 1 - 4%
Arsenic 1 - 6%
The recovered slimes are first washed and filtered and then are melted at 850 to 900°C under
reducing conditions, usually with the addition of coal or coke fines at about two to three per cent of the
weight of material processed. A short rotary furnace can be used for this operation. Arsenic and some
antimony tend to fume or collect in a lead antimonite slag (PbO.Sb2O3). The bulk of the lead, silver,
bismuth, copper and gold form a molten metal phase, which is transferred to a converter where it is
blown with air at around 900°C. Residual arsenic and antimony will fume and are removed in the
gas stream. Lead, some antimony, copper and bismuth form a slag. Slag is tapped at an intermediate
stage and oxidation is continued at 1000°C until all antimony is removed. Final slag contains
predominantly copper and bismuth, and the metal is essentially a silver doré.
The silver doré is separated and refined following the same procedures outlined in Chapter 12 for
thermal refining.
The bismuth-rich slags from the converter operation and from doré cupellation can be reduced in a
short rotary furnace with coal and some sulfur addition to give a bismuth–lead alloy and a copper
matte. The bismuth–lead alloy can be refined by a similar sequence as used for the thermal refining of
lead, as follows:
• oxidation to remove arsenic, antimony and lead;
• silver removal by zinc addition;
• zinc removal by chlorine, which also removes any residual lead as a chloride slag; and
• final caustic treatment to yield a refined bismuth metal.
OTHER ELECTROLYTIC REFINING SYSTEMS

The San Gavino lead refinery in Sardinia operated a system based on a sulfamic acid electrolyte from
1955 until the early 1960s. The choice was influenced by the lack of suitable materials to produce a
fluosilicate electrolyte and the fact that most of the major impurities – bismuth, arsenic, antimony and
silver – were virtually insoluble, tin formed an unstable salt and the polarisation potential for copper
was very high while that for lead was quite low. This gave a performance similar to that of a
fluosilicate electrolyte although with higher power costs. Tin remains in the anode slimes due to its
low solubility, giving an advantage for the use of sulfamic acid electrolyte for bullion containing high
levels of tin (Stracchi et al, 1967).
Electrolyte composition was 80 to 85 g/L lead and 45 to 50 g/L free sulfamic acid (HNH2SO3).
One to two grams per litre of tannic acid (tannin) was also used as a smoothing agent. Current
densities used were around 90 amps/m2, and it was found that as the current density increased
to 100 amps/m2 or above there was an increasing degree of decomposition of sulfamic acid.

Decomposition resulted in the formation of ammonium sulfate and hence caused the precipitation of
lead sulfate from solution. The losses amounted to 4 kg of sulfamic acid and 2.5 kg of PbO per tonne
of refined lead at 90 amps/m2, but increased rapidly with the current density. Cell voltage was also 0.7
at these conditions with an energy consumption of 210 kWh/t of lead. This is significantly higher than
for the fluosilicate system, which has a much higher solution conductivity. As a consequence San
Gavino changed to the fluosilicate electrolyte and was able to double the productivity of the refinery
at significantly lower cost (Freni, 1965).
Fluoboric acid (HBF4) is a very similar alternative to fluosilicic acid (H2SiF6) as a basis for the
electrolytic refining of lead, but is a significantly more expensive reagent. It was used at the
Norddeutsche Affinerie refinery in Germany in the 1950s but has been replaced with the more
conventional fluosilicate system. Fluoborate has the advantage of higher solution conductivity and
can produce smooth dense cathode deposits at much higher current densities than are possible with
fluosilicates. It also has an HF vapour pressure an order of magnitude lower than fluosilicate solution
and can operate at higher temperatures. However, cost has dictated against the use of fluoborates in
the conventional Betts refining process.
A range of electrolytic technologies using fluoborates have been developed by Engitec SpA in
Italy, basically as an electrowinning technology (see Chapter 9), but this has also been adapted as a
novel approach to lead electrorefining (Olper, 1998). This technology uses a ferric/ferrous couple to
oxidise and dissolve lead from granulated bullion. The dissolved lead is then electrodeposited on a
cathode in a compartmented cell, the depleted solution flows into an anode compartment where iron is
re-oxidised to the ferric state, and the solution returns to the leaching stage. The reactions involved are
shown in Equations 13.7 to 13.9:
Leaching reaction: Pb + 2Fe(BF4)3 = Pb(BF4)2 + 2Fe(BF4)2 (13.7)
Cathode reaction: Pb(BF4)2 + 2e + 2H+ = Pb + 2HBF4 (13.8)
Anode reaction: 2Fe(BF4)2 + 2HBF4 = 2Fe(BF4)3 + 2H+ + 2e (13.9)
The cell uses a graphite anode within a fabric diaphragm compartment from which the spent
electrolyte is drawn. Filtered leach solution as feed electrolyte is fed to the open topped cathode
compartment containing a stainless steel cathode from which the deposited lead is stripped. Current
densities are of the order of 300 amps/m2, which are 60 per cent higher than commonly used in the
Betts process.
Virtually all impurities in the lead bullion are retained in a leach residue, comparable to the anode
slimes in the Betts process, but the leaching process can be continuous with the addition of fresh
granulated lead and the separation of residue by filtration of the leach solution. There is no recycle of
unconsumed lead.
Ferric iron will oxidise tin to Sn4+, which will precipitate in the leaching stage as metastannic acid
(H4SnO4) and is hence separated with the leach residue. It is therefore possible to process smelter
bullion directly without softening, although decopperising will still be beneficial to provide a separate
copper-rich stream, to reduce the quantity of mixed leach residue for further processing and to
minimise interference with subsequent silver recovery.
The disadvantage with this approach is the higher cell voltages resulting from the use of a
diaphragm and the oxidation of iron at the anode with an E0 of +0.77 volts and an equilibrium cell
voltage of 0.91. The resultant energy consumption is around 500 kWh/t of refined lead compared with
around 150 kWh/t for the Betts process.

REFERENCES
Betts, A G, 1908. Lead Refining by Electrolysis (John Wiley and Sons: Hoboken).
Freni, E R, 1965. Electrolytic lead refining in Sardinia, Journal of Metals, November, pp 1206-1214.
Gonzalez-Dominguez, J A, Kirby, R C and Heim, H, 1995. An evaluation of lead electrowinning in H2SiF6 –
PbSiF6 electrolytes, in Proceedings Zinc and Lead ’95 Symposium, Sendai, pp 713-721.
Gonzalez-Dominiguez, J A, Peters, E and Dreisinger, D B, 1991. The refining of lead by the Betts process, J of
Applied Electrochemistry, 21:189-202.
Kubota, H, Kusakabe, T, Takei, K and Takewaki, M, 1995. Current operations of Sumitomo Metal Mining’s
Betts lead electrorefining, in Proceedings Zinc and Lead ’95 Symposium, Sendai, pp 353-366.
Mantel, C L, 1960. Electrochemical Engineering, fourth edition, pp 185-192 (McGraw Hill).
Olper, M, 1998. Fluoborate technology – A new challenging way for primary and secondary lead processing, in
Proceedings Zinc and Lead Processing Symposium, pp 185-198 (The Metallurgical Society and Canadian
Institute of Mining and Metallurgy: Montreal).
Siegmund, A H J, 2000. Primary lead production – A survey of existing smelters and refineries, in Proceedings
Lead-Zinc 2000 Symposium, pp 55-116 (The Minerals, Metals and Materials Society (TMS): Warrendale).
Stracchi, P M, Peruzzi, R, Rozzoli, A, Sinigaglia, D and Vicentini, B, 1967. The refining of lead by the Betts
process, Electrochim Met, 2:95.
Tanaka, T, 1977. Adhesion of anode slime on anode surface in electrolytic refining of lead, Metallurgical
Transactions B, 8(4):651-660.

CHAPTER 14
Alloying and Casting
HANDLING MOLTEN LEAD AND ALLOYING
Remelting, alloying and holding molten lead in preparation for casting operations is usually done
in standard refining kettles as described in Chapter 12. Kettle capacity varies depending on alloy
lot sizes but can range from 10 - 300 t, with larger kettles used for straight casting of pure refined
lead.
Alloys are prepared in batches by adding weighed components to an agitated kettle. In the case of
antimony, antimonial lead of highly variable composition is often available from the reduction of
antimony rich slags, and is used for the preparation of antimonial alloys. Composition is checked by
spectrographic analysis and is adjusted and re-checked before casting.
Molten lead is transferred from the kettle to the casting installation by a submerged centrifugal
pump through steel piping. The piping is lagged and often electrically or open flame heated to prevent
freezing at low flow rates.
The kettle is drossed periodically by manual skimming and the dross can be recycled to
a short rotary furnace for reduction and conversion back to metallic lead. Depending on the
alloying components it may be necessary to recycle the lead bullion so produced back to the
refinery feed.
SPECIFICATIONS
Most primary lead is sold as ‘soft lead’ or ‘pig lead’, with a purity of at least 99.90 per cent. High
quality lead is specified as ‘four nines’ or 99.99 per cent plus. Specifications for impurity contents are
given in various Standards as shown in Table 14.1. Otherwise a wide range of alloys is produced to
customer specifications, particularly antimonial and calcium–tin alloys and have not been
standardised. Each battery manufacturer tends to have its own particular requirements to suit its own
manufacturing needs and battery specifications.
CASTING
Lead is commonly traded in the form of 25 kg ingots (pig lead), or as blocks of 500 kg, one tonne or
two tonne weight. Typical dimensions are shown in Figure 14.1. Impure bullion as feed to an
independent refinery is also commonly traded and is often cast and handled as four tonne blocks.
The 25 kg ingots are often assembled into bundles of approximately one tonne. Such a bundle is
made up of 42 ingots as seven layers, each of six ingots arranged in alternate direction per layer to give
a bundle 560 mm square by 490 mm high. Four steel straps are used to hold the bundle together, with
two straps in each direction. The bundle is arranged such that the tines of a fork-lift can get under the
bottom layer for easy handling.
Two tonne blocks vary significantly but may be 850 mm square at the top surface by 300 mm high.
Similarly the four tonne blocks used for unrefined bullion are close to 1 m square at the top surface
and about 450 mm high.

CHAPTER 14 – Alloying and Casting
TABLE 14.1
Composition of standard grades of lead.
Element United States Germany United India

ASTM pig lead specification DIN 1719 – 1951 Kingdom IS 27 – 1965
BS 29 – 1955 BS 334 –
1934
Corroding Chemical Acid Common Pure Pure Smelter Pure Chemical Pb Pb
copper de-silvered Pb Pb lead copper type A 99.99 99.94
99.99 99.985 lead
Ag max (%) 0.0015 0.020 0.002 0.002 0.001 0.001 0.001 0.0025 0.002 0.001 0.001
Ag min (%) 0.002
Cu max (%) 0.0015 0.080 0.080 0.0025 0.001 0.001 0.001 0.08 0.003 0.001 0.001
Cu min (%) 0.040 0.040 0.04
Ag + Cu 0.0025
max (%)
As max (%) 0.001 0.001 0.001 0.001 Trace 0.001 0.001
Sb max (%) 0.001 0.002 0.002 0.002 0.002 0.001 0.002
Sn max (%) 0.001 0.001 0.001 0.001 Trace 0.001 0.001
As + Sb + 0.002 0.002 0.002 0.005
Sn max (%)
Zn max (%) 0.001 0.001 0.001 0.002 0.001 0.001 0.001 0.001 0.002 0.001 0.001
Fe max (%) 0.002 0.002 0.002 0.002 0.001 0.001 0.001 0.001 0.003 0.001 0.001
Bi max (%) 0.050 0.005 0.025 0.150 0.005 0.01 0.05 0.01 0.005 0.005 0.05
Cd max (%) Trace
Co max (%) 0.001
Ni max (%) 0.001
Lead min 99.94 99.90 99.90 99.95 99.99 99.985 99.94 99.90 99.99 99.99 99.94
(%)
600 mm
600 mm
70 mm 300 mm
80 mm
560 mm
25 kg Ingot 400 mm 400 mm
One Tonne Block
FIG 14.1 - Typical ingot dimensions.
Ingot (or pig) casting

Two general types of machine are used for ingot casting – the rotary wheel caster and the straight line
chain mould machine. The casting wheel uses a rotary table with water-cooled moulds arranged around
the outer periphery of the wheel. Molten metal is poured into the moulds at a fixed station. The mould

then moves around with the wheel until close to the return position when the mould is rotated through
180 degrees and the ingots released onto a collection conveyor. The mould is then returned to its
upright position ready for refilling. These machines were the first of the mechanised casting lines
and have largely been superseded. They are not highly productive for their size and the relatively
large floor area they occupy. Steady movement of the mould is difficult to achieve, and as a result
the ingots may have ripple marks on the surface, which are less attractive to customers than a
smooth surface finish.
The straight line machines use the principle of a continuous line of moulds attached to two parallel
chains driven by a variable speed tractor or caterpillar type drive. The line is inclined upwards from
the pouring end and passes through a hood where the top surface is initially heated until full freezing
of lead in the moulds has occurred, followed by water sprays to finally cool the ingots. Lead ingots are
released as the chain turns over at the upper end to return. At the lower end lead is poured into the
moulds at a controlled rate, usually set by the speed of the pump in the relevant supply kettle with fine
adjustment of flow using a needle valve or equivalent device. The machine speed can also be set and
adjusted to give the required production rate.
There are many different pouring devices aimed at interrupting the flow of molten lead between
one mould filling and the next arriving at the filling position. These devices are in the form of wheels
and tilting (or oscillating) ladles. Their performance is largely judged by trouble-free operation and
the consistency of weight of each ingot. To minimise dross formation, gentle flow of metal into the
mould is important, without generating turbulence or air entrapment, such as would occur by pouring
from a significant height above the mould. Submerged pouring systems are gaining favour, since they
can minimise splash and dross formation.
Following the pouring position there is a skimming station where dross is skimmed from the
surface of the ingot. Complete removal of dross is important for the production of high quality ingots
with a smooth surface appearance. Many automated skimming devices have been designed and
trialled, but few have been able to perform with complete satisfaction and this commonly remains a
manual task in most plants. Improved robotics technology mimicking manual operations has the
promise of fully automating this boring and tiring (but essential) task.
Ingots released from the casting machine are sorted and aligned on a conveyor and then can be
automatically stacked into bundles. Otherwise the bundle stacking task is performed manually.
Straight line machines can achieve casting rates of around 20 tonnes per hour.
Block casting
Lead blocks are usually cast in water-cooled steel moulds on a wheel casting machine. In this case the
moulds are filled at one position to set level and the time of rotation of the wheel allows for
solidification and adequate cooling before the mould returns to the filling station. At some position
before this point, the blocks are lifted from the moulds using a hoist or crane, which either attaches to
two steel lifting eyes cast into the block or uses a vacuum lifting pad which attaches to the top surface
of the block. The steel lifting eyes are normally used for four tonne bullion blocks for subsequent
refining, whereas other means are used for pure lead and alloys, usually as one or two tonne blocks.
The smaller blocks are then handled by fork-lift truck.
The cooling time for large blocks of four tonnes is of the order of one hour.
Blocks are usually stamped with relevant product information such lot numbers, grade and
weight, and edge flashings are manually trimmed before despatch.

Sheet lead casting

Soft lead is produced as sheet by direct casting using a rotating water-cooled drum immersed in a bath
of molten lead. The lead solidifies on the surface of the drum and is peeled off from the top surface as
the drum rotates, as shown in Figure 14.2.
Finishing Rolls
Water Cooled Drum
Coil of Finished Lead Sheet Lead Sheet
Molten Lead Bath
FIG 14.2 - Schematic of lead sheet casting.
Sheet thickness is controlled by the speed of the drum, the depth of immersion, the temperature of
the molten lead bath and the intensity of water cooling applied to the inside of the drum. The sheet is
usually run through a set of finishing rolls to provide a smooth surface and a precise gauge. Standard
gauges are expressed as weight per unit area and are shown in Table 14.2. Width of the sheet is normally
900 to 1000 mm and is usually produced as a roll on a mandrel containing 1500 to 2000 kg of lead.
Alloys may also be produced in this way, for example for the production of battery grids by
punching and expanding.
TABLE 14.2
Standard lead sheet gauges.
2
Weight ( kg/m ) Thickness (mm)
5 0.441
8 0.705
10 0.882
15 1.323
20 1.764

PART E
ENVIRONMENTAL AND ECONOMIC ISSUES
This part of the text covers the critical issues associated with the environmental
impact of lead, its effect on human health and the necessary controls. Energy
consumption for key processes is reviewed as well as processing costs and
economics.
Chapter 15 Health and Environmental Issues

Chapter 16 Energy Consumption
Chapter 17 Costs and Economics of Lead Production
CHAPTER 15
Health and Environment Issues
INTRODUCTION
The effects of lead on human health and its impact on the environment have been a significant concern
to society for a long time, and have been investigated perhaps more thoroughly than for most other
metals. This has led to the development of regulations controlling the lead industry in most developed
countries and greatly influences the design and operation of lead processing plants. Of prime
importance is the limitation and control of exposure of personnel working in the industry to lead in a
harmful form, and the requirement to monitor the health of those personnel as well as emissions to the
external environment. Because of the importance of this aspect of lead processing, and the influence it
has on processes and methods of operation, it is useful to provide some understanding of the
underlying science and reasoning behind the controls and regulations imposed on the industry.
LEAD IN THE ENVIRONMENT

Although lead is a ubiquitous heavy metal it is relatively rare, constituting only 13 parts per million
(ppm) of the earth’s crust compared with 50 and 70 ppm for copper and zinc respectively. It is more
concentrated in granites at around 49 ppm due to its radiogenic origins. It has been concentrated as
sulfide minerals largely from precipitation from hot brines. Apart from the weathering of sulfides its
concentration in surface soils tends to relate to the presence of human activity, and is derived from its
use in paints, pesticides, combustion of coal and most importantly the use of lead in automobile fuel.
Lead is strongly bound within soils and is quite insoluble, limiting bioavailability and limiting its
dispersion over time.
Many of the uses of lead, which contributed to environmental contamination, such as automotive
fuel and paints, have been phased out leaving most contamination as an historic legacy. Urban dust
containing lead from these sources has been a major source of wider human exposure, but has
declined markedly in recent decades as a result of ‘safe use’ and ‘abatement’ programs which flowed
from a better understanding of the toxicity profile of lead.
Most urban soils contain lead at between 15 and 40 ppm, and a soil is regarded as contaminated
if it has over 500 ppm total lead content. Sea water contains 0.3 mg/L lead with fresh waters
substantially lower. Drinking water standards are 15 µg/L in the USA and vary between 10 and
25 µg/L. Effluent standards vary from less than 0.5 mg/L to below 0.1 mg/L.
Marine organisms tend to concentrate heavy metals, particularly shellfish, but lead has substantially
lower concentration factors than other metals at 2600:1 compared with 32 500 for zinc, 10 500 for
copper and 4500 for cadmium. There are often greater concerns for environmental contamination from
other metals associated with lead smelting such as arsenic, antimony, cadmium, selenium and thallium.
The impact of lead on the environment per se is not of prime importance and it is its entry to the
food chain and potential for human exposure that is the primary determinant of emission and
contamination standards.
THE TOXICOLOGY OF LEAD

Ingestion is the main means of intake of lead into the blood stream. Absorption through the skin or in
the lungs is minor, and inhaled lead in dust is usually expelled from the lungs in mucous and is

CHAPTER 15 – Health and Environment Issues
absorbed in the stomach. Adult humans absorb between five and 15 per cent of ingested lead and
generally retain less than five per cent of the amount absorbed (Goyer, 1996).
Due to metabolic differences young children absorb more ingested lead at around 30 to
40 per cent. Lead competes with several essential elements (iron, calcium and zinc) and dietary
deficiencies in these elements will increase the absorption of lead. This is a particularly important
issue for children and proper nutrition is essential to minimising risk.
Once absorbed, lead is deposited in mineral tissue such as bones and teeth, in some soft tissues
such as the liver, kidneys and brain, and some is retained in the blood stream. The distribution of total
body lead to the bones is about 70 per cent, increasing to 90 per cent with age.
Lead in blood is excreted and under particular physiological and pathological conditions, such as
osteoporosis, chronic disease, pregnancy and lactation, lead can be released from the bones into the
blood stream. This coupled with the sensitivity of young children places women of childbearing age at
a high level of susceptibility.
The measurement of bone lead is the most definitive indicator but is quite difficult to assess and
interpret. Consequently the blood lead level (BLL) is used as the principal indicator of exposure. It is
usually expressed in micrograms per decilitre of blood and can be measured from finger prick
samples as a first order screen or from drawn blood samples.
The impacts of high levels of lead exposure can be severe, with massive nervous system breakdown
(encephalopathy) and kidney failure. Table 15.1 lists health effects at high levels of lead in blood.
TABLE 15.1
Lead health effects for high level exposure (Boreiko, 2000; Wilson, 2000).
Lethality Children: BLL > 125 µg/dL

Adults: BLL > 300 - 400 µg/dL
Encephalopathy Children: BLL > 80 µg/dL
Adults: BLL > 100 µg/dL
Colic BLL > 60 - 100 µg/dL
Kidney toxicity Prolonged exposure > 60 µg/dL
Anaemia BLL > 50 µg/dL
Neurobehavioural performance 40 - 50 µg/dL
Male reproduction Subtle changes above 40 µg/dL
Female reproduction Miscarriage at high exposure
Subtle effects possible at 15 - 30 µg/dL
The chief impacts of lead on human health at lower levels of exposure are neurotoxicity and some
kidney effects. Nerve conduction is reversibly slowed in peripheral nerves at blood lead levels of
30 µg/dL, and significant effects can occur above 60 µg/dL. Kidney disease can be caused but requires
prolonged exposure at relatively high levels. At BLL up to 60 - 80 µg/dL there can be biological
changes in the kidney but they are largely reversible. Lead contained in the bones can affect skeletal
growth in children and can affect vitamin D metabolism.
Although there have been suggestions of causality, there is no definitive evidence of the
carcinogenic potential of lead, and lead exposure is not considered to be of concern from this
viewpoint. High levels of lead have induced tumours in animals and for this reason alone it has been
classified as a ‘possible’ human carcinogen. However, most studies have found no relationship with
cancer but those which have been inconclusive, have concurrent exposure to confounding
substances such as arsenic and to smoking.

Studies into elevated blood pressure show no significant relationship or are inconclusive;
however, suggestions have been made that a 1 mm of mercury increase in blood pressure could be
associated with a doubling of the blood lead level. For an individual this is of little consequence in
comparison with other effects.
The effect on childhood development has been a particular concern to society and there have
been many epidemiological studies relating to lead exposure effects on early childhood functions
such as psychomotor, cognitive and behavioural problems. The effect on IQ development has been
given as one to three IQ points decrease for a 10 µg/dL increase above 10 - 15 µg/dL. The general
conclusions are that while low levels of lead exposure can cause such a small IQ deficit, there are
many confounding factors with larger impacts which have not been adequately controlled. These
are nutrition and key mineral deficiencies, general health history, parental IQ, parental attention and
child rearing practices and general socio-economic status, which may in turn influence the above
factors. There is also the effect of reverse causality, where children of lower IQ may have a greater
tendency to a behaviour which increases exposure to lead (Pocock, Smith and Baghurst, 1994).
EXPOSURE PATHWAYS
Exposure of the general public to lead is usually through eating or smoking in the presence of lead
contamination, or by the inhalation of dusts and fumes in an occupational environment, particularly
lead materials processing.
Dietary intake in food and drinking water is relatively minor and has been estimated at around
20 µg per day for the average USA population. Of the other sources, hygiene is most important in
limiting intake, and smoking will greatly increase risk. Occupational exposure involves the greatest
risk and strict controls are necessary for those involved in the lead smelting industry.
Blood lead levels (BLL)

As a result of various studies and the conclusion of the toxicity effect levels as indicated above, public
health standards have been promulgated by most national health authorities, such as the Centers for
Disease Control and Prevention (CDC) in the USA. These standards stipulate values above which
BLL is regarded as elevated, or values above which medical intervention is recommended. BLL for
the general population, based on the effects on children has been progressively lowered from
55 µg/dL pre-1970 to 10 µg/dL in 1991. Unfortunately these levels are often regarded as ‘poisoning
limits’, whereas symptomatic lead poisoning is well above as indicated in Table 15.1. The CDC action
guidelines for intervention are shown in Table 15.2.
A number of surveys of children in US cities were conducted from 1976 to 1994 under the
National Health and Nutrition Examination Survey (NHANES). Results are shown in Table 15.3 and
indicate a dramatic drop in BLL as a result of various controls and abatement programs, but most
particularly due to the removal of lead from automotive fuel.
OCCUPATIONAL STANDARDS AND CONTROLS

An extensive body of legislation has been developed in most countries for the protection of workers
involved in the processing of lead. Controls are primarily targeted at limiting the lead content of air to
which workers are exposed. Cleanliness standards are also applied and the monitoring of all exposed
workers is mandatory, involving regular blood lead determinations and record evaluation to
determine trends.

TABLE 15.2
Centers for Disease Control and Prevention’s recommended actions for children.
BLL µg/dL Recommended action
<10 • Reassess or rescreen in one year. No additional action necessary unless exposure sources change.
10 - 14 • Provide family lead education.
• Provide follow up testing.
• Refer to social services, if necessary.
15 - 19 • Provide family lead education.
• Provide follow up testing.
• Refer to social services, if necessary.
• If BLLs persist (ie two venous BLLs in this range at least three months apart) or worsen, proceed according to
actions for BLLs 20 - 44.
20 - 44 • Provide coordination of care (case management).
• Provide clinical management.
• Provide environmental investigation.
• Provide lead hazard control.
45 - 69 • Within 48 hours, begin coordination of care (case management), clinical management, environmental
investigation and lead hazard control.
>70 • Hospitalise child and begin medical treatment immediately. Begin coordination of care (case management),
clinical management, environmental investigation and lead hazard control immediately.
TABLE 15.3
Decline in blood lead level for children aged one to five years from 1976 to 1994.
Mean BLL Prevalence of BLL Prevalence of BLL

(µg/dL) >10 µg/dL >20 µg/dL
NHANES II (1976 - 1980) 15 88% 24.7%
NHANES III Phase 1 (1988 - 1991) 3.6 8.9% 1.1%
NHANES III Phase 2 (1991 - 1994) 2.7 4.4% 0.4%
Blood sampling may be capillary sampling from a finger prick or by directly drawing blood from a
vein. The finger prick method may be a useful a first screen, but is prone to contamination from
particles of lead on the skin, and thorough washing prior to sampling is necessary. Analysis requires
the use of a certified laboratory and atomic absorption methods are usually employed.
Maximum blood lead levels are usually stipulated above which a worker must be removed from
further exposure. These levels are generally in the range of 50 to 70 µg/dL for men and 20 - 40 µg/dL
for women. In many places women of childbearing age are not employed where lead exposure can
occur. It is also common in the industry to have warning levels and also a requirement that a worker
cannot return to the workplace where exposure has occurred until the BLL drops by at least
10 µg/dL below the removal limit. Table 15.4 shows BLL removal limits in a wide range
of countries.
BLLs are not strongly correlated with exposure such as lead in air, and depend to a large extent on
the individual’s habits and hygiene, and particularly smoking history. Smoking in the workplace is
commonly banned and smokers are often unsuitable for employment in high exposure situations due
to their impaired ability to remove dust from the lungs. Conditions for employment often also
require workers to be clean shaven, since beards will retain dust and interfere with the proper sealing
of respirators.

TABLE 15.4
Maximum blood lead levels for occupational exposure for men (Wilson, 2000).
Maximum lead level (µg/dL) Country

80 India, Namibia, South Africa
70 Belgium, Denmark, European Economic Community (EEC), France, Germany,
Greece, Ireland, Italy, Luxembourg, Netherlands, Spain, Thailand
60 Israel, Japan, Morocco, Peru, United Kingdom
50 Australia, Canada, Finland, Norway, Sweden, USA
Exposure controls
Lead in air is the primary control required and maximum levels for routine occupational exposure
without adverse health effects are normally in the range of 50 to 150 µg/m3, expressed as an eight hour
time weighted average. In relation to lead smelting operations, exposure to associated metals can also
be significant and relevant threshold limit values (TLVs) listed by the US Occupational Safety and
Health Administration (OSHA) and the American Conferences of Governmental Industrial
Hygienists (ACGIH) are given in Table 15.5.
TABLE 15.5
Threshold limit values for occupational exposure.
3
Element Maximum lead in air (µg/m )
Lead 50
Antimony 500
Arsenic 10
Bismuth 500
Cadmium 10
Copper 200
Selenium 200
Tellurium 100
Thallium 100
Zinc 5000
Air sampling may be by static samplers or by personal samplers worn by individuals. The latter
give a more accurate picture of likely levels of exposure to plant operators, but can be subjected to
tampering. Samplers consist of a micropore filter capable of capturing particles of 0.2 µm, and a pump
to draw air through the filter. For personal samplers the air rate is of the order of 2 L/min, whereas for
static samplers the air rate is substantially greater at around 2 L/s.
Emissions of lead dusts are controlled by ventilation at all point sources of dust and fume.
Ventilation air is filtered in a bag house before discharge to atmosphere. In some cases two bag filters
in series may be used to ensure no escape of dust with failure of the primary filter. Wet scrubbers may
also be used where moist gases are to be processed or where acid mists are present. Because of the
very fine nature of lead fumes, other collection devices such as cyclones or electrostatic precipitators
are not suitably efficient and are not generally used for ventilation duties.
In situations where exposure cannot be adequately controlled by ventilation, such as in equipment
maintenance or clean-up operations, respirators must be worn. These should be tight fitting to provide

an adequate seal to the face and should be fitted with replaceable filter cartridges which are usually
changed every day. An alternative is a full head and face shield, incorporated into a safety helmet with
clear visor, supplied with a flow of fresh filtered air from a belt mounted pump and filter unit. This
provides far more comfort, particularly in a hot environment, but is relatively expensive and needs
battery charging between use.
Protective clothing in the form of boiler suits, safety helmets, safety glasses, gloves and boots are
normally supplied to all smelter workers and clothing is washed on a daily basis. Change rooms are
designed in two parts as ‘clean’ and ‘dirty’ rooms with showering facilities between the two. Entry to
the workplace is through the ‘dirty’ room and at the end of a shift workers will enter the ‘dirty’ room,
remove work clothing and either store in a locker or place in a bin for washing. They will then pass
through a shower to the ‘clean’ room fitted with lockers for normal clothing. Contaminated work
clothing, towels, etc should be laundered on site where there is provision to handle contaminated wash
water in a suitable effluent treatment facility.
Eating should not be permitted in a lead work environment and it is usual practice to provide a
canteen on the ‘clean’ side of the change facility, so that workers must remove work clothes and
wash before eating. Within the workplace facilities need to be provided for washing such as by
means of a foot-operated washing sink, together with suitable drinking water fountains, also
preferably foot operated.
Good housekeeping and workplace cleanliness is an essential part of controlling exposure. Design
for ease of cleaning is an important aspect of any new facility, with the provision of smooth floors,
avoidance of ledges and horizontal surfaces, which can collect dust, and the provision of vacuum
cleaning facilities. Cleaning should include attention to regular road sweeping and washing down to
prevent wind blown dust. Conveyor systems need to be fully enclosed and all transfer points need
to be fully ventilated. Housekeeping measures of this nature will make a major difference to both
workplace air and to emissions to the external environment.
EXTERNAL ENVIRONMENTAL CONTROLS
Apart from the internal workplace environment, any lead processing facility must control its
emissions of lead in air and water and the quality of the surrounding external environment. Air
quality is usually monitored by the use of high volume samplers located at strategic points on, or
outside the boundary of the processing plant, and such measurements are usually supervised by the
regulating authority. Standards for ambient lead in air concentrations apply and are issued under
‘Clean Air’ regulations and range from 0.5 to 2.0 µg/m3. Some particular standards are shown in
Table 15.6.
TABLE 15.6
Ambient lead in air standards.
Country Lead in air (µg/m3)
Australia 0.5 averaged over 12 months
European Union 2.0 averaged over 24 hours
United Kingdom 0.5 averaged over 12 months
0.25 after December 2008
USA 1.5 averaged over three months
WHO recommendation 0.5 averaged over 12 months

Liquid effluents are similarly required to meet local standards and in this case due to the relative
insolubility of lead it is often associated metals that require closest attention. Liquid effluents are
commonly processed by lime neutralisation to precipitate metals, aiming for pH levels of the order of
nine to ten. Typical effluent discharge standards are given in Table 15.7.
TABLE 15.7
Typical discharge water standards.
Element Typical limit (mg/L)
Lead 0.2
Zinc 1.5
Copper 0.3
Cadmium 0.03
Manganese 0.5
Arsenic 0.25
Mercury 0.01
Selenium 0.02
Thallium 0.01
Chlorine 250
Fluorine 2.0
Ambient water quality maximum concentration of lead in drinking water has typically been
50 µg/L, but in the USA has been changed to an ‘action limit’ of 15 µg/L. Standards to protect aquatic
life are given as 65 µg/L for freshwater systems and 210 µg/L for saltwater systems.
Effluent treatment
There are many effluent treatment strategies depending on particular circumstances, but if it can be
generalised, effluents may be grouped into two broad categories for separate handling approaches:
Category 1: dilute streams which do not contain deleterious impurities and can be recycled for
reuse in the smelting operation.
Category 2: effluents containing impurity elements which represent outlets from the plant circuit
and should not be returned.
Category 1 effluents may be separately collected in ponds and can be used as process water after
neutralisation of any acidity. The total proportion of effluents in this category should be maximised so
as to minimise the requirements for effluent processing and generation of associated solid wastes.
Category 2 effluents are predominantly weak acid bleed solution from smelter gas cleaning
operations. This requires neutralisation and processing to remove all regulated elements – mainly
lead, arsenic, antimony, zinc, cadmium, manganese, mercury, selenium and fluoride. It is generally
the case that alkali metals, chloride and some sulfate can be tolerated in discharged effluent within set
limits, and can provide an outlet for these elements from the smelting operation.
The usual treatment procedure involves lime neutralisation to a pH of around ten often coupled
with a sulfide precipitation polishing stage to scavenge base metals to low levels. The concentration of
lead under these conditions is around 0.1 mg/L and is not a limiting factor. Lime neutralisation may be
conducted in two stages; first to a pH of up to four to neutralise free acid and to produce a relatively
clean gypsum for sale as a by-product, followed by a second high pH stage and sodium sulfide

addition to produce a contaminated gypsum. This approach significantly reduces the quantity of final
effluent treatment solids for disposal. However, if the effluent treatment solids are recycled to the
smelting operation the calcium from lime can be used as a flux to form slag, and the minimisation of
final solids in this way is not necessary. In this situation the first stage neutralisation can use limestone
rather than lime with a significant saving in reagent costs.
A generalised flow sheet for a typical lime neutralisation effluent treatment procedure is given in
Figure 15.1. Critical operating features of the lime neutralisation plant are the settling and filtration
characteristics of the final solids, which require careful pH control and the use of flocculants.
Combined Solution for
Treatment
Limestone
First Stage
Neutralisation
pH 4
Lime
Wash Water Second Stage

Neutralisation
pH 10 NaHS
Filter
By-product Gypsum
Effluent Solids to
Discard Disposal
FIG 15.1 - Generalised effluent treatment – using lime neutralisation.
Disposal of the final effluent treatment solids follows many avenues, but commonly is recycled to
the lead smelting operation, where the contained calcium can be used as a flux. Otherwise it can be
placed in separate sealed ponds or sent to toxic landfill.
PRODUCT CONTROLS AND LIFE CYCLE MANAGEMENT

In order to limit the input of lead into the environment many regulatory controls for the use of lead
products have been introduced. Restrictions on the use of lead in paint and in automotive fuel are
widespread. Other measures include bans on the use of lead shot for sporting ammunition and
restrictions on the lead content of waste materials. Most of these regulatory restrictions are specific to
individual countries, but one international treaty under the administration of the United Nations
Environmental Program is the Basel Convention to control the cross border transfer of industrial

waste. This treaty prohibits the transfer of waste from developed countries to undeveloped countries
with poor or non-existent environmental regulations. It has promoted a high degree of recycling
within developed countries, and in particular the recycling of lead acid batteries.
Another initiative to broaden the scope of lead acid battery recycling in developing countries and
to promote a sustainable life cycle on a global basis is the ‘Green Lead Initiative’. Member
corporations or organisations within ‘Green LeadTM’ will be appraised and certified as complying
with its aims and must only trade with other accredited members. Thus mines will sell to accredited
smelters who in turn will sell to accredited battery manufacturers who sell only to accredited retailers.
The retailers must have used battery collection facilities in place and supply accredited secondary
smelting operations. Consumers will be encouraged to purchase batteries only from certified battery
retailers and to return used batteries.
These types of controls and voluntary initiatives are important in minimising the impact of lead on
the natural environment and in countering extreme calls for bans on the use of lead.
REFERENCES
Boreiko, C J, 2000. Lead and zinc: A study of technological contrasts and shared regulatory concerns, in
Proceedings Lead-Zinc 2000 Symposium, pp 39-52 (The Minerals, Metals and Materials Society (TMS):
Warrendale).
Goyer, R A, 1996. Casarett and Doull’s Toxic Effects of Metals in Toxicology – The Basic Science of Poisons,
fifth edition (ed: C D Klaassen) (McGraw Hill: New York).
Piomelli, S, Rosen, J F, Chisolm, J J and Graef, J W, 1984. Management of childhood lead poisoning, J of
Pediatrics, 105:523.
Pocock, S J, Smith, M and Baghurst, P, 1994. Environmental lead and children’s intelligence: A systematic
review of epidemiological evidence, British Medical Journal, 309:1189-1196.
Wilson, D N, 2000. Health and hygiene in the modern lead and zinc industry, in Proceedings Lead-Zinc 2000
Symposium, pp 289-306 (The Minerals, Metals and Materials Society (TMS): Warrendale).

CHAPTER 16
Energy Consumption
PURPOSE AND SCOPE
The consumption of energy for lead production has not been anywhere near as high as for other metals
such as zinc or aluminium, and hence technology change has not focused on this aspect to the same
extent. Focus for technology change has been more on the elimination of costly fuels such as coke and
replacement with coal, and the confinement of the process to reduce environmental emissions.
Nevertheless energy use for the smelting and production of metals in general is an issue of growing
significance as the environmental consequences of energy production and use receive closer attention
and scrutiny. The purpose of this chapter is to quantify, in a general way, the total energy use for the
production of lead by the major process options.
The production of lead metal can be divided into two broad areas – the basic smelting operation to
produce a crude lead bullion, and the refining operation. Since the sinter plant–blast furnace method
of smelting coupled with thermal refining has been the workhorse of the industry; they are examined
in greater detail herein as a benchmark for other processes.
Smelting processes are assumed to terminate at the production of crude bullion, excluding the
copper drossing operation which has been included in the refining operations.
In the evaluation of energy inputs to the various smelting processes the following heat values have
been used for individual fuels:
• coal 30.7 GJ/t
• coke 28.5 GJ/t
• natural gas 37 MJ/Nm3
• electric power 10.91 MJ/kWh heat energy equivalent
The electric power heat energy equivalent is the typical fuel heat energy required to generate
1 kWh of electrical energy.
ENERGY CONSUMPTION FOR THE SINTER PLANT–BLAST FURNACE

The following provides generalised quantification of the various components of the energy balance
for the sinter plant–blast furnace process and draws on generalised mass balance data shown in
Table 16.1 on the basis of one tonne of product lead.
TABLE 16.1
Mass balance information for the sinter plant–blast furnace.
Component Quantity tonnes per tonne of product lead
Concentrate feed 1.7
Fluxes added 0.7
Sinter produced 2.3
Sulfur burned 0.3
Sulfuric acid produced 0.8
Coke used in blast furnace 0.22
Slag produced 1.1

CHAPTER 16 – Energy Consumption
Concentrate handling
The handling of incoming concentrates, their storage, blending with flux materials and feeding to the
sinter plant requires the use of mobile equipment, feed bins and conveyor systems. Electric power
used is around 5 kWh/t of materials handled or 12 kWh/t of product lead. Fuels used for mobile
equipment represents 75 MJ/t of material handled or 180 MJ/t of product lead.
Sinter plant
Fuel is supplied as natural gas to the ignition stove of the sinter plant at around 300 MJ/t of product
lead. Coke breeze is often added to the charge particularly when residues are processed and may
represent around 8 kg/t of sinter charge or 18 kg/t of product lead providing a heat value input of
510 MJ/t of product lead.
Heat generated by the roasting reactions is lost from the hood of the machine and in sinter gases from
which heat is not recovered as steam. Otherwise energy input is in the form of electric power to a wide
range of fans to supply combustion air and handle sinter plant gases, as well as miscellaneous pumps,
conveyors, the drive motors for the sinter strand and product sinter crushers, and feed conditioning
equipment. Total electrical power input is related to the sulfur burned, which defines the gas flow and
size of the sinter hearth area and is 300 kWh/t of sulfur burned or 90 kWh/t of product lead.
Gas cleaning and sulfuric acid production
It is assumed that a conventional wet gas scrubbing system and double absorption acid plant are
included. Power is used for fans and blowers as well as acid circulation pumps and cooling towers.
Typical electric power consumption for plants based on six to seven per cent SO2 in acid plant feed
gas, is 120 kWh/t of acid produced. In most lead sinter plants the gas is lower in SO2 at around five per
cent, which will raise power consumption to 150 kWh/t of acid produced, which equates to 120 kWh/t
of product lead.
Fuel for preheating and start-up is more frequent with sinter gas feed and is taken as 25 Nm3 of gas
per tonne of acid produced, equivalent to 930 MJ/t of acid or 750 MJ/t of product lead.
Blast furnace
The primary energy input is from the combustion of coke at 0.22 t/t of lead, representing an input of
6270 MJ/t of product lead. Electric power is used for blast air blowers and gas handling fans as well
as fans for ventilation air. Total power use is estimated at 80 kWh/t of bullion, and natural gas use
for miscellaneous heating uses 5 Nm3/t of lead, equivalent to 185 MJ/t of product lead.
Most furnaces operate with some oxygen enrichment and a nominal figure of 20 kg/t of lead has
been assumed equivalent to a power input of 10 kWh/t of product lead.
No heat is recovered from blast furnace operations.
Summary
Table 16.2 summarises the energy inputs to the smelting stage and production of crude lead
bullion.

TABLE 16.2
Summary of energy inputs for the sinter plant–blast furnace.
Plant section Electrical energy Electrical fuel Coke or coal Fuel Total fuel
(kWh/t) equivalent (MJ/t) (MJ/t) (MJ/t) equivalent (MJ/t)
Concentrate handling 12 130 75 205
Sinter plant 90 980 510 300 1790
Gas cleaning/acid 120 1310 750 2060
Blast furnace 90 980 6270 185 7435
Ventilation 40 450 450
Total 312 3850 6780 1310 11 940
THERMAL REFINING OF LEAD BULLION

Refining operations are assumed to cover all crude bullion impurity separation procedures including
the first copper drossing operation, which is often regarded as part of primary smelting as distinct
from refining operations.
All these operations are normally carried out in standard refining kettles or kettles modified for the
specific operation. Energy input primarily involves electrical energy input for agitation, lead pumping
and ventilation duties, plus heating of the kettles by natural gas to maintain temperature or to run
through temperature cycles as required for the particular separation. The natural gas used in each case
depends on the temperature cycles used and the batch time required for each operation. Estimates for
each of the refining operations are given in Table 16.3.
TABLE 16.3
Energy inputs for thermal refining.
Plant section Electrical energy Electrical fuel Coke or coal Fuels Total fuel
Copper drossing 4.5 50 150 1500 1700
Softening 3 30 750 780
Oxygen for softening 2.5 25 25
Softener slag treatment 2 20 120 40 180
Desilverising 14 150 690 840
Zinc for desilvering 420
Vacuum dezincing 6 65 310 375
Debismuthising 14 150 1450 1600
Magnesium/calcium 900
Caustic refining 3 35 250 285
Casting and despatch 5 55 100 155
Ventilation system 24 250 250
Total 78 830 270 5090 7510
ELECTROLYTIC LEAD REFINING

As an alternative to thermal refining, lead may be refined by the Betts electrolytic process. However,
this still requires a number of steps of thermal refining, such as copper drossing, softening and final
caustic refining.

As detailed in Chapter 13 the electrical energy required for electrolysis is around 150 kWh/t of
product lead. Some additional power for solution handling and fuels is required for the anode casting
operation and for melting cathode lead in preparation for casting and starter sheet preparation.
Estimates are provided in Table 16.4.
TABLE 16.4
Energy inputs for electrolytic refining.
Copper drossing 4.5 50 150 1500 1700
Softening 3 30 750 780
Oxygen for softening 2.5 25 25
Softener slag treatment 2 20 120 40 180
Anode casting 2 10 80 90
Electrolytic refining 152 1660 1660
Cathode melting 1 10 150 160
Ventilation system 16 175 175
Total 190 2055 270 2770 5095
The energy input for electrolytic refining is significantly less than for thermal refining and the
difference is close to the energy input for bismuth separation. If in a particular situation bismuth
separation is not required, there would no energy advantage for conventional electrolytic refining.
DIRECT SMELTING PROCESSES

Direct smelting processes provide alternatives to the sinter plant–blast furnace above, up to the stage
of crude bullion production, but still require the addition of refining operations to produce high-grade
lead. Three alternatives have been evaluated – the Kivcet process, the QSL process and the Isasmelt
process – as typical of the top submerged lance slag bath reactor. Evaluations are based on
comparable feeds, predominantly lead concentrates with low residue inputs.
The extensive use of oxygen is common in these cases and associated electrical energy input for its
production has been taken as 500 kWh per tonne of oxygen. The recovery of heat is also possible with
these processes in contrast to the sinter plant and blast furnace. Recovered energy is taken as the heat
content of recovered steam, taken as 2.65 MJ/kg of steam.
Smelter gases are relatively rich in SO2, significantly reducing the gas cleaning and acid
production requirements in comparison with a sinter plant.
The Kivcet process

Operating parameters for the Kivcet process have been assumed as follows per tonne of product lead:
• oxygen requirements 365 Nm3 (0.52 tonnes)
• coal input 100 kg
• electrode carbon use 2.3 kg

• electrode power 300 kWh

• other power 125 kWh
• natural gas general use 20 Nm3
• natural gas for feed drying 50 Nm3
• steam recovered 1.4 tonnes
Estimates of energy inputs are given in Table 16.5.
TABLE 16.5
Summary of energy inputs for the Kivcet process.
Concentrate drying 2 20 1850 1870
Flash furnace 425 4740 3135 740 8615
Oxygen use 260 2845 2845
Total 784 8660 3135 2915 14 710
Steam recovered -3710
Net total 11 000
On this basis the Kivcet process has very similar net energy consumption to the sinter plant–blast
furnace. This may be surprising for an intensive process, but results from the high use of electric
power for both the electric furnace and for oxygen production and the low efficiency of conversion of
heat energy to electrical energy in comparison with its direct use.
The Queneau-Schuhmann-Lurgi (QSL) process

Operating parameters for the QSL process have been assumed as follows per tonne of product lead:
• oxygen requirements 450 Nm3 (0.64 tonnes)
• coal input 175 kg
• electric power 280 kWh
• natural gas general use 20 Nm3
• steam recovered 1.0 tonnes
The Isasmelt process

It is assumed that the Isasmelt process operates as two stages with two reactors as discussed in
Chapter 7. The first is an oxidation stage and the second reduces first stage slag. Process oxygen
requirements are provided as enriched air at 35 per cent rather than pure oxygen in the above
alternatives. This will reduce the energy required for oxygen production but will increase the energy
required for air supply and gas handling.

TABLE 16.6
Summary of energy inputs for the Queneau-Schuhmann-Lurgi (QSL) process.
QSL furnace 280 3055 5370 740 9165
Oxygen use 320 3490 3490
Total 702 7655 5370 1065 14 090
Net total 11 440
Operating parameters for the Isasmelt process have been assumed as follows per tonne of product lead:
• oxygen requirements 285 Nm3 (0.41 tonnes) to Stage 1
• coke fines to Stage 1 6 kg
• coal input to Stage 2 150 kg
• natural gas to Stage 1 3.5 Nm3
• natural gas to Stage 2 25 Nm3
• electric power 320 kWh (200 to Stage 1, 120 to Stage 2)
• steam recovered 1.0 tonne
TABLE 16.7
Summary of energy inputs for the Isasmelt process.
Stage 1 furnace 200 2200 170 140 2510
Oxygen use 205 2240 2240
Stage 2 furnace 120 1310 4605 925 6840
Total 657 7210 4775 1590 13 575
Net total 10 725
ELECTROCHEMICAL LEAD EXTRACTION PROCESSES

A number of processes have been reviewed in Chapter 9, but none of these have yet been
commercialised and no actual data is available on energy consumption. These processes produce
relatively high purity lead and do not require a full refining procedure other than a final caustic
treatment of melted cathodes to remove final traces of some impurities such as arsenic and antimony.

The following provides theoretical estimates for direct comparison with the other smelting
processes plus refining reviewed above. The basis used for this estimate is a full hydrometallurgical
system using ferric iron to effect the oxidation of PbS to produce soluble lead and elemental sulfur,
followed by solution purification with lead powder and electrolysis of the purified solution in a
diaphragm electrolytic cell to deposit lead on the cathode and reoxidise iron to ferric iron at the anode
for recycle to the leaching stage. Possible systems using this approach are fluoborates and
fluosilicates as well as chlorides, and are possibly the most likely to be developed in the future. There
are differences in the conductivity of the different systems with significant effect on cell voltages and
hence electrolytic energy use. Assumed cell voltages for electrowinning lead from the different
systems and the corresponding energy use for 95 per cent current efficiency in all cases have been
taken as follows:
• chloride system 3.5 volts and 950 kWh/t of cathode lead
• fluosilicate system 2.7 volts and 735 kWh/t of cathode lead
• fluoborate system 2.2 volts and 600 kWh/t of cathode lead
There are thus distinct advantages in the use of fluoborates and this has been used as the basis for
energy input estimates. These systems will recover relatively pure cathode lead and valuable
by-products such as silver and copper must be recovered from purification cements. An allowance is
made for the pyrometallurgical processing of these materials to achieve separate by-product
recoveries and is taken as the energy required for normal thermal refining for the lead used but
excluding debismuthising (4590 MJ/t for five per cent of cathode lead or 230 MJ/t of product lead plus
the full quantity of zinc for desilvering at 420 MJ/t of product lead).
Assumed operating parameters per tonne of product lead are as follows:
• electrical energy for leaching and solution handling 180 kWh/t
• electrical energy for electrowinning 600 kWh/t
• lead powder for purification as five per cent 30 kWh/t
TABLE 16.8
Summary of energy inputs for electrowinning.
Plant section Electrical energy Electrical fuel Coke or coal Fuel Total fuel
Leaching/solution handling 180 1960 1960
Electrowinning 600 6550 6550
Purification Pb powder 30 325 325
By-product recovery 3 31 14 180 225
Zinc for desilvering 420
Cathode melting 1 10 150 160
Total 853 9301 14 655 10 390

For a process based on the chloride system rather than fluoborates, electrolytic power will increase
from 600 to 950 kWh/t and the total energy input will increase from 10 390 MJ/t of lead to 14 400 MJ/t.
COMPARISON OF EXTRACTION PROCESSES

Table 16.9 compares the total energy inputs required for production of refined lead from sulfide
concentrates.
TABLE 16.9
Comparison of smelting and refining processes’ energy inputs.
Smelting process Refining process Energy input Energy recovery Energy input Total net energy
smelting (MJ/t of Pb) refining input
(MJ/t of Pb) (MJ/t of Pb) (MJ/t of Pb)
Sinter – BF Thermal 11 940 7510 19 450
Sinter – BF Electrolytic 11 940 5095 17 035
Kivcet Thermal 14 710 -3710 7510 18 510
Kivcet Electrolytic 14 710 -3710 5095 16 095
QSL Thermal 14 090 -2650 7510 18 950
QSL Electrolytic 14 090 -2650 5095 16 535
Isasmelt Thermal 13 575 -2850 7510 18 235
Isasmelt Electrolytic 13 575 -2850 5095 15 820
Leach – electrowinning (Fluoborate) 10 390 10 390
Leach – electrowinning (Chloride) 14 400 14 400
Table 16.9 suggests that there is little difference in the overall net energy input for most of the
alternative smelting processes, but there is potentially a significant saving with the use of leaching
electrowinning techniques. Electrolytic refining offers the lowest energy use for full refining, but as
noted above if bismuth removal is not required there is little difference between the two approaches.
In general the energy input required for smelting sulfide concentrates to crude lead bullion is of the
order of 11 to 12 GJ per tonne of lead, and the energy required to produce refined lead is 17 to 19 GJ per
tonne.
The adoption of direct smelting methods is not dictated by energy savings but by other issues such
as the reduction in the vast volumes of gas to be handled by the sinter–blast furnace process and the
consequent reduction in plant capital cost. Elimination of the use of coke as a high cost reductant can
be a key consideration. Environmental containment and occupational health issues are also a major
factor in adoption of direct smelting methods.
ENERGY CONSUMPTION IN SUPPLY OF LEAD CONCENTRATES

In order to determine the total energy requirements for the production of lead metal it is necessary to
include the energy inputs for mining and mineral separation operations. Lead is most commonly now
mined in combination with other metals, particularly zinc and sometimes copper. In this situation the
energy consumed in mining and smelting operations can be assigned to the total product metals
recovered and is typically as follows:
• mining operations 5000 MJ/t of metal recovered
• ore crushing 900 MJ/t of metal recovered

• grinding and flotation 3500 MJ/t of metal recovered

• total mine site energy input 9400 MJ/t of metal recovered
Transport of concentrate from the mine site to the smelter is highly variable depending both on
distances and the mode of transport, such as road, rail or sea. A typical figure for transport may be of
the order of 400 MJ/t of concentrate or 700 MJ/t of contained lead. In this case the energy consumed in
supply of lead in concentrate form to the smelter is 10 100 MJ/t of lead.
Adding the energy required for concentrate supply to the energy inputs for smelting gives the total
energy consumption for the production of primary lead by the standard blast furnace–thermal refining
approach as close to 30 000 MJ/t of refined lead.
ENERGY CONSUMPTION FOR SECONDARY LEAD PRODUCTION
As detailed in Chapter 11 secondary lead smelting is basically concerned with the processing of scrap
lead–acid batteries, with metallic scrap representing a minor part. There are many processes in use,
but the following analysis of energy consumption examines the most common approach involving
battery breaking and separation, followed by separate processing of metallics and battery pastes in a
short rotary furnace.
The assumed performance parameters have been taken as follows:
• battery waste lead content 60 per cent
• metallic lead portion of total lead 40 per cent
• paste lead proportion of total lead 60 per cent
• battery breaking:
• power consumption 45 kWh/t of scrap
• fuel use for paste desulfurisation 270 MJ/t of scrap
• melting metallic lead components:
• power consumption 60 kWh/t of lead
• fuel consumption 610 MJ/t of lead
• smelting battery pastes and reduction to bullion:
• power consumption 200 kWh/t of lead
• coal addition 80 kg/t of lead
• fuel consumption 2500 MJ/t of lead
In addition the product lead may require some refining, particularly to remove antimony and tin,
and it is assumed that caustic refining will be sufficient for this purpose.
Table 16.10 summarises the energy inputs required for the production of high-grade secondary
lead.
On the above basis the energy required for the recovery of secondary lead is of the order of
35 per cent of the energy required for primary lead production from sulfide concentrates. If the energy
required for mining, mineral separation and supply of lead concentrates to the primary smelters is
considered, the total energy for secondary lead recovery is less than 25 per cent of the total for primary
lead.

TABLE 16.10
Summary of energy inputs for secondary lead processing (data per tonne of product lead).
Material handling 5 55 80 135
Battery breaking 75 820 450 1270
Metallics melting 24 260 245 505
Paste smelting 120 1310 1475 1500 4285
Total 251 2740 1475 2525 6740

CHAPTER 17
Costs and Economics of Lead Production
PURPOSE AND BASIS
The objective of this chapter is to provide a general outline of the costs associated with the
production of lead by different processes and to give an indication of the important factors affecting
economic performance. The basis for comparison of different processes is the sinter plant–blast
furnace, followed by thermal refining as the principal method of production of primary lead. No
new smelters using this technology have been constructed for many decades. Consequently there is
a lack of data on actual construction costs and the figures provided herein must be regarded as broad
estimates at best.
Hopefully the following chapter provides a comparative framework and cost analysis, which can
be updated from time to time. The framework is aimed at identifying the major cost elements that
influence the conduct of the industry, as well as giving an indication of the relative importance of each
cost element.
Information is drawn from personal sources within the industry and its suppliers, and from a range
of published cost data. This data covers a long period of time and it has been necessary to update costs
to the present time frame. All data has been expressed in US dollars as at June 2005, and may be
adjusted by CPI rates from that date.
SMELTING BY THE SINTER PLANT–BLAST FURNACE
The design of a lead smelter depends to a significant extent on the nature of the feed materials
processed, particularly the grade of the concentrates. In simple terms this is due to the large possible
variation in the sulfur to lead ratio in feed materials and hence the size of the sinter plant required,
which is dictated by the sulfur burning capacity. Usually lead sinter has a relatively common lead
composition at around 45 per cent and hence the lead blast furnace sizing is not so critically dependent
on the nature of the feed. For this reason the cost estimates provided are based on a standard
concentrate feed of 60 per cent Pb and 20 per cent S content. Capacity is standardised at
100 000 tonnes per annum (t/a) lead production, representing the median capacity smelter.
By-products and impurity elements are also highly significant to the economics of lead smelting
operations, but in terms of costs, are associated more with the refining operation than the smelting
operation.
The assumptions used for construction of cost estimates and economic parameters are shown in
Table 17.1.
For a sinter plant producing 100 000 t/a of lead on the above assumed inputs, and with an operating
time of 320 days per year, derived performance data is shown in Table 17.2.
Capital costs
The construction costs for a new lead smelter have been developed for construction under USA or
equivalent conditions. Construction costs in other localities will depend on the cost of construction
labour, the use of local construction materials, and the extent of inclusion of locally manufactured

CHAPTER 17 – Costs and Economics of Lead Production
TABLE 17.1
Assumptions used for lead smelter estimates.
Parameter Value
Lead production (t/a) 100 000
Concentrate grade Pb 60%
S 20%
Fe 6%
CaO 0.5%
SiO2 3%
Ag 1000 g/t
Au 3 g/t
Cu 0.5%
Sulfur recovery to acid 85%
SO2 content of sinter gas 5%
Pb content of sinter 45%
FeO content of slag 30%
CaO content of slag 16%
SiO2 content of slag 22%
Pb content of slag 1.5%
TABLE 17.2
Derived performance data for the sinter plant–blast furnace (100 000 t/a of lead).
Parameter Derived value

Lead recovery from concentrate 98.3%
Concentrate required (t/a) 169 500
Sinter gas volume Nm3/h 52 500
Acid produced (t/a) 86 500
Acid produced (t/d) 270
Fluxes – total input (t/a) 93 000
Net sinter output (t/a) 222 000
Slag produced (t/a) 115 000
Coke burned in BF (t/a) 20 000
equipment such as drives, filters, electrical supply equipment, etc. It needs to be recognised that for
construction in lesser-developed countries, the cost per worker may be substantially lower, but due to
the lower labour productivity the overall labour cost component may not be greatly reduced.
Construction costs for remote locations can also be elevated due to the need to locate labour for the
construction period. This may be minimised by off-site prefabrication of as much equipment as
possible.
The assumed configuration of the sample plant is illustrated in Figure 17.1 and covers current
practice for a plant treating average sulfide concentrates by sintering and processing of sinter in a blast
furnace to produce crude lead bullion. Refining of the crude lead bullion is considered in a separate
section.

Lead Concentrates
Fluxes
Raw Materials
Storage
Ventilation
Feed
Blending
Acid
Sinter Plant Gas Cleaning
Production
Coke
Gas Cooling
Blast Furnace
& Cleaning
Slag Bullion Sulfuric Acid

Granulation Handling To Sale
Slag to Bullion to
Disposal Refinery
FIG 17.1 - Generalised flow sheet and plant subdivision.
The broad subdivision of costs as illustrated in Figure 17.1 may be defined as follows:
Raw materials handling Concentrate and flux materials receival, storage and controlled blending
and feed blending facilities to provide sinter feed.
Sinter plant Conventional up-draught sinter plant including feed mixing with return
sinter, feed conditioning and moisture control, sinter strand, product
sinter crushing and screening, sinter storage.
Gas cleaning Dust removal by drop-out chambers and electrostatic precipitators, cooling
and wet scrubbing, and wet gas mist removal by electrostatic precipitators.
Acid plant Conventional double absorption acid plant based on a five per cent SO2
feed gas.
Blast furnace Covers furnace charging system with sinter and coke, blast air supply,
shaft furnace, furnace cooling facilities, tapping facilities and forehearth.
Also includes blast furnace gas cooling and dust removal system
(bag-house).
Ventilation Total system for collection of dusts from all areas of the smelter and
associated dust removal equipment.
Slag disposal Includes slag granulation, separation and disposal facilities.
Bullion handling Handling equipment such as cranes, transfer cars, ladles, etc for transfer
of crude bullion from the smelter to the refinery.
Effluent treatment Covers a lime neutralisation plant for processing weak acid effluent from
gas cleaning and general effluents that cannot be recycled as process water.

Utilities and services Includes allowances to cover the connection of power and water,
drainage works, maintenance facilities, laboratories and offices. This is
estimated at 12 per cent of direct plant costs for the above items.
Site works Site earthworks, roads, access, fencing and drainage. This is estimated at
six per cent of direct plant costs.
Costs given for each section are fully constructed costs but exclude project engineering and
supervision, which is estimated separately as 15 per cent of the project cost. An allowance for licence
fees for propriety equipment and processes has been included at two per cent of the project cost.
Capital costs for the sinter plant–blast furnace smelter are given in Table 17.3 for a smelter with an
output of 100 000 t/a of lead, and corresponding with the parameters outlined in Tables 17.1 and 17.2.
TABLE 17.3
Lead smelter capital costs – sinter plant–blast furnace (cost basis – June 2005).
Plant section US$ million US$/t of lead pa

Raw material handling 14 140
Sinter plant 38 380
Gas cleaning 21 210
Acid plant 11 110
Blast furnace 55 550
Ventilation 22 220
Slag disposal 8 80
Bullion handling 8 80
Effluent treatment 5 50
Sub total 180 1800
Utilities and services at 12% 22 220
Site works at 6% 11 110
Sub total – direct plant cost 213 2130
Land and access 12 120
Licence fees 4 40
Engineering at 15% of direct costs 32 320
Sub total – indirect costs 48 480
Total plant capital cost 261 2610
Clearly circumstances and location will significantly change these figures, but Table 17.3 should
provide a guide to the major items to be considered and the general order of cost for new facilities
under USA conditions.
Direct operating costs

Direct operating costs may be broadly subdivided into labour (for operating and maintenance),
maintenance materials, electric power, reduction carbon (coke), other fuels, and operating materials
and supplies. Typical costs for a standard sinter plant–blast furnace smelter as at June 2005 are given
in Table 17.4 for a plant of 100 000 t/a of lead annual capacity. The subdivision of plant sections
corresponds with capital cost items given in Table 17.3.

TABLE 17.4
Direct operating costs for a 100 000 t/a lead smelter. Sinter plant–blast furnace (costs in US$ as at June 2000).
Plant section Number Man hours Labour cost Power Electric Maint Materials Coke Other fuels Total Total
employed per t $000’s kWh/t power materials and $000’s $000’s $000’s $ t Pb
$000’s $000’s supplies
$000’s
Raw material 16 27.2 880 12 72 336 1517 30 2836 28.4
handling
Sinter plant 45 76.5 2475 90 540 921 338 286 120 4680 46.8
Gas cleaning 10 17 550 45 270 523 75 1418 14.2
Acid plant 14 23.8 770 75 450 261 105 300 1886 18.9
Blast furnace 50 85 2750 90 540 1529 750 3520 74 9163 91.6
Ventilation 12 20.4 660 40 240 548 270 1718 17.2
Slag disposal 8 13.6 440 5 30 209 60 739 7.4

Bullion handling 8 13.6 440 2 12 200 60 712 7.1
Effluent treatment 10 17 550 3 18 114 225 907 9.1
Administration 35 58.8 1903 6.5 39 0 1730 3672 36.7
Totals 208 353 11 418 2211 4640 5131 3806 524 27 730 277.3

Total per tonne of 114.2 22.1 46.4 51.3 38.1 5.2 277.3
lead
Notes:
1. Power is costed at 6 US cents per kWh.
2. Coke is costed at US$160 per tonne with a thermal value of 28.5 GJ/t.
3. Natural gas fuel is costed at US$4 per GJ.
273
Labour costs are estimated from the number of employees required in each section covering both
operating and maintenance, and an average annual employment cost of US$55 000 per employee.
Employment cost should be the total including direct wages and all associated expenses such as taxes,
pension scheme costs, insurances and benefits.
Maintenance materials are simply estimated as 2.5 per cent of the direct construction capital cost
for each section. This cost will be lower for a new plant but should rise to the 2.5 per cent level for a
well-established plant.
Power is estimated from typical consumption figures for each area and a power cost of six cents
per kilowatt hour in this example. Similarly coke and other fuels are estimated on the basis of typical
energy consumption data provided in Chapter 16.
Materials and supplies are again typical in dollar terms and represent a range of reagents and
consumables as well as external services provided to each section. Oxygen is included in the cost of
materials and supplies for the blast furnace at around $1.50/t of lead bullion for marginal blast air
enrichment by two per cent.
The cost of administration reflects higher salaried support and management staff, as well as
services such as insurance and site taxes. These costs will vary widely depending on the location of
the plant and whether it is a stand-alone operation or part of an industrial complex.
As for the capital cost data, these figures are designed to provide a guide to the major operating cost
items to be considered in any smelter evaluation. Total smelting costs are close to US$277/t of lead
produced from the smelting operation. Of this cost 41 per cent represents labour costs, 24 per cent is for
energy and 35 per cent is for materials (including maintenance materials at 16 per cent).
SMELTING BY THE KIVCET PROCESS
The Kivcet process as a means of primary lead smelting replaces the sinter plant and blast furnace
with a single unit, with significantly reduced requirements for labour and for environmental
containment. Oxygen is used in place of air with greatly reduced gas volumes, significantly reducing
the cost of gas handling equipment, but at the expense of added energy for oxygen production. Lead
levels in slag are higher in this case at 3.5 per cent rather than 1.5 per cent assumed for the blast
furnace. This will lower overall lead recovery unless slag fuming facilities are included. Cost
estimates are provided on the same general basis of concentrate feed composition as used for the sinter
plant–blast furnace estimates above and using energy data given in Chapter 16.
Capital costs
Table 17.5 gives the capital cost estimate for the production of 100 000 t/a of lead in bullion by the
Kivcet process.
Total capital costs for the Kivcet plant at US$2015 per annual tonne of lead in bullion is lower by
23 per cent than the comparable capital for a sinter plant and blast furnace at US$2610 per annual tonne.

Direct operating costs for a Kivcet smelter as at June 2005 are given in Table 17.6 for a plant of
100 000 t/a of lead annual capacity. The subdivision of plant sections corresponds with capital cost
items given in Table 17.5.

TABLE 17.5
Lead smelter capital costs – Kivcet process (cost basis – June 2005).

Kivcet plant 77 773
Gas cleaning 8 83
Acid plant 11 108
Ventilation 8 77
Slag disposal 8 83
Sub total 138 1385
Licence fees 3 30
operating and maintenance, and an average annual employment cost of US$55000 per employee.
for each Section. This cost will be lower for a new plant but should rise to the 2.5 per cent level for a
well established plant. Coal is used in the Kivcet furnace at a cost of US$80/t in place of coke used for
the blast furnace at US$160/t.
per kilowatt hour in this example. Similarly coal and other fuels are estimated on the basis of typical
energy consumption data provided in Chapter 16. Gas fuels are higher in this case due to its use for
Kivcet furnace feed drying. In this case waste heat steam can be used to generate power and give a
credit of 337 kWh per tonne of lead.
Materials and supplies are estimates of a range of reagents and consumables as well as external
services provided to each section.
As for the capital cost data, these figures are designed to provide a guide to the major operating
cost items to be considered in any smelter evaluation. Total smelting costs are close to US$195/t of
lead produced from the smelting operation. Of this cost 38 per cent represents labour costs, 24 per
cent is for energy and 38 per cent is for materials (including maintenance materials at 18 per cent).
Without waste heat energy recovery total costs would rise to $211/t of lead with energy representing
32 per cent.

276

TABLE 17.6
Direct operating costs for a 100 000 t/a Kivcet lead smelter (costs in US$ as at June 2000).
Plant section Number Man hours Labour cost Power Electric Maint Materials Coal Other fuels Total Total
$000’s
Raw material 16 27.2 880 12 72 341 1509 30 2831 28.3
handling
Kivcet plant 36 61.2 1980 425 2550 1932 540 800 1036 8837 88.4
Oxygen supply 2 3.4 110 260 1560 1670 16.7
Gas cleaning 10 17 550 11 90 207 75 922 9.2
Acid plant 14 23.8 770 55 330 269 105 100 1574 15.7
Ventilation 5 8.5 275 15 90 193 113 671 6.7
Slag disposal 8 13.6 440 5 30 209 60 739 7.4

Administration 22 37.1 1199 4.2 26 0 1090 2315 23.1
Waste heat credit 5 8.5 275 -337 -2022 70 38 -1640 -16.4
Totals 136 231 7469 2750 3510 3814 800 1166 19 508 195.1
lead
Notes:
2. Coal is costed at US$80 per tonne with a thermal value of 30.7 GJ/t.
SMELTING BY THE ISASMELT PROCESS

The Isasmelt process as a means of primary lead smelting replaces the sinter plant and blast furnace
with a two top submerged lance reactors. Oxygen enriched air is used, reducing gas volumes and the
cost of gas handling equipment, but at the expense of added energy for oxygen production. Lead
levels in slag are taken as relatively high in this case at five per cent rather than 1.5 per cent assumed
for the blast furnace. Lower levels can be achieved but at high residence times in the reduction stage
and higher equipment costs. This will lower overall lead recovery unless slag fuming facilities are
included. Cost estimates are provided on the same general basis of concentrate feed composition as
used for the sinter plant–blast furnace estimates above and using energy data given in Chapter 16.
Capital costs
Table 17.7 gives the capital cost estimate for the production of 100 000 t/a of lead in bullion by the
Isasmelt process.
TABLE 17.7
Lead smelter capital costs – Isasmelt process (cost basis – June 2005).

Isasmelt plant 62 618
Gas cleaning 8 83
Acid plant 11 108
Ventilation 12 119
Slag disposal 8 83
Sub total 127 1270
Licence fees 3 30
Total capital costs for the Isasmelt plant at US$1870 per annual tonne of lead in bullion is lower by
28 per cent than the comparable capital for a sinter plant and blast furnace at US$2610 per annual tonne.

Direct operating costs for an Isasmelt lead smelter as at June 2005 are given in Table 17.8 for a plant
of 100 000 t/a of lead annual capacity. The subdivision of plant sections corresponds with capital cost
items given in Table 17.7.

278

TABLE 17.8
Direct operating costs for a 100 000 t/a Isasmelt lead smelter (costs in US$ as at June 2000).
Plant section Number Man hours Labour cost Power Electric Maint Materials Coal Other fuels Total Total
$000’s
Raw material 16 27.2 880 12 72 341 1509 30 2828 28.3
handling
Isasmelt plant 50 85 2750 320 1920 1897 750 1240 426 8983 89.8
Oxygen supply 2 3.4 110 205 1230 1340 13.4
Gas cleaning 10 17 550 35 210 207 75 1042 10.4
Acid plant 14 23.8 770 55 330 284 105 180 1669 16.7
Ventilation 5 8.5 275 30 180 299 113 866 8.7
Slag disposal 8 13.6 440 5 34 209 60 743 7.4

Administration 25 41.8 1353 4.8 29 0 1230 2612 26.1
Waste heat credit 5 8.5 275 -260 -1560 70 38 -1178 -11.8
Totals 153 259 8393 2485 3600 4157 1240 636 20 510 205.1
lead
Notes:
2. Coal is costed at US$80 per tonne with a thermal value of 30.7 GJ/t.

operating and maintenance, and an average annual employment cost of US$55 000 per employee.
for each section. This cost will be lower for a new plant but should rise to the 2.5 per cent level for a
well established plant. Coal is used in the Isasmelt furnace at a cost of US$80/t in place of coke used
for the blast furnace at US$160/t.
per kilowatt in this example. Similarly coal and other fuels are estimated on the basis of typical energy
consumption data provided in Chapter 16. In this case waste heat steam can be used to generate power
and give a credit of 195 kWh per tonne of lead.
Materials and supplies are estimates of a range of reagents and consumables as well as external
services provided to each section.
As for the capital cost data, these figures are designed to provide a guide to the major operating
cost items to be considered in any smelter evaluation. Total smelting costs are estimated at US$205/t
of lead produced from the smelting operation, essentially the same as for the Kivcet process. Of this
cost 41 per cent represents labour costs, 21 per cent is for energy and 38 per cent is for materials
(including maintenance materials at 18 per cent).
COMPARISON OF SMELTING TECHNOLOGIES

Table 17.9 gives a comparison of estimated capital and operating cost for the standard sinter plant–
blast furnace technology with the Kivcet and Isasmelt processes as two examples of direct smelting
technologies.
TABLE 17.9
Comparison of smelting process costs (costs in US$ per tonne of lead).
Process Sinter plant–blast furnace Kivcet Isasmelt

Capital ($/t/a) 2610 2015 1870
Labour 114.2 74.7 83.9
Energy 65.4 47.2 43.6
Materials 97.7 73.2 77.6
Total 277.3 195.1 205.1
Lead recovery to bullion 98.3% 96.2% 94.6%
The two direct smelting technologies show similar overall direct operating costs, although the
Isasmelt process may have lower capital cost. However, lead losses in slag are higher and recovery
correspondingly lower for the Isasmelt process, which will raise raw material costs. This is covered in
more detail below in the section on overall economics for refined lead production.

Competitive cost curve

The competitive position of a smelter in comparison with others is shown by use of the cumulative
cost curve in which the direct cash cost for each of the Western world’s smelters is plotted against the
cumulative tonnage capacity, arranged in ascending cost order. The general form of the curve is
shown in Figure 17.2 for Western world lead smelters, predominantly sinter plant–blast furnace
smelters, but also including later direct smelting operations.
600
500
Direct cash cost US$/ tonne Pb
400
300
200
100
0
0 500 1000 1500 2000 2500
Cumulative production 000's tonnes
FIG 17.2 - World lead smelter direct cash costs (excluding refining).
This data shows that 85 per cent of production is from plants with direct operating costs within the
range of $160 to $350/t of lead produced. The first quartile boundary is $195/t, and the third quartile
upper boundary is $320/t. The above estimate for the sinter plant–blast furnace technology is around
the average mid range of the curve, whereas the direct smelting technologies fall close to the first
quartile boundary.
The curve covers a broad range and is not particularly flat, which is usually the case for a mature
commodity. However in the case of lead, economics can be dictated to a large extent by the recovery
of by-products such as silver or low raw material costs, and relatively high costs expressed per tonne
of lead can be tolerated enabling such smelters to survive. Secondary residues or lead residues from
zinc or other smelting operations can be used to significantly reduce raw material costs.
LEAD REFINING
Although lead refining operations are often part of a primary smelting complex they can be
independent and can be separated from a costing viewpoint. There are two main refining technologies
– thermal and electrolytic, as discussed in Chapters 12 and 13 respectively. In this case costs are
provided for removal of the full range of impurities and represent the maximum cost position.
Depending on the nature of the raw materials processed by a smelter, this may not be necessary and
some impurity removal steps can either be simplified or eliminated. In this sense it is difficult to
compare the costs of individual refining operations.

Capital costs of thermal refining

As discussed in Chapter 12, thermal refining involves six principal impurity removal stages, plus
ingot casting and support services such as ventilation. The six impurity removal stages are:
• copper removal or copper drossing;
• softening or arsenic, antimony and tin removal;
• silver and precious metal removal;
• zinc removal;
• bismuth removal; and
• caustic refining.
The basis for cost estimates is the treatment of 100 000 tonnes per year of product lead.
Generalised capital costs for a thermal refinery are shown in Table 17.10. Costs for each stage
can vary widely and those given are for full refining at stage using standard refining kettles for each
stage.
TABLE 17.10
Thermal lead refinery capital costs (cost basis – June 2005).

Copper drossing 6 60
Softening – oxygen pans 4 40
Desilverising 4 40
Dezincing 3 30
Debismuthising 4 40
Caustic refining 3 30
Holding kettles 1.5 15
Ingot casting 10 100
Ventilation 15 150
Sub total 50.5 505
Sub total – direct plant cost 59.5 595
Licence fees 1 10
Total refinery capital cost 72 715
Capital costs for electrolytic refining

As detailed in Chapter 13, electrolytic refining retains some of the thermal refining steps but replaces
the removal of silver (and consequently zinc) and bismuth by the electrolytic refining stage. It
generally produces a higher grade lead which can command a premium sale price.

Table 17.11 gives a generalised estimate of the capital costs of the electrolytic lead refinery. This
is based on general performance data given in Table 13.3 and Table 13.4 and assumes the electrolytic
plant will contain 370 cells each holding 28 anodes and consuming 1850 kW AC for the refining of
100 000 t/a of lead. Apart from the cells the electrolytic plant includes anode casting and cathode
starting sheet fabrication facilities.
TABLE 17.11
Electrolytic lead refinery capital costs (cost basis – June 2005).

Copper drossing 6 60
Softening – oxygen pans 4 40
Anode casting 2 20
Cathode starter sheet fabrication 2 20
Electrolytic plant 40 400
Caustic refining 3 30
Holding kettles 1.5 15
Ingot casting 10 100
Ventilation 7 70
Sub total 75.5 755
Site works at 6% 4.5 45
Licence fees 1 10
Total refinery capital cost 105 1050
On the basis of the above estimates the capital costs of electrolytic refining are substantially
greater than for thermal refining by approximately 47 per cent.
Operating costs
Estimates for operating costs for both thermal and electrolytic refining are given in Table 17.12 on the
same basis as used for smelting operating cost estimates given above.
Comparison of refining processes

Costs of the two refining technologies are compared in Table 17.13.
The electrolytic refinery has substantially higher capital costs than the thermal refining process
which relies on a series of standard refining kettles. Operating costs are also higher by US$11/t of
product lead, although energy costs are marginally lower for electrolytic refining. It is possible that
product premiums from the electrolytic refinery could cover the additional direct cost, but would not
cover the return required for the additional capital cost.

TABLE 17.12
Direct operating costs for a 100 000 t/a lead refinery (costs in US$ as at June 2000).
Plant section Number Man hours Labour cost Power kWh/t Electric Maint Materials Other fuels Total Total
employed per t $000’s power materials and supplies $000’s $000’s $ t Pb
$000’s $000’s $000’s
Thermal refinery
Copper drossing 14 23.8 770 4.5 27 150 185 600 1732 17.3
Softening 10 17 550 7.5 45 100 139 316 1150 11.5
Desilverising 8 13.6 440 14 84 100 68 276 968 9.7
Dezincing 10 17 550 6 36 75 75 124 860 8.6
Debismuthising 14 23.8 770 14 84 100 129 580 1663 16.6
Caustic refining 8 13.6 440 3 18 75 60 100 693 6.9
Holding kettle 4 6.8 220 1 6 38 30 20 314 3.1
Casting 24 40.8 1320 4 24 250 180 20 1794 17.9

Ventilation 12 20.4 660 24 144 375 90 1269 12.7
Administration 21 35.4 1144 4 24 75 1040 2283 22.8
Totals 125 212 6864 492 1338 1996 2036 12 725 127.3

Total per tonne of lead 68.6 4.9 13.4 20.0 20.4 127.3
Electrolytic refinery
Copper drossing 14 23.8 770 4.5 27 150 185 600 1732 17.3
Softening 10 17 550 7.5 45 100 139 316 1150 11.5
Electrolytic plant 46 78.2 2530 155.4 932 900 345 150 4857 48.6
Caustic refining 8 13.6 440 3 18 75 60 100 693 6.9
Holding kettle 4 6.8 220 1 6 38 30 20 314 3.1
Casting 24 40.8 1320 4 24 250 180 20 1794 17.9
Ventilation 8 13.6 440 12 72 235 50 797 8.0
Administration 23 38.8 1254 4 24 78 1140 2496 25.0
Totals 137 233 7524 1148 1826 2129 1206 13 833 138.3
Total per tonne of lead 75.2 11.5 18.3 21.3 12.1 138.3
Note: Power is costed at 6 US cents per kWh, and natural gas fuel is costed at US$4 per GJ.
283
TABLE 17.13
Comparison of refining process costs (costs in US$ per tonne of lead).
Process Thermal refinery Electrolytic refinery

Capital ($/t/a) 715 1050
Labour 68.6 75.2
Energy 25.3 23.6
Materials 33.4 39.6
Total 127.3 138.3
Most electrolytic refineries were built before the successful application of the Kroll-Betterton
process for bismuth removal as the only reasonable approach for bismuth removal. Since that time no
new electrolytic refineries have been installed and the adverse economics are clearly indicated by
these figures.
METAL PRICING
Generally lead product prices are set by international metal exchanges, principally the London Metal
Exchange (LME). Product price is therefore usually outside the control of the producer.
The demand for metals as commodities is determined by the international trade cycle. Supply and
demand are rarely in equilibrium, and for this reason there is a need for an international terminal market
as a gathering of traders to purchase and sell metal, establishing a net supply-demand balance and
setting prices accordingly. The bulk of metal traded on world markets is contracted directly between
producer and consumer, but is priced on the basis of the international terminal market quotation.
The LME has three functions in relation to metal trading:
1. To register prices as set by supply and demand trends. This is done on a daily basis.
2. To receive and deliver physical metal which is held by traders in LME warehouses. A warrant
is issued giving title to metal held in a number of warehouses worldwide.
3. To provide facilities for hedging contracts of which both forward selling and buying contracts
are available.
The market trades seven base metals including lead, and there are four opportunities to trade each
day. Daily prices are quoted at the end of each morning trade as representative of the contracts made.
Both a cash and three month forward delivery price are quoted. The three month price may be above
the cash price (termed a ‘Contango’) or below the cash price (termed a ‘Backwardation’).
The LME market, in large part, reflects future expectations as well as current market conditions.
Pricing is generally determined by market dynamics, considering factors such as:
• consumption demand and growth projections;
• supply chain projections for both mines and smelters; and
• stock holdings in smelters, LME warehouses and with end consumers – or market liquidity.
The timing of changes in these market fundamentals can give rise to significant differences
between the present and future metal prices. The involvement of option traders and hedge funds
speculating on these balances is another important issue, and this activity can significantly influence
pricing, deviating the market away from its underlying fundamentals in the short term.

To some extent forward pricing is responsive to metal stocks, and will generally fall if stocks
move well above normal levels, and vice versa.
The alternative to price setting by a terminal market is the use of a ‘Producer Price’, set by a cartel
of producers, or by one major producer which others follow. This scheme was used up until the mid
1980s when both Producer Price and terminal market pricing schemes operated. Generally LME
pricing is regarded as more independent, reflecting the market supply and demand balance. It can be
manipulated by traders, but only over short periods of time. Metal can always be sold at negotiated
prices between producer and consumer, but since the smelter is often separate from the mine
supplying concentrate, a common metal pricing system is needed for both mine and smelter products,
and the Producer Pricing approach is not particularly practical or equitable.
Metal held in LME warehouses must conform to set quality standards, and for lead there are a
number of standards as given in Table 14.1 in Chapter 14.
BY-PRODUCTS
For the typical lead smelter the principal by-products will be silver and gold, copper dross, sulfuric
acid and antimony metal, usually in the form of antimonial lead alloy. Other possibilities are arsenic
compounds and zinc oxide if slag fuming facilities are installed.
Silver and gold

Silver is a key by-product and can return realised metal values of up to 50 per cent or more of the
primary lead value. It is, however, highly variable and depends on the raw materials used. Silver is
efficiently recovered into the primary lead bullion from most sulfide concentrates. It is separated
during refining as a zinc–silver alloy which is further processed by distillation and cupellation to give
a silver doré, which is electrolytically refined to pure silver. Gold is recovered with silver and
separated during the final silver refining stage to yield a gold doré which can be sold for final refining.
Both metals are cast into bars for sale at metal exchange prices with minimal realisation costs.
The example used as the basis for cost estimates in this Chapter assumes a lead concentrate
containing 60 per cent lead, 1000 g/t silver and 3 g/t gold. For recoveries of 96 per cent and 93 per
cent for silver and gold respectively, and for prices of US$10 per troy ounce for silver and US$600
per troy ounce for gold, the returns are US$523/t of product lead for silver and US$91/t of product
lead for gold.
Copper matte
Copper drossing as the first stage in refining can yield a copper sulfide material for sale to a copper
smelter. Often such drosses only contain ten to 15 per cent copper and receive a poor return. However,
this can be upgraded to a rich copper matte with recovery of entrained lead by using a short rotary or
reverberatory furnace. With continuous copper drossing, matte grades can be up to 50 per cent
copper, but are typically between 30 and 45 per cent.
Apart from sulfur the other main constituent of copper matte is lead, which is not favoured by
copper smelters in large amounts due to the effects on refractories. Hence prices paid for this material
can reflect standard copper concentrate terms but with penalties for the lead content. A decision on
whether to install dross upgrading or continuous copper drossing equipment will depend on the level
of copper normally encountered in smelter feed concentrates.

In the example used for the basis of cost estimates in this chapter, the copper content of
concentrates is 0.5 per cent and for a blast furnace slag of 0.15 per cent copper, recovery into matte
would be around 80 per cent, which would yield 0.017 tonnes of copper matte containing 40 per
cent copper per tonne of lead produced. Taking smelting charges and penalties at US$1000/t of
contained copper and the LME copper prices at US$7500/t, the return for copper matte is US$44/t
of lead produced.
Sulfuric acid
The sulfur to lead ratio in lead concentrates is highly dependent on the concentrate grade and hence
the quantity of sulfuric acid produced will vary accordingly. For a typical lead smelting operation as
detailed above, with a concentrate feed of 60 per cent Pb, the sulfuric acid production will be close to
0.865 tonnes per tonne of lead produced. Acid produced from the sintering operation will be ‘black’
acid, discoloured by organic carbon distilled from entrained flotation reagents and kerogen material
in the sinter feed, whereas acid produced from direct smelting processes will be ‘white’ acid due to the
higher temperatures which destroy the organic species present and oxidises the carbon to CO 2.
Black acid has limited application, such as the manufacture of fertilisers, otherwise it must be
treated to remove the colouration by oxidation of the carbon with hydrogen peroxide. In either case
the return from ‘black’ acid will be at a discount to the return from ‘white’ acid, and for example could
be taken as around US$10/t.
The net sale price for ‘white’ sulfuric acid will vary greatly depending on smelter location and
proximity to acid markets, but by way of example may be taken as US$20/t ex works. This represents
a credit of 0.865 × 20 = $17.3/t of lead produced, whereas as ‘black’ acid the return will be around
$8.65/t of lead produced.
In addition, the basic price of sulfuric acid as a traded commodity depends on the world market
price of raw sulfur or brimstone. The supply-demand balance for brimstone can vary widely and is
dependent on the general availability of smelter acid as well as other factors such as its production rate
and the stock position. Given also that freight costs for shipping sulfuric acid from the smelter can be
significant, particularly for smelters in remote locations, there are many situations where returns from
acid sales can be negative, representing a disposal cost. Regular output of acid is essential to maintain
smelter operation, as storage is limited, and often there can be no option but to accept poor or negative
returns.
Other by-products
Antimonial-lead alloys are the main additional by-product, but returns depend on local demand and
the particular alloys required, and are difficult to quantify in a general way. With the popularity of
calcium–lead alloys for sealed, maintenance free batteries, the price of antimonial alloys declined, but
has resurged due to increased demand for specialised batteries. Clearly this market is quite volatile.
In some instances other by-products such as tellurium, tin, bismuth, germanium and selenium can
provide valuable returns to the smelter, but this is unusual.
OVERALL ECONOMICS FOR REFINED LEAD PRODUCTION

Revenues are obtained from the sale of lead metal and by-products.
Generally lead is sold at a premium to the LME price. The premium is in part established by the
cost of accessing metal from alternative sources such as a LME warehouse or another supplier, and

will vary according to the location of the customer. Premiums are also received for upgraded metal
such as alloys. For the purposes of example the overall metal price premium may be taken as an
average level of US$50/t of lead sold.
Costs borne by the smelter and refinery in producing lead metal are:
• The cost of concentrates. In accordance with Chapter 3 ‘Commercial Terms for Purchase of
Standard Lead Concentrates’ concentrate feed has been costed on the basis of a 60 per cent lead
content, 1000 g/t of silver and 3 g/t of gold, and a treatment charge of US$265/t of concentrate at a
lead price of US$1100/t, giving a net cost of US$650/t of concentrate.
• The direct cash costs for the smelter operation. These have been summarised in Table 17.9 for
three different smelter technologies.
• The direct cash costs for lead bullion refining. These have been summarised in Table 17.13 for the
two different refining technologies.
• Annual capital expenditure required to sustain the smelter operation. This represents the
ongoing annual expenditure on equipment replacement and modification. It may be estimated as
50 per cent of the cost of new plant spread over 30 years. This recognises an average plant life
of 30 years and assumes that part of the installation, such as structures, would not need
replacement.
• The cost of delivery of product metal to the customer including handling, freight, insurance and
sales organisation expenses. This will vary greatly from one plant to another and will depend on
relative locations of the smelter and its customers. These costs will be low for plants located in
Europe and Japan, but will be high for plants located in Canada and Australia for example. For
assessment purposes an average delivery cost is taken as US$40/t of lead.
Lead price is the main variable and uncertainty in any assessment of smelter economics, and is
outside the control of the smelter operator. A new venture or investment in lead extraction facilities,
whether mine or smelter, must be able to withstand wide movements in the lead price and at least
remain cash positive at all points in the expected price cycle.
Projection of future pricing is perhaps the most difficult issue and the greatest uncertainty facing
any new investment.
Basis used for evaluation of economics of lead production
Assumptions used in evaluating raw material costs and revenues are as follows:
Metal prices (LME) Lead US$1100 per tonne
Copper US$7500 per tonne
Silver US$10 per troy ounce
Gold US$600 per troy ounce
Concentrate grades Lead 60 per cent
Copper 0.5 per cent
Silver 1000 g/t
Gold 3 g/t

Recoveries Lead 98.3 per cent for blast furnace

96.2 per cent for Kivcet
94.6 per cent for Isasmelt
Copper 80 per cent
Silver 96 per cent
Gold 93 per cent
Economic evaluation of lead production
Using the above assumptions Table 17.14 details the costs and returns of lead production using the
sinter plant–blast furnace process and the Kivcet process as an example of direct smelting technology,
both followed by thermal refining.
TABLE 17.14
Economics of lead production.
Item Sinter plant–blast furnace process Kivcet process

US$/tonne of lead US$/tonne of lead
Smelter capital 2610 2015
Refinery capital 715 715
Total capital 3325 2730
Revenues
Lead sales at LME price 1100 1100
Premium 50 50
Silver 523 535
Gold 91 93
Copper matte 44 45
Sulfuric acid 8.6 18.7
Total revenue 1817 1842
Costs
Raw materials 1102 1127
Smelter operating 277.3 195.1
Refinery operating 127.3 127.3
Sustaining capital 55.4 45.5
Delivery costs 40 40
Total costs 1602 1535
Cash margin 215 307
As return on investment 6.5% 11.2%
The returns on investment indicated would not normally be regarded as sufficiently attractive to
justify investment, and smelter costs need to be substantially reduced, or returns by way of
treatment charges need to be substantially increased. New direct smelting technologies offer
improved economics but returns have been insufficient to justify new greenfields smelters at
prevailing metal prices.

This particular situation results from the lack of a need for new smelting facilities over many years
and the fully depreciated state of most of the primary smelters. Through competitive pressures,
smelting charges have been pushed down to levels where direct costs are covered with reduced
margin to cover capital charges. However, coupled with the environmental benefits, direct smelting is
the only option for primary smelting plant replacement or expansion.
The impact of lead price on the margin, and return on investment for the sinter plant–blast furnace
process is given in Table 17.15. From this it can be seen that the margin increases by around $29/tonne
of lead produced for every $100/tonne increase in the lead price. This reflects the distribution of lead
price gains between the concentrate supplier and the smelter and is a function of the concentrate
purchase terms – particularly the escalation of the treatment charge with the lead price.
TABLE 17.15
Effect of lead price on smelter economics.
LME lead price (US$/t) 800 900 1000 1100 1200 1300 1400 1500
Revenues (US$/t Pb) 1517 1617 1717 1817 1917 2017 2117 2217
Concentrate cost (US$/t Pb) 888 960 1031 1102 1173 1244 1316 1387
Other costs (US$/t Pb) 500 500 500 500 500 500 500 500
Margin (US$/t Pb) 129 157 186 215 244 273 301 330
Return on investment (%) 3.9 4.7 5.6 6.5 7.3 8.2 9.0 9.9
Although the above illustrates the factors involved in lead smelter economics there are wide
variations in the costs and returns for lead smelters. It is therefore not possible to define costs in a general
way, as in the above examples, and a detailed assessment of each individual situation is necessary.
ECONOMICS OF SECONDARY LEAD PRODUCTION

As an example, indicative costs are provided for the treatment of scrap lead-acid automotive batteries
to produce refined lead using battery breaking and paste desulfurisation, followed by melting and
reduction in a short rotary furnace, as described in Chapters 10 and 11. A typical small scale unit
handling 35 000 tonnes per year of batteries is considered with a lead production of around
19 000 tonnes per year. Relevant production data is as follows:
• batteries processed 35 000 t/a
• refined lead produced 19 000 t/a
• wastes for disposal (slag, gypsum, plastics) 6500 t/a
• polypropylene recovered 2100 t/a
A plant of this size will have a battery breaker and shredder, separation plant to recover metallic
lead, pastes, polypropylene and other plastic and a single rotary furnace of 7 - 8 m3 working volume.
Capital costs will be of the order of US$15 million for battery handling, breaking and separation,
and US$10 million for the smelting furnace and ancillaries. The total cost of US$25 million represents
US$715/t of batteries per annum or US$1315/t of lead per annum.
Operating costs are detailed in Table 17.16.
If the cost of collection and transport of scrap batteries is taken as $100/t (or $194/t of lead), then
the total cost of refined lead produced is US$633/t.

TABLE 17.16
Operating cost for secondary lead production.
Item Quantity per annum Unit cost Annual cost $000’s Cost per t Pb
Battery breaking
Labour 26 $55 000 pa 1430 75.2
Power 4.8 m kWh $0.08 384 20.0
Fuels 11 000 GJ $4.5 50 2.6
Soda ash 2950 t $250 738 38.8
Lime 980 t $80 78 4.1
Other supplies 195 10.2
Maintenance materials 2% capital 300 15.8
Sub total 3175 167.1
Smelting operation
Labour 17 $55 000 pa 935 49.2
Power 2.7 m kWh $0.08 216 11.4
Fuels 66 000 GJ $4.5 297 15.6
Fluxes 1800 $50 90 4.7
Oxygen 4000 t $160 640 33.6
Other supplies 143 7.5
Maintenance materials 2.5% capital 250 13.2
Caustic refining costs 380 20
Waste disposal 6500 t $60 390 20.5
Sub total 3341 175.8
Administration
Labour 3 75 000 225 11.8
Supplies and services 350 18.4
Sub total 575 30.2
Sustaining capital cost 5% capital 1250 65.8
Grand total 8341 438.9
Credit may be obtained from the recovery of polypropylene at 110 kg/t of lead produced. With a
current value of US$1.30/kg the credit is worth $143/t of lead or 33 per cent of the direct processing
costs, and will reduce the overall direct cost of refined lead to $490/t. This is clearly a most significant
by-product.
With an LME lead price of US$1100/t the profit margin is $467/t of lead or 35 per cent of fixed
capital. Production of lead by this approach is therefore quite profitable in comparison with primary
lead production at the assumed lead price, and may be a factor in depressing the returns for primary
lead smelters in a situation where the growth in new lead consumption has been negligible over many
years. However, it should be noted that the returns from secondary smelting are far more sensitive to
lead price since there is no compensating reduction in raw material costs as the lead price falls, which
is the case for primary smelters. The sensitivity of the operating cash margin to lead price is illustrated
in Table 17.17.
The cash break-even lead price in the above example would be US$624/t, below which the
secondary smelter would operate at a cash loss.

TABLE 17.17
Price sensitivity of secondary smelters.
LME lead price (US$/tonne) 700 800 900 1000 1100

Return (US$/t Pb) 750 850 950 1050 1150
Costs (US$/t Pb)
Scrap collection 194 194 194 194 194
Smelting 440 440 440 440 440
Realisation 40 40 40 40 40
Total costs 674 674 674 674 674
Margin (US$/t Pb) 76 176 276 376 476
Return on investment (%) 5.8 13.3 21.0 28.6 36.2
The relative sensitivities of cash margin to LME lead price is shown in Figure 17.3. For primary
smelters a fall in lead price will cause a proportional fall in raw material costs and a decline in
allowable treatment charge, but the decline in treatment charge will be only a fraction of the lead price
decline and in some contracts may in fact have a floor below which it cannot fall. This has the effect of
significantly reducing metal price sensitivity.
Primary Secondary
1000
800
Cash m argin US$/t Pb
600
400
200
-200
400 600 800 1000 1200 1400 1600
Lead Price US$/t
FIG 17.3 - Sensitivity of operating cash margin to lead price for primary and secondary smelters.
In the past, the high sensitivity of secondary lead production to lead price has acted to limit any
decline in the lead price, since it reaches a point where some secondary operation is not viable and
production is reduced, decreasing supply and hence forcing an increase in price or at least a halt in any
price decline. Primary smelters will remain cash positive at the point where secondary smelters
become cash negative.
The reverse situation does not apply to secondary lead, since scrap availability is relatively
inflexible, and any significant growth in lead demand must be met from increased primary lead
production. This will result in increased concentrate demand and cause an increase in lead price.

The above may present a somewhat simplistic view, but does illustrate the interplay of primary
and secondary operations in influencing lead price movements. The other major factor is of course
mine supply.

Sponsors
The Australasian Institute of Mining and Metallurgy would like to thank the
following sponsors for their generous support of this volume.
v
APPENDIX 1
Properties of Lead and Associated Compounds
LEAD METAL PROPERTIES
Atomic number 82
Atomic weight 207.19
Stable isotopes, relative abundance
Mass number 204 206 207 208
Per cent abundance 1.48 23.6 22.6 52.3
Valence Usually 2, sometimes 4 or 1
Melting point 327.4°C

Boiling point (at 760 mm Hg) 1751°C
Vapour pressure
Temperature °C 987 1167 1417 1611 1751
Vap pressure mm Hg 1.0 10.0 100.0 400.0 760
Density Solid at 20°C 11.34

Solid at 327.4°C 11.005
Liquid at 327.4°C 10.686
Coefficient of linear thermal expansion (polycrystalline) 29.3 × 10-6 °C-1

87.9 × 10 °C
-6 -1
Coefficient of volumetric thermal expansion
-1 -1
Heat capacity of solid 23.6 + 0.00962 . T J.mole .°C (T in °K )
-1 -1
Heat capacity of liquid 32.4 - 0.00305 . T J.mole .°C
-1 -1
Heat capacity of vapour 20.79 J.mole .°C
-1
Heat of fusion 5425.38 J.mole at 327.4°C
-1
Heat of vaporisation 175068.1 J.mole at 1525°C
Thermal conductivity of solid (25°C) 0.347 J.sec-1.cm-1.°C-1

-1 -1 -1
Thermal conductivity of solid (327.4°C) 0.310 J.sec .cm .°C
-1 -1 -1
Thermal conductivity of liquid (327.4°C) 0.159 J.sec .cm .°C
-1
Liquid surface tension 4.70 Nm.cm

APPENDIX 1 – Properties of Lead and Associated Compounds
-6 -3
Electrical resistivity at 20°C (polycrystalline solid) 20.648. 10 ohm.cm
Temperature coefficient per °C 0.00336
Tensile strength 126.55 - 175.77 kg cm -2
Modulus of elasticity 0.155 × 106 kg cm-2
BINARY LEAD RICH EUTECTICS
Metal % Pb by weight Liquidus temp °C Lead rich compound

Ag 95.3 304
Ca 90.0 630 CaPb3
Cu 99.94 326
K 98.1 277 KPb4
Na 97.3 307 NaPb3
Li 99.3 235 LiPb
Mg 97.8 253 Mg2Pb
Cd 82.6 248
Zn 99.5 318.2
Sn 38.1 183
Sb 88.9 252
As 97.2 288
Te 99.975 326.3 PbTe
Se 79.5 860 PbSe
PROPERTIES OF LEAD OXIDES
Oxide PbO PbO2 Pb3O4

Molecular weight 223.21 239.19 685.57
Colour α Red Dark brown or black Orange to red
β Yellow
Structure α Tetragonal Orthorhombic or Spinel
β Orthorhombic tetragonal
Density α 9.2 - 9,5 9.165 - 9.40 9.1
β 9.5 - 9.9
Transition temperature 488.5°C
Melting point 888°C Decomposes at 290°C 830°C in oxygen
Decomposes at 500°C
Heat of formation (kJ/mole) α -219.28 -276.65 -734.29
β -217.86
Free energy of formation (kJ/mole) α -188.82 -212.42 -617.14
β -188.07
Entropy (J/°C.mole) α 65.27 76.48 211.29
β 67.36
Heat capacity (J/°C.mole) α 45.77 62.22 142.26
β 45.85

VAPOUR PRESSURES
Vapour pressures (P) expressed in mm of mercury and as a function of temperature may be expressed
by the following equations, where T is the temperature in °K.
Lead metal log(P) = 7.518 - 9386/T
Lead monoxide (PbO) log(P) = 9.457 - 11476/T
Lead sulfide (PbS) log(P) = 10.196 - 11368/T
SILVER METAL PROPERTIES
Atomic number 47
Atomic weight 107.868
Stable isotopes, relative abundance
Mass number 107 109
Per cent 51.82 48.18
Melting point 960.8°C

Boiling point (at 760 mm Hg) 2212°C
Density (Solid at 25°C) 10.5
Heat capacity of solid 25.54 J.mole-1°C-1 (T in °K)

Heat capacity of liquid 30.54 J.mole-1°C-1 (T in °K)
Heat capacity of vapour 20.8 J.mole-1°C-1 (T in °K)
Heat of fusion 11 945 J.mole-1 (at 960.8°C)
Heat of vaporisation 254 052 J.mole-1 (at 2212°C)

THERMODYNAMIC PROPERTIES OF COMPOUNDS INVOLVED

IN LEAD EXTRACTION
Source: Handbook of Chemistry and Physics – CRC.
Compound Mol wt Density (298°K) Heat of formation Free energy of

g/cm3 (298°K) kJ/mole formation
(298°K) kJ/mole
Pb (liquid) 207.19 11.344
PbS 239.27 7.5 -94.31 -92.67
PbO (yellow) 223.21 9.53 -217.86 -188.49
PbO2 239.21 9.375 -276.65 -218.99
PbSO4 303.27 6.2 -918.39 -811.24
PbCO3 267.22 6.60 -700.00 -626.34
PbSiO3 283.27 6.49 -1082.82 -999.97
PbCl2 279.12 5.80 -359.20 -313.97
FeS2 119.98 5.0 -177.90 -166.69
FeS 87.91 4.6 -95.06 -97.57
FeO 71.85 5.7 -266.52 -244.35
Fe2O3 159.69 5.24 -822.16 -740.99
SiO2 60.07 2.65 -859.39 -805.00
SO2 64.06 -296.81 -299.91
H2SO4 98.06 1.834 -810.40 -733.92
CaCO3 100.09 2.711 -1211.13 -1133.03
CaO 56.08 3.32 -634.71 -603.75
CaSO4.2H2O 172.14 2.32 -2005.52 -1780.17
ZnS – sphalerite 97.44 4.102 -202.92 -198.32
ZnS – wurtzite 97.44 4.087 -189.53 -184.93
ZnO 81.38 5.606 -348.38 -318.19
ZnSO4 161.45 3.74 -978.55 -871.56
ZnCO3 125.39 4.42 -812.53 -731.36
Zn2SiO4 222.85 4.05
Zn (g) 65.37 0.0029 130.44 94.93
CO (g) 28.01 0.00125 -110.54 -137.28
CO2 (g) 44.01 0.00197 -393.51 -394.38
CH4 (g) 16.04 0.000717 -74.85 -50.79
H2O (g) 18.01 -241.84 -228.59

HEAT CAPACITIES AT CONSTANT PRESSURE

(Joule. mole-1. °K-1 as a function of temperature T°K)
Cp = a + b T + c T2 + d T-2
Suitable for elevated temperatures around 1000°C.
Compound a b c d
Pb (liquid) 28.451
PbO 43.221 0.01331
PbO2 53.137 0.03263
PbCl2 66.442 0.03493
PbS 44.476 0.01678
PbSO4 110.458
FeS2 74.768 0.005565 -1 274 028
FeS 50.417 0.01142
FeO 52.802 0.006242 -318 821
Fe2O3 103.428 0.06711 -1 771 506
Fe3O4 172.255 0.07874 -4 098 228
Fe (solid) 25.606 0.01406
Fe (liquid) 34.10
SiO2 45.815 0.02301
CaCO3 82.341 0.04975 -1 286 998
CaO 41.84 0.02025 -451 872
CaSO4 77.487 0.09192 -656 051
Zn (g) 20.786
ZnO 49.003 0.005104 -912 279
ZnS 49.246 0.005272 -485 344
ZnSO4 117.152
SO2 (g) 47.697 0.005916 -855 628
SO3 (g) 58.158 0.02552 -1 347 248
C 17.154 0.004268 -878 640
CO (g) 26.861 0.006966 -8.2 E-7
CO2 (g) 25.999 0.04350 -1.48 E-5
CH4 (g) 14.146 0.07550 -1.8 E-5
H2 (g) 29.066 -0.00084 2.013 E-6
H2O (g) 30.359 0.009615 1.184 E-6

INDEX
Index Terms Links
Accretions
in boiler systems 112
in the blast furnace 70
Agricola 17
Alcoa
bipolar electrolytic cell 155
Alloying methods 243
Aluminium
for copper separation 205
American water jacketed furnace 22
Anode slimes
in lead refining 238
Anodes
for electrolytic refining 233
Antimony 221
recovery from softener slag 206
recovery in Harris process 208
removal from lead 205
Arsenic 221
Ausmelt furnace
See Slag bath reactor
Ausmelt process 123
for secondary lead 188
reactor design 125
Autogenous grinding 33
This page has been reformatted by Knovel to provide easier navigation.

Index Terms Links
Balbach-Thum cell 216

Battery – lead acid
breaking and separation 170
composition 168
Battery paste
desulfurisation 172
Battery paste analysis 170
Betts process 227 230
performance details 236
Bismuth 222
recovery 239
Blast furnace 65
accretions 81
capacity determinants 81
coke requirements 70
construction 75
development and evolution 21
energy consumption 259
energy use 260
feeding 80
feeding practice 77
gas handling 80
heat balance 83
oxygen enrichment 83
performance data 81
Port Pirie design 78
reaction zones 67
slag composition 72 73
tapping requirements 79
treatment of reverb slags 179

Index Terms Links
Blood lead levels 250 251

Blue Powder 92
Boliden lead process 105
Bulk concentrates
commercial terms 40
By-products
revenues 285
By-products from zinc production 286
Cadmium 222
Calcium 222
use for bismuth separation 219
Castilian blast furnace 22
Casting machines 244
Cathode starting sheets
for lead refining 233
Caustic soda refining 220
Cementation
for solution purification 160
Chloride complexes of lead and silver 156
Chlorine
for zinc separation 219
from electrolytic process 154
removal from fume 145
Chrome magnesite refractories 104
Coke
reactivity 70
reactivity in ISF 96
sizing for blast furnace 70
use in blast furnace 70
use in Kivcet process 113
use in the ISF 96
Coke layer in the Kivcet process 113

Index Terms Links
Condenser
lead splash 92
Converting
lead bullion 106
Copper 222
removal with aluminium 205
Copper dross
treatment with sodium 204
Copper dross treatment 204
Copper drossing 201
continuous method 202
Copper matte
as a by-product 285
Cost curve for world plants 280
Costs
comparison of refining processes 282
for Isasmelt process 277
for Kivcet process 274
for refining operations 280
of sinter plant blast furnace 269
of smelting and refining operations 269
smelting process comparisons 279
Cupellation 27 216
Current modulation in electrolytic
refining 236
Davey desilvering process 213

Dehalogenation
See Chlorine removal
of zinc fume 145
Desulfurisation of battery paste 172

Index Terms Links
Direct smelting 27
energy use 262
fuel requirements 100
principles 99
processes 99
Dithionic acid
electrolyte 152
Dwight Lloyd sintering machine 25 46
Economics
of refined lead production 286
Economics of secondary lead
production 289
Effluent standards 255
Effluent treatment methods 255
Electric furnace
for lead smelting 105
for slag cleaning 129
in Kivcet process 114
treatment of secondary slags 180
use for slag fuming 146
Electrode potentials, standard 228
Electrolysis
of lead chloride 151
Electrolytic cells
for molten salt electrolysis 153
Electrolytic refining
anode slimes treatment 238
anodes 233
cathodes 235
cell voltage 229
cells 230
chemical principles 227

Index Terms Links
Electrolytic refining (Cont.)

costs 281
electrolyte control 235
fluoborate electrolyte 240
performance 236
starter sheets 235
sulfamic acid electrolyte 239
Electrowinning
of primary lead 151
Electrowinning processes
energy use 264
Energy
consumption in smelting and
refining 259
Energy consumption
comparison for extraction 266
processes
for concentrate production 266
Engitec Fluobor process 162
Engitec secondary lead process 192
Environmental impact of lead 249
Environmental lead controls 254
Faber Du Faur furnace 215

Ferric chloride 156
Flash smelting See Kivcet process
Flash smelting shaft
Kivcet 110
Flotation See Froth flotation
Flotation process See Froth flotation

Index Terms Links
Flue dusts
handling and treatment 147
Fluoborate
electrolysis systems 162
electrolyte 152
Fluorine
in sinter gas 61
removal from fume 145
Fluosilicate
electrolysis systems 161
electrolyte 152
Fluosilicic acid 235
Froth flotation 32 33
collectors 34
depressants 34
flow sheets 35
Fume
treatment prior to
zinc extraction 144
Fuming
iron formation during 143
Ginatta process 193

Gold 222
by-product returns 285
chlorine refining 217
refining 217
separation from silver 217
Graphite anodes 158
Gravity concentration 32

Index Terms Links
Halex 159
Harris process 206
treatment of caustic slags 207
two-stage configuration 208
Health effects of lead 249
Hearth furnace 19
Heat balances
smelting processes 99
Heat capacities of compounds 297
Howard press 215
Huntington-Herbelein process 24 46
Imperial Smelting Furnace See ISF process

Impurities in lead 221
Indium 222
Ingot dimensions 244
Intec process 159
Iron 223
formation during fuming 143
formation during ZnO reduction 133
Isasmelt process 120
costs 277
energy use 263
ISF
blast air preheat 91
blast air rates 96
coke use 96
furnace accretions 95
furnace capacity 96

Index Terms Links
ISF (Cont.)
furnace design 92
furnace top temperature control 92
process 89
slag and bullion tapping 95
slag formation and composition 92
tuyere characteristics 94
Kaldo process 106 188

Kinetics of ZnO reduction from slags 132
Kivcet furnace
construction 116
gas offtake shaft 111
Kivcet process 109
costs 274
energy use 262
performance 114
Kroll Betterton process 219
Lance
processes using 119
Lance reactors
Lead
casting methods 243
consumption 6
health exposure limits 251
in air standards 254
in slag from direct smelting 101
metal cycle 8
metal quality specifications 243

Index Terms Links
Lead (Cont.)
mine production 6
presence in the environment 249
secondary production 7
standard ingot dimensions 243
toxicity 249
uses 5
Lead blast furnace slags
fuming 135
Lead block casting 245
Lead bullion
commercial terms 41
from the ISF 95
Lead carbonate 172
Lead chloride
aqueous electrolysis 158
molten salt electrolysis 153
preparation from sulfide 156
solubility 156
Lead concentrates
commercial specifications 36 37
commercial terms 38
grade versus recovery 36
Lead dioxide
formation at anode 152 161 191 192
in hydrometallurgical processing 189
Lead metal properties 293
Lead minerals 31
Lead oxides
properties 294
Lead sheet
production equipment 246

Index Terms Links
Lead smelting
capacity of smelters 8
historical developments 29
industry structure 7
primary smelters 9
secondary capacity 13
Lead, sulfur, oxygen system 101
Lead-copper-sulfur system 200
Lead-silver phase diagram 210
Lead-zinc phase diagram 212
Leferrer furnace 215
Lime in waste water treatment 255
London Metal Exchange 284
metal prices 38
Magnesium 223
use for bismuth separation 219
Magnetite formation 104
Matte 25
treatment of 147
Medieval furnaces 17
Melilite
importance in sinter structure 49
Mercury 223
removal from sinter gas 61
Metal payment in concentrates 39
Minemet process 159
Mineral separation 32
Moebius cell 216
Molten salt electrolysis
impurities 155

Index Terms Links
Nickel 223
Occupational exposure controls 253

Occupational health standards 251
Oliforno process 185
Ore size reduction 33
Outokumpu lead process 125
Oxygen
enrichment in ISF blast air 96
in blast furnace 83
in Isasmelt process 121
in QSL process 116
use for softening lead 205
Oxygen stoichiometry
in Ausmelt process 121
Parkes process 211

Pattinson process 27 210
Peak bed temperature – sinter 48
Penalty elements
in lead concentrates 39
PLACID process 158 193
Platinum Group Metals 223
Polypropylene
recovery from batteries 170
Port Pirie blast furnace 23
Pricing of metals 284

Index Terms Links
QSL process 116

energy use 263
performance 118
Reaction zones in blast furnace 67

Refining
by electrolytic methods 227
by thermal methods 197
energy use in electrolytic process 261
energy use in thermal process 261
equipment 199
kettles 199
secondary lead 193 221
Refractory protection
by magnetite 104
Retorting of silver crusts 215
Reverberatory furnace
Reverberatory hearth 20
Roasting 23
Rotary furnaces 181
for secondary smelting 185
performance with soda slags 187
Rotary kiln
for secondary smelting 183
secondary smelting
performance 184
RSR electrolytic process 161

Index Terms Links
Scotch hearth 18
Secondary lead
economics 289
effect of lead price on economics 290
energy consumption for recovery 267
Secondary lead residues 174
Secondary raw materials 41
pretreatment 167
Secondary smelting 175
processes 13
Selenium 223
Short rotary furnace See Rotary furnace
Silver 223
by-product returns 285
continuous removal process 214
cupellation 216
electrolytic refining 216
parting 217
properties 295
recovery efficiency 215
recovery methods 26
treatment of zinc alloy 214
zinc phase diagram 211
Silver minerals 31
Sinter
composition for blast furnace 49
composition for ISF 91
handling problems 54
physical structure 49
quality 48
Sinter charge preparation 50

Index Terms Links
Sinter gas handling 60

Sinter gas scrubbing liquor 62
Sinter machine
capacity and performance 56
downdraft 47
effect of concentrate grade 59
returns control 54
Sintering 45
coke additions 51
early processes 25
feed moisture control 51
fuel requirements 50
gas distribution and recycle 53
machine feeding 52
recycle ratios 51
updraught versus downdraught 55
Sirosmelt reactors 119
Skimmings from ingot casting 245
Slag
composition for blast furnace 73
granulation 79
ISF composition 92
Slag bath reactor
design and operation 142
zinc fuming process 141
Slag cleaning 129
Slag fuming 130
conventional furnace
batch operation 136
design 135
zinc recovery 138
furnace boiler 139
furnace design 135
furnace operation 136

Index Terms Links
Slag fuming (Cont.)

high intensity processes 144
using slag bath reactor 141
zinc elimination rates 137
Slag fuming conventional furnace
coal use 139
Slag viscosity 72
Sliming of lead minerals 33
Smelter by-products 40 285
Smelting
Soda slags
disposal issues 183
in secondary smelting 181
Sodium hydroxide 206
use for final lead refining 220
Sodium nitrate 206 220
Sodium sulfate
from waste battery processing 173
Sodium-iron-sulfur system 182
Softener slag
treatment 206
Softening 205
Speiss 26 95
St Joe Minerals process 157
Submerged lance
reactor See Slag bath reactor
Sulfamic acid
electrolyte 152
Sulfate reducing bacteria 174
Sulfur
in blast furnace 85
in bullion from direct smelting 101
removal from battery paste 172

Index Terms Links
Sulfur dioxide
content of gas for acid production 61
discontinuous production 108
efficiency of conversion to sulfuric
acid 62
Sulfur drossing
for copper removal 201 203
Sulfuric acid
black acid 63
by-product 286
production equipment 62
recovery from batteries 171
TBRC
for lead smelting 106
secondary smelting 188
Tecnicas Reunidas 158
Tellurium 223
separation from lead and recovery 210
Temperature
critical ISF exit gas 91
Thallium 224
Thermal refining 197
costs 281
Thermodynamic properties of
compounds 296
Tin 224
Titanium anodes 158

Index Terms Links
Top submerged lance processes

for direct smelting 119
for slag fuming 140
secondary smelting 188
Toxicology of lead 249
Treatment charge 39
Tuyeres
design for blast furnace 91 94
in the blast furnace 78
raceways 94
UOP process 157

US Bureau of Mines
Molten salt electrolytic cell 154
US Bureau of Mines process 157
Vacuum dezincing 217

Vapour pressure
lead compounds 103
of lead compounds 295
Vapour pressure of zinc 131
Volatilisation of lead in direct smelting 103
Waste heat recovery

in slag fuming 139
Water
quality standards for lead 255
Water jackets
slag fuming furnace 135

Index Terms Links
Williams process 214

Wohwill process 217
Zinc 224
in blast furnace feed 26
limits in lead concentrates 38
quality specifications 285
separation by chlorine 219
use for desilverising 211
vacuum distillation equipment 217
Zinc fuming
from lead slags 130
kinetics 132
reduction equilibria 132
Zinc oxide See Fume
activity in slag 131
Zinc vapour pressure 131
Zinc-silver phase diagram 211

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The Extractive

The Australasian Institute of Mining and Metallurgy

THE AUSTRALASIAN INSTITUTE OF MINING AND METALLURGY

No part of this publication may be reproduced, stored in a retrieval system or transmitted

ISBN 978 1 921522 02 4

Desktop published by:

Compiled on CD ROM by:

Part B – Primary Smelting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

Part C – Secondary Smelting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165

Part E – Environmental and Economic Issues . . . . . . . . . . . . . . . . . . . . . . . . . . 247

Chapter 1 Industry Perspective and Introduction

The Extractive Metallurgy of Lead Spectrum Series Volume 15 3

4 Spectrum Series Volume 15 The Extractive Metallurgy of Lead

A generalised list of the major uses of lead may be given as follows:

The Extractive Metallurgy of Lead Spectrum Series Volume 15 5

End use 1960 2005

WORLD SUPPLY AND DEMAND

1000 Consumption Mine Production

FIG 1.1 - Global lead consumption and mine production.

Region Metal (t) Mine (t)

6 Spectrum Series Volume 15 The Extractive Metallurgy of Lead

THE LEAD SMELTING INDUSTRY

Country Mined lead production (tonnes of contained lead)

The Extractive Metallurgy of Lead Spectrum Series Volume 15 7

USA 1 338 000 290 000 1 048 000

Lead Bullion Waste Zinc

Copper Matte Silver and Gold

FIG 1.2 - Lead extraction industry schematic.

8 Spectrum Series Volume 15 The Extractive Metallurgy of Lead

Lead Residues from

Secondary Smelting Primary Smelting Recycle

Recycle Metal Scrap

FIG 1.3 - Lead metal cycle.

The Extractive Metallurgy of Lead Spectrum Series Volume 15 9

Recycles Fluxes – silica, lime, ironstone

Gas Sulfuric Acid

Lead bullion to refinery

FIG 1.4 - Sinter plant–blast furnace flow sheet.

10 Spectrum Series Volume 15 The Extractive Metallurgy of Lead

Process type Capacity (t/a) Percentage of total Number of smelters

FIG 1.5 - Distribution of world primary lead smelter capacity.

The Extractive Metallurgy of Lead Spectrum Series Volume 15 11

12 Spectrum Series Volume 15 The Extractive Metallurgy of Lead

SECONDARY LEAD PRODUCTION

The Extractive Metallurgy of Lead Spectrum Series Volume 15 13

FIG 1.6 - Distribution of world secondary lead smelter capacity.

FIG 1.7 - World lead smelters – size distribution.

14 Spectrum Series Volume 15 The Extractive Metallurgy of Lead

REFERENCES AND FURTHER READING

The Extractive Metallurgy of Lead Spectrum Series Volume 15 15

LEAD PRODUCTION IN EARLY TIMES

The Extractive Metallurgy of Lead Spectrum Series Volume 15 17

FIG 2.1 - Medieval smelting furnaces (from Agricola, 1950).

18 Spectrum Series Volume 15 The Extractive Metallurgy of Lead

Charge and Fuel Bed

The Extractive Metallurgy of Lead Spectrum Series Volume 15 19

FIG 2.3 - Reverberatory lead furnace.

PbSO4 + 2PbS = 3Pb + 2SO2 (2.1)