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Physical Chemistry of Metallurgical Processes

ISBN: 978-1-119-07833-3
624 pages
February 2016
Physical Chemistry of Metallurgical Processes (1119078334) cover image

Description

This book covers various metallurgical topics, viz. roasting of sulfide minerals, matte smelting, slag, reduction of oxides and reduction smelting, interfacial phenomena, steelmaking, secondary steelmaking, role of halides in extraction of metals, refining, hydrometallurgy and electrometallurgy.

Each chapter is illustrated with appropriate examples of applications of the technique in extraction of some common, reactive, rare or refractory metal together with worked out problems explaining the principle of the operation.
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Table of Contents

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

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Author Information

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".

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Reviews

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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