Handbook of Ferroalloys

Theory and Technology

Edited by

Michael Gasik

AMSTERDAM • BOSTON • HEIDELBERG • L O N D O N • NEW YORK • OXFORD • PARIS

SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO

ELSEVIER Butterworth-Heinemann is an Imprint of Elsevier

 Contents

Preface xiii
Contributors xv

Section I
General
1. Introduction
Michael M. Casik Editor
1.1 Introduction to Ferroalloys 3
1.2 The Scope and Structure of the Book 5
Acknowledgments 7
References 7

2. Basics of Ferroalloys
Lauri Holappa
2.1 Introduction: Background for Ferroalloys Development
arid Production 9
2.2 Ferroalloys in the Development of Steels 12
2.3 A Case: Ferroalloys for Stainless Steels 14
2.4 Recent Ferroalloys Production and Markets Development 17
2.5 Energy and Emissions Issues of the Ferroalloys Industry 22
2.5.1 Energy Demand for Ferroalloys Making 22
2.5.2 CO2 Emissions from Ferroalloys Production 23
2.6 Future Outlook for the Ferroalloys Industry 26
References t 27

3. Theory of Ferroalloys Processing

Heikki Jalkanen and Michael Casik
3.1 General Theory of the Processes of Ferroalloys
Production 29
3.1.1 Introduction to Ferroalloys and their Processing 29
3.1.2 Processes in Materials Production 35
3.1.3 Thermodynamics of Pyrometallurgical
(High-Temperature Chemical) Processes 37
3.1.4 Kinetics of Pyrometallurgical Processes 58
 Contents

3.1.5 Basics of Heat Transfer in Ferroalloys Processing 65

3.1.6 Basics of Mass and Momentum Transfer
in Ferroalloys Processing 70
3.2 Ferroalloys Components and Their Properties 72
3.2.1 Metallic Melts 72
3.2.2 Oxide Melts (Slags and Fluxes) 74
3.2.3 Carbon Reductants for Ferroalloys Processing 79
References 81

4. Ferroalloys Processing Equipment

Isobel Me Dougall
4.1 Introduction to Ferroalloys Processing Technology 83
4.1.1 Ferroalloys Basic Furnace Design and Operation 85
4.1.2 Ferrochrome, Ferrosilicon, Ferromanganese,
and Silicomanganese Furnaces 92
4.1.3 Silicon Metal Furnaces 98
4.1.4 Ferronickel Furnaces 101
4.1.5 DC Furnaces 105
4.1.6 Electrical Supply and Operation 107
4.1.7 Furnace Linings 119
4.1.8 Furnace Principal Operating Stages 121
4.1.9 Furnace Control 122
4.1.10 Processing Hazards and Risk Management 122
4.2 Equipment for Furnace Feed Processing 127
4.2.1 Agglomeration 128
4.2.2 Sintering of Manganese Ore 129
4.2.3 Preheating 131
4.2.4 Prereduction 133
4.3 Downstream Processing 133
4.3.1 Refining 133
4.3.2 Casting 134
4.4 Other Furnaces for Ferroalloys Processing 137
Acknowledgments 138
References 138

5. Electrical and Thermal Operations of Furnaces

for Ferroalloys Production
Gudrun Saevarsdottir
5.1 Introduction to Furnace Operations for Ferroalloys Processing 139
5.2 Basics of Electric Circuit Theory 140
5.2.1 Direct and Alternating Current and Voltage 140
5.2.2 Resistive Circuits 143
5.2.3 Reactance Circuits 143
5.2.4 Impedance and Power in AC Circuits 145
5.3 Ferroalloy Smelting Furnaces as Electrical Circuits 147
Contents

5.3.1 DC Furnaces 147

5.3.2 AC Furnaces 148
5.4 Modes of Heat Dissipation in Furnaces 153
5.4.1 Electric Arc 153
5.4.2 Electric Arc Models 156
5.4.3 Resistive Heating 160
5.4.4 Current Paths and Distribution of Heat Dissipation 162
5.5 Electric Operations and Control of the Furnace 165
5.5.1 Power Control 166
5.5.2 Electrode Control 166
5.6 Environmental Issues of Ferroalloys Furnace Operations 170
5.6.1 Particulates Emissions 170
5.6.2 Gaseous Emissions 173
5.6.3 Heat Emissions and Losses 174
References 174

Section II
Major (bulk) Ferroalloys
6. Ferrosilicon and Silicon Technology
Merete Tangstad
6.1 Introduction to Silicon and Its Ferroalloys 179
6.1.1 Properties of Silicon 180
6.1.2 Silicon Interaction with Other Elements 181
6.2 Raw Materials, Silicon, and Ferrosilicon Compositions 186
6.2.1 Sources of Silica 186
6.2.2 Carbon Reductants 191
6.2.3 Compositions of Silicon and Ferrosilicon 195
6.3 Silicon and Ferrosilicon Smelting Technology 198
6.3.1 Basic Principles of Operation 198
6.3.2 Smelting Process 201
6.4 Casting and Refining Operations 211
6.4.1 Casting 211
6.4.2 Refining of Silicon and Ferrosilicon 212
6.5 Energy Savings and Environmental Issues in Silicon
and Ferrosilicon Production 215
6.5.1 Energy Recovery 215
6.5.2 Emissions Control 217
References 219

7. Manganese Ferroalloys Technology

Merete Tangstad
7.1 Introduction to Manganese Ferroalloys 222
7.1.1 History and Background of Manganese 222
7.2 Properties of Manganese and Its Compounds 222
(_ viii ") Contents

7.2.1 Properties of Manganese 222

7.2.2 Interaction of Manganese with Oxygen
and Carbon 223
7.2.3 Interaction of Manganese with Other Elements 225
7.2.4 Manganese in Oxide Systems and Slags 229
7.3 Manganese Ores Processing and Reduction 231
7.3.1 Manganese Ores 231
7.3.2 Agglomeration Processes 234
7.4 Manganese Ferroalloys 238
7.4.1 Manganese Alloy Specifications 238
7.4.2 Impurities in Manganese Alloys 240
7.5 Smelting Technologies for Manganese Alloys 240
7.5.1 Basics of Reduction Processes 240
7.5.2 Outline of Industrial Practice 242
7.6 Technology of Ferromanganese 246
7.6.1 High-Carbon Ferromanganese Production 246
7.6.2 Production of Commercial Silicomanganese
(FeSiMn) 250
7.6.3 Post-Tap Hole Processing for FeMn and SiMn 252
7.6.4 Production of Manganese Metal 253
7.7 Refining Operations for Low-Carbon Manganese
Ferroalloys 256
7.7.1 Production of Low-Carbon Ferromanganese 256
7.7.2 Production of Low-Carbon Silicomanganese 258
7.8 Manganese Ferroalloys Postprocessing 259
7.8.1 Casting 259
7.8.2 Crushing and Sieving 260
7.9 Nitrided Manganese Ferroalloys 261
7.10 Energy Use in Manganese Ferroalloys Processing 262
7.11 Potential Hazards of Operations 263
Acknowledgments 265
References 265

8. Technology of Chromium and Its Ferroalloys

Mihail I. Casik
8.1 Properties of Chromium 268
8.1.1 Phase Equilibria with Major Chromium-Containing
Systems 268
8.1.2 Phase Equilibria with Chromium Oxide 276
8.2 Chromium Raw Materials and Their Processing 280
8.2.1 Chromium Minerals Overview 280
8.2.2 Chromium Resources Overview 283
8.2.3 Chromium Ores and Chromites Processing 285
8.3 Chromium Ferroalloys Technology 289
8.3.1 Technology of Low-Carbon Ferrochrome 289
8.3.2 Technology of Medium-Carbon Ferrochrome 297
8.3.3 Technology of Ferrosilicochrome (FeSiCr) 299
Contents

8.3.4 Technology of Ultra-Low-Carbon FeCr 303

8.3.5 Technology of Nitrided Ferrochromium (FeCrN) 305
8.4 Production of Metallic Chromium and Its Alloys
by Aluminum Reduction 307
8.5 Environmental Issues of Chromium and Its Ferroalloys
Processing 312
8.5.1 Human Health Hazards of Chromium and Its Compounds 312
8.5.2 Dust and Wastewaters Treatment from Chromium
Ferroalloys Processing 313
8.5.3 Fire and Explosion Hazards of Chromium Ferroalloys 314
References 314

9. High Carbon Ferrochrome Technology

Johan Basson, Jorma Daavittila
9.1 Introduction 318
9.1.1 High Carbon Ferrochrome and Its Production Base 318
9.1.2 Uses and Applications of High Carbon
Ferrochrome 326
9.2 Technology Routes for the Production of High Carbon
Ferrochrome 328
9.2.1 Introduction 328
9.2.2 Open/Semiclosed Submerged Arc AC Furnaces 331
9.2.3 Closed Submerged Arc AC Furnaces 335
9.2.4 Prereduction and Submerged Arc AC Smelting 340
9.2.5 Open Arc DC Furnaces 344
9.2.6 Other Technology Routes 348
9.3 Post Tap Hole Practices and Product Types 350
9.3.1 Alloy and Slag Tapping 350
9.3.2 Product Types 351
9.3.3 Slag Handling and Utilization 353
9.4 Environmental Control and Occupational Health 354
9.4.1 Environmental Impact of High Carbon Ferrochrome
Production 354
9.4.2 Occupational Health Hazards 360
References , 363

Section III
Minor Ferroalloys
10. Technology of Ferronickel
Oleg Polyakov
10.1 Properties of Nickel and Its Compounds 367
10.2 Nickel Raw Materials 371
10.3 Ferronickel Smelting and Refining 371
10.3.1 Ferronickel and Its Smelting 371
( x ) Contents

10.3.2 Refining and Casting of Ferronickel 373

References 374

11. Technology of Tungsten Ferroalloys

Michael Casik
11.1 Properties of Tungsten and Its Compounds 377
11.2 Minerals, Ores, and Concentrates of Tungsten 380
11.3 Technology for Producing Ferrotungsten 382
11.3.1 Reduction by Carbon and Silicon 382
11.3.2 Reduction by Aluminum 385
References 385

12. Technology of Molybdenum Ferroalloys

Michael Gasik
12.1 Properties of Molybdenum and Its Compounds 387
12.2 Minerals, Ores, and Concentrates of Molybdenum 392
12.3 Oxidative Roasting of Molybdenite Concentrates 392
12.4 Technology for Producing Ferromolybdenum 393
References 395

13. Technology of Vanadium Ferroalloys

Michael Casik
13.1 Properties of Vanadium and Its Compounds 397
13.2 Sources of Vanadium 401
13.3 Treatment of Vanadium Raw Materials 402
13.3.1 Chemical Treatment of Vanadium Raw Materials 404
13.3.2 Metallurgical Processing of Vanadium
Raw Materials 404
13.3.3 Reduction of Vanadium from Oxides 405
13.4 Technology of Ferrovanadium 405
13.4.1 Reduction by Silicon 405
13.4.2 Technology of Ferrovanadium by Reduction
by Aluminum 407
13.5 Technology of Other Ferrovanadium Alloys 407
13.6 The Technology of Nitrided Ferrovanadium 408
References 409

14. Technology of Niobium Ferroalloys

Mihail I. Casik
14.1 Properties of Niobium 411
14.2 Sources of Niobium and Its Reduction 415
14.2.1 Minerals of Niobium 415
14.2.2 Reduction of Niobium 416
Contents (^ xi ~)

14.3 Technology of Niobium Ferroalloys 416

References 419

15. Technology of Titanium Ferroalloys

Michael Gasik
15.1 Properties of Titanium and Its Compounds 421
15.2 Sources of Titanium and Methods of Its Reduction 425
15.2.1 Titanium Raw Materials 425
15.2.2 Reduction of Titanium from Oxides 428
15.3 Technology of Titanium Ferroalloys 429
References 432

16. Technology of Zirconium Ferroalloys

Michael Gasik
16.1 Properties of Zirconium and Its Main Compounds 435
16.2 Sources of Zirconium and Its Reduction 441
16.3 Technology of Zirconium Ferroalloys 443
16.3.1 Ferrosilicozirconium 443
16.3.2 Technology for Producing Ferro-aluminum-
zirconium 446
References 447

17. Boron Ferroalloys

Oleg Polyakov
17.1 Properties of Boron and Its Compounds 449
17.2 Boron Sources and Its Reduction 452
17.3 Technology of Boron Alloys 453
17.3.1 Boron Alloys Types 453
17.3.2 Ferroboron Technology 453
17.3.3 Technology of Other Boron Alloys 456
References 457

18. Technology of Ferroalloys with Rare-Earth Metals

Oleg Polyakov
18.1 Properties of Rare-Earth Metals and Their Compounds 459
18.1.1 Yttrium 461
18.1.2 Lanthanum 462
18.1.3 Cerium 464
18.2 Minerals, Ores, and Concentrates of Rare-Earth Metals 465
18.3 Technology for Producing Ferroalloys with REM 466
18.3.1 Reduction by Carbon 467
18.3.2 Reduction by Aluminum 468
References 469
Q xii ~) Contents

19. Technology of Ferroalloys with Alkaline-Earth Metals

Mihail I. Gasik
19.1 Calcium and Its Alloys 472
19.1.1 Properties of Calcium and Its Systems 472
19.1.2 Technology Used for Smelting Calcium Carbide 475
19.1.3 Smelting Technology Used for Calcium-Silicon
Alloy 477
19.2 Magnesium 480
19.2.1 Properties of Magnesium and Its Systems 480
19.2.2 Technology for Producing Magnesium
and Ferroalloys 483
19.3 Strontium 485
19.3.1 Properties of Strontium and Its Systems 485
19.3.2 Smelting Technology of Strontium Alloys 487
19.4 Barium 488
19.4.1 Properties of Barium and Its Systems 488
19.4.2 Smelting Technology of Ferrosilicobarium 490
19.4.3 Smelting Technology of Al-Ba Alloys 491
19.5 Metallurgical Lime 491
References 494

20. Complex Ferroalloys and Other Master Alloys

Oleg Polyakov
20.1 Complex Ferroalloys 495
20.1.1 Relevancy of Complex Ferroalloys Development 495
20.1.2 Ferroalloys and Master Alloys with Aluminum 496
20.1.3 Ferroalloys with Other Elements 498
20.2 Ferroalloys with Nonmetallic Elements 500
20.3 Exothermic Ferroalloys 503
References 504

General References 507

Index 509