Preface xi
Foreword xvii
List of Symbols xix
1 Introduction 1
1.1 Thermodynamic Quantities and their Interrelationships 5
1.1.1 General Thermodynamics 5
1.1.2 Solution Thermodynamics 15
Further Reading 37
2 Roasting of Sulfide Minerals 39
2.1 Methods of Roasting 40
2.2 Objectives 41
2.3 Chemistry of Roasting 42
2.4 Thermodynamics of Roasting 43
2.5 Kinetics of Roasting 47
2.6 Predominance Area Diagrams as a Useful Guide in Feed
Preparation 51
2.7 Problems 53
References 68
3 Sulfide Smelting 71
3.1 Matte Smelting of Chalcopyrite 72
3.1.1 Flash Smelting 74
3.1.2 Submerged Tuyere Smelting 76
3.1.3 Matte Converting 76
3.1.4 Ausmelt/Isasmelt: Top Submerged Lancing (TSL) Technology
80
3.2 Matte Smelting of Galena 83
3.3 Matte Smelting of Nickel Sulfide 85
3.3.1 Theory of Direct Conversion of Molten Nickel Sulfide into
Nickel 87
3.4 Continuous Converting 89
3.4.1 Noranda Continuous Converting Process 90
3.4.2 Outokumpu Flash Converting Process 90
3.4.3 Mitsubishi Continuous Converting Process 91
3.5 Direct Metal Extraction from Concentrates 92
3.5.1 Outokumpu Flash Smelting Process 93
3.5.2 Mitsubishi Process 94
3.6 Problems 96
References 100
4 Metallurgical Slag 103
4.1 Structure of Oxides 103
4.1.1 Role of Ion Dimension 104
4.1.2 Metal–Oxygen Bonds 106
4.2 Structure of Slag 108
4.3 Properties of Slag 110
4.3.1 Basicity of Slag 110
4.3.2 Oxidizing Power of Slag 112
4.3.3 Sulfide Capacity of Slag 112
4.3.4 Electrical and Thermal Conductivity 113
4.3.5 Viscosity 113
4.3.6 Surface Tension 117
4.3.7 Diffusivity 117
4.4 Constitution of Metallurgical Slag 118
4.4.1 State of Oxidation of Slag 120
4.5 Slag Theories 125
4.5.1 Ionic Theories 126
4.5.2 Molecular Theory 130
4.6 Problems 131
References 143
5 Reduction of Oxides and Reduction Smelting 145
5.1 Reduction Methods 146
5.2 Thermodynamics of Reduction of Oxides 147
5.2.1 Metallothermic Reduction 148
5.2.2 Thermal Decomposition 154
5.2.3 Reduction with Carbon Monoxide 155
5.2.4 Reduction with Hydrogen 159
5.3 Kinetics of Reduction of Oxides 161
5.3.1 Chemical Reaction with Porous and Nonporous Product Film
162
5.4 Commercial Processes 170
5.4.1 Production of Iron 170
5.4.2 Production of Zinc 174
5.4.3 Production of Tungsten and Molybdenum 177
5.5 Problems 179
References 196
6 Interfacial Phenomena 199
6.1 Precipitation 201
6.2 Nucleation of Gas Bubbles in a Liquid Metal 205
6.2.1 Role of Interfaces in Slag–Metal Reactions 208
6.3 Emulsion and Foam 209
6.4 Froth Flotation 211
6.5 Other Applications 213
6.6 Problems 214
References 230
7 Steelmaking 233
7.1 Steelmaking Processes 234
7.1.1 Bessemer Process 234
7.1.2 Open Hearth Process 235
7.1.3 Electric Arc Furnace (EAF) Process 236
7.1.4 Top-Blown Basic Oxygen Converter Process 236
7.1.5 Rotating Oxygen-Blown Converter Process 238
7.1.6 Bottom-Blown Oxygen Converter Process 239
7.1.7 Hybrid/Bath Agitated/Combined-Blown Process 240
7.2 Physicochemical Principles 242
7.2.1 Sulfur Reactions 242
7.2.2 Phosphorus Reactions 246
7.2.3 Silicon Reactions 250
7.2.4 Manganese Reactions 251
7.2.5 Carbon Reactions 253
7.2.6 Kinetics of Slag–Metal Reactions 256
7.3 Pre-treatment of Hot Metal 261
7.3.1 External Desiliconization 262
7.3.2 External Desulfurization 262
7.3.3 External Dephosphorization 262
7.3.4 Simultaneous Removal of Sulfur and Phosphorus 263
7.4 Chemistry of Refining 264
7.4.1 Bessemer Process 264
7.4.2 Open Hearth Process 266
7.4.3 Electric Arc Furnace (EAF) Process 266
7.4.4 Top-Blown Basic Oxygen Converter Process 267
7.4.5 Rotating Oxygen-Blown Converter Process 272
7.4.6 Bottom-Blown Oxygen Converter Process 274
7.4.7 Hybrid/Bath Agitated/Combined-Blown Process 276
7.5 Problems 279
References 286
8 Secondary Steelmaking 289
8.1 Inert Gas Purging (IGP) 290
8.2 Ladle Furnace (LF) 291
8.3 Deoxidation 291
8.3.1 Choice of Deoxidizers 293
8.3.2 Complex Deoxidizers 294
8.3.3 Vacuum Deoxidation 299
8.3.4 Deoxidation Practice 299
8.3.5 Removal of Deoxidation Products 300
8.4 Stainless Steelmaking 301
8.4.1 Physicochemical Principles 302
8.4.2 Stainless Steelmaking Processes 305
8.5 Injection Metallurgy (IM) 307
8.6 Refining with Synthetic Slag 309
8.7 Vacuum Degassing 311
8.7.1 Nitrogen in Iron and Steel 312
8.7.2 Hydrogen in Iron and Steel 315
8.7.3 Vacuum Treatment of Steel 319
8.8 Problems 325
References 348
9 Role of Halides in Extraction of Metals 351
9.1 Preparation of Halides 354
9.1.1 Complex Fluoride Processes 354
9.1.2 Halogenation of Oxides 355
9.1.3 Halogenation of Ferro-Alloys 359
9.1.4 Crystallization from Aqueous Solution 360
9.2 Purification of Chlorides 362
9.2.1 Purification of Titanium Tetrachloride 363
9.2.2 Purification of Columbium Pentachloride 363
9.2.3 Purification of Vanadium Tetrachloride 363
9.3 Metal Production 364
9.3.1 Metallothermic Reduction 365
9.3.2 Fused Salt Electrolytic Process 369
9.4 Purification 369
9.4.1 Disproportionate Process 369
9.4.2 Iodide Process 370
9.5 Problems 370
References 380
10 Refining 383
10.1 Principle 384
10.2 Methods of Refining 384
10.2.1 Fire Refining 385
10.2.2 Metal–Metal Refining 391
10.2.3 Metal–Gas Refining 394
10.2.4 Miscellaneous Group 400
10.3 Ultra-purification 400
10.3.1 Zone Refining 400
10.3.2 Electro-transport 403
10.3.3 Iodide Decomposition 404
10.4 Refining along with Melting and Consolidation 409
10.5 Problems 410
References 420
11 Hydrometallurgy 423
11.1 Leaching 425
11.1.1 Leaching Methods 427
11.2 Breakdown of Refractory Minerals 431
11.2.1 Concentrated Sulfuric Acid Breakdown 432
11.2.2 Concentrated Alkali Breakdown 432
11.3 Physicochemical Aspects of Leaching 433
11.3.1 Thermodynamics of Aqueous Solutions 433
11.3.2 Stability Limit of Water 435
11.3.3 Potential-pH Diagrams 437
11.3.4 Electrochemical Phenomenon in Leaching 444
11.3.5 Kinetics of Leaching 448
11.4 Treatment of Leach Liquor 465
11.4.1 Chemical Precipitation 466
11.4.2 Fractional Crystallization 467
11.4.3 Ion Exchange 468
11.4.4 Solvent Extraction 476
11.5 Recovery of Metals from Leach Liquor 492
11.5.1 Precipitation of Metal Sulfides 492
11.5.2 Cementation 495
11.5.3 Gaseous Reduction 502
11.6 Problems 507
References 519
12 Electrometallurgy 523
12.1 Principle 525
12.1.1 Cell Potential 527
12.1.2 Discharge Potential 530
12.1.3 Current and Energy Efficiency 532
12.2 Applications 534
12.2.1 Electrowinning 534
12.2.2 Electrorefining 545
12.3 Problems 549
References 556
Appendixes 559
Index 585
Professor M. Shamsuddin had served as Professor and Head of the Department of Metallurgical Engineering at Banaras Hindu University for four decades. He spent three years (June 1978-June 1981) in the United States: one year each at the University of Chicago, University of Utah, Salt Lake City and the Massachusetts Institute of Technology, Cambridge. At MIT, he held the position of a Visiting Associate Professor on invitation from Prof. John F. Elliott of Department of Materials Science & Engineering to teach a graduate course entitled "Physical Chemistry of Metallurgical Processes".
Review of the book ‘Physical Chemistry of Metallurgical
Processes’
by M. Shamsuddin, TMS and Wiley, ISBN 978-1-119-07833-3, 2016
from
H. Y. Sohn, Distinguished Professor
Departments of Metallurgical Engineering
and of Chemical Engineering
University of Utah
Salt Lake City, Utah
U.S.A.
The recent progress in materials development has compelled
modification of syllabi in Metallurgical Engineering discipline. In
order to introduce new courses on materials, chemical metallurgy
contents have been reduced. Considering the requirement and
circumstances this book, which discusses the physical chemistry of
various steps involved in the extraction of different types of
metals, is an important contribution in the field of chemical
metallurgy. It is well known that the exploitation of many low
grade and complex ores/minerals has been possible in recent years
by a thorough understanding of slag-metal reactions with the aid of
thermodynamics and reaction kinetics. The physical chemistry
principles that are a key to extraction technologies play a
decisive role in the development as well as improvement of
processing methods. As a consequence, metallurgists and chemical
engineers often face problems in selecting the appropriate
technique for the treatment of concentrate. In order to overcome
such a challenging task a sound knowledge of physical chemistry of
different extraction methods is extremely useful. Since the
chemistry of the extraction process varies according to the nature
of the metal, a comprehensive and collective treatment in one book
is much desired.
This is a noteworthy book for three reasons: Firstly, it includes
discussions on physicochemical principles involved in different
chemical processes, such as roasting of sulfide minerals, matte
smelting/converting, reduction smelting, interfacial phenomena,
steelmaking, deoxidation, metal extraction with halides, refining,
degassing, leaching, solution purification, precipitation, and
cementation, during extraction/production of not only common metals
but also rare, reactive and refractory metals by pyro- and
hydrometallurgical methods. Secondly, it provides a number of
worked out examples in each chapter, which make understanding of
the process easier. The problems require imagination and critical
analyses. At the same time, they also encourage readers for
creative application of thermodynamic data. Thirdly, the
author has systematically summarized and presented scattered
information on physicochemical aspects of metal extraction from
previously published books and journal articles.
The book will undoubtedly fulfil the needs of students and teachers
by providing information on the principles and methods of
extraction of different metals in one place. I am confident that
the book will be in demand throughout the world by universities and
institutes offering courses in Metallurgy, Chemical Engineering and
Technology, and also by various metallurgical and chemical research
laboratories. It will be more useful to students of metallurgical
engineering specializing in chemical/extractive metallurgy, but the
basic principles of various unit processes involved in extraction
will also be appreciated by chemical engineering students.
In addition to his long tenure at Banaras Hindu University,
Professor Shamsuddin has had diversified interactions with faculty
members of two premier institutions, namely Department of
Metallurgical Engineering, University of Utah, Salt Lake City and
Department of Materials Science and Engineering, Massachusetts
Institute of Technology, USA, on various aspects of metal
extraction, thermodynamics and kinetics. I have no reservation in
stating most strongly that this book on “Physical Chemistry of
Metallurgical Processes” will achieve a high standard in the field
of chemical/extractive metallurgy and be appreciated by
metallurgists and chemical engineers.
Review of the book ‘Physical Chemistry of Metallurgical
Processes’
by M. Shamsuddin, TMS and Wiley, ISBN 978-1-119-07833-3, 2016
from
Professor T. R. Mankhand
Department of Metallurgical Eng.
Indian Institute of Technology (Banaras Hindu University)
The author, based on his four decades of teaching and research
experience in metallurgical thermodynamics and chemical extractive
metallurgy has made a comprehensive presentation of the most
relevant knowledge relating to role of physical chemistry in the
extraction of various metals. A diverse variety of metallurgical
topics covered including roasting of sulphide minerals, sulphide
smelting, metallurgical slag, reduction of oxides and reduction
smelting, interfacial phenomenon, steel making, secondary
steelmaking, role of halides in extraction of metals, refining,
hydrometallurgy and electrometallurgy. Each chapter is illustrated
with appropriate examples related to extraction of metals with
worked out problems explaining the principle of the process.
This book will fulfill need of students and teachers for providing
information and understanding of the principles and methods of
extraction of common, rare, reactive and refractory metals in one
place. This will also help to explore the potential for future
innovation to carry out more effective and efficient methods of
extraction and processing. It will not only serve as a text book
for undergraduate and postgraduate students of metallurgical
engineering but also as a reference book for the practicing
engineer.
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