Hydrometallurgy: Principles and Applications

551 Pages·2008·5.93 MB·English

by  Thomas Havlik

Hydrometallurgy
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Hydrometallurgy
Principles and applications
Tomás› Havlík
Cambridge International Science Publishing Limited
in association with
Woodhead Publishing Limited
CRC Press
Boca Raton Boston New York Washington, DC
W
OODHEAD PUBLISHING LIMITED
Cambridge, England
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Contents
Introduction....................................................................................... xi
1. Current situation in copper production...................................1
1.1. Copper hydrometallurgy........................................................................11
2. Ore minerals........................................................................... 17
3. Phase equilibrium of copper and
iron sulphides.......................................................................... 29
3.1. One-component systems.......................................................................29
3.1.1. Sulphur....................................................................................................29
3.1.1.1. Allotropic modifications of solid sulphur ............................................32
3.1.1.2. Phase diagram.........................................................................................37
3.2. Multi-component systems.....................................................................38
3.2.1. The copper–sulphur equilibrium phase system...................................38
3.2.2. The iron–sulphur equilibrium phase system........................................43
3.2.3. The copper–iron–sulphur equilibrium phase system..........................48
4. Equilibrium in aqueous solutions.......................................... 60
4.1. Ionic activities........................................................................................65
4.1.1. Debye–Hückel theory............................................................................ 65
4.1.1.1. Extension to more concentrated solutions...........................................69
4.1.1.2. Extension to mixed electrolytes.............................................................71
4.1.2. Pitzer method..........................................................................................72
4.1.2.1. Calculation of φ for salts in mixed electrolytes.....................................76
4.1.2.2. Calculation of γ for salts in mixed electrolytes.....................................78
4.1.2.3. Calculation of γ for single ions............................................................79
4.1.2.4. Studies of complex systems...................................................................80
4.2. Formation of metallic complexes and equilibrium constant ................81
4.3. Thermodynamics of equilibrium constants..........................................85
4.3.1. Selection of the values of equilibrium constants.................................91
5. Thermodynamic studies of heterogeneous systems
in an aqueous medium ........................................................... 96
5.1. Theoretical principle of the E–pH diagrams....................................... 100
5.1.1. pH and its principle.............................................................................. 102
5.1.2. Potential E and its principle................................................................. 104
5.2. Calculation and construction of E–pH diagrams............................... 113
5.2.1. E–pH diagrams at elevated temperatures........................................... 116
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5.3. Potential–pH diagrams in leaching of copper sulphides................... 127
5.3.1. S–H O equilibrium system ................................................................... 129
2
5.3.2. Cu–S–H O equilibrium system ............................................................ 145
2
5.3.3. Fe–S–H O equilibrium system............................................................. 153
2
5.3.4. Cu–Fe–S–H O equilibrium system...................................................... 154
2
5.3.5. Cu–S–Cl–H O equilibrium system....................................................... 157
2
5.3.6. Fe–S–Cl–H O equilibrium system....................................................... 159
2
5.3.7. Equilibrium diagram of the Cu–Fe–S–Cl–H O system....................... 163
2
5.4. Species diagrams.................................................................................. 167
6. Software and databases for thermodynamic calculations 173
7. Kinetics of heterogeneous reactions of leaching
processes .............................................................................. 184
7.1. Effect of variables on the kinetics of a heterogeneous reaction ...... 190
7.2. Elementary phenomena at the interface.............................................. 211
7.2.1. Intrinsic kinetics of heterogeneous reactions on solid surfaces...... 216
7.2.1.1. Kinetics of processes of leaching a single particle ........................... 216
7.2.1.2. Kinetics of leaching processes in multi-particle systems................. 228
8. Leaching in chloride media ................................................. 242
8.1. Main aspects of leaching chalcopyrite in a chloride medium........... 243
9. Extracting metals from solutions ....................................... 255
9.1. Cementation.......................................................................................... 255
9.2. Cementation of amalgams.................................................................... 259
9.3. Reduction with gaseous hydrogen..................................................... 261
9.4. Liquid extraction................................................................................... 264
9.5. Ion exchange......................................................................................... 268
9.6. Precipitation of sparingly soluble compounds.................................. 270
9.7. Crystallisation ...................................................................................... 274
9.8. Electrolysis and electrolytic refining.................................................. 276
9.8.1. Electrowinning of metals...................................................................... 278
9.8.2. Electrolytic refining.............................................................................. 289
10. Effect of the electronic structure on leaching of
sulphide semiconductors ..................................................... 294
10.1. Leaching kinetics and electrochemistry of sulphides ....................... 300
10.1.1. Leaching of chalcopyrite ..................................................................... 301
11. Experimental methods of investigating hydrometallurgical
processes .............................................................................. 309
11.1. Experimental methods of examination of leaching processes........... 315
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11.1.1. Leaching equipment............................................................................. 318
11.1.2. Experimental procedure........................................................................ 324
11.2. Changes of pH in relation to temperature .......................................... 334
12. Leaching of copper sulphides ............................................. 341
12.1. Copper sulphides of the Cu Fe S type............................................... 341
x y z
12.1.1. Leaching of chalcopyrite by ferric sulphate ...................................... 361
12.1.2. Leaching of chalcopyrite by ferric chloride ....................................... 364
12.1.3. Leaching of chalcopyrite by ferric chloride with the addition of
carbon tetrachloride............................................................................. 366
12.1.4. Leaching of chalcopyrite in sulphuric acid using ozone as the
oxidation agent..................................................................................... 368
12.1.5. Leaching of chalcopyrite in the high-frequency field....................... 375
12.1.6. Leaching of chalcopyrite in the microwave field ............................... 378
12.1.7. Leaching of chalcopyrite in the presence of deep nodules as an
oxidation agent..................................................................................... 384
12.2. Copper sulphides of the Cu S type..................................................... 388
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12.3. Copper sulphides of the type Cu Me S 398
...............................................................................
x y z
13. Morphology and behaviour of sulphur in the leaching
of sulphides........................................................................... 421
14. Study of the fine structure................................................... 444
14.1. Examples of the application of X-ray diffractometry in
hydrometallurgy................................................................................... 446
15. Mechanism of leaching of copper sulphides in an acid
medium .................................................................................. 468
16. The current state and prospects of hydrometallurgical
processes .............................................................................. 479
16.1. History of hydrometallurgical processes............................................ 484
Index ............................................................................................... 535
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This book is devoted to the life and work of Univ. Prof. Dr.-
Ing. Dr. h.c. mult. Roland Kammel – a friend, to whom I am
very grateful not only for his support in my professional field
but especially for his human approach.
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