Nowosielska 2017

The leaching of metal sulfides in
ammoniacal carbonate solutions
Anna Nowosielska
This thesis is presented for the Degree of Honours in Mineral Science,

Murdoch University
School of Engineering and Information Technology

June 2017
Supervisor : Dr. Aleks Nikoloski
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Declaration
I declare that this thesis is my own account of my research and

contains, as its main content, work which has not previously been
submitted for a degree or examination at any tertiary educational
institution.
Anna Nowosielska
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Abstract
The leaching of metal sulfides in ammoniacal solutions is of industrial importance for

the production of copper, nickel and cobalt. In some processes, such as the Sherritt
Gordon process, they are introduced as feed; while in others, such as the Caron process,
they form in-situ, as intermediate products. The focus of this study is to understand the
leaching behaviour of the in situ formed copper, nickel and cobalt sulfides, but the
findings are expected to be relevant to the other related systems.
The Caron process involves an oxidative dissolution of pre-reduced iron-based nickel

and cobalt alloy grains in an aqueous solution containing ammonia and ammonium
carbonate. Under the process conditions, these iron-based alloy grains undergo
passivation because of the formation of an iron oxide surface layer, as nickel and cobalt
become trapped within the passive iron matrix, resulting in reduced extractions.
Thiosulfate ions have been reported to facilitate the leaching process. The presence of
metal ammines and thiosulfate ions in the same system, however, has been observed to
result in a formation of a metal sulfide layer on the surface of the dissolving iron-based
alloy grains. This, on the other hand, results in a partial loss of nickel and cobalt from
the solution, while also further increasing the tendency for iron passivation. It has been
postulated, that after iron passivates, nickel and cobalt from the sulfide layer redissolve,
however, there is little evidence of this, or the effect of process parameters on the rate
and extent of such re-dissolution. The present study is aiming to shed some light on these
processes.
The dissolution of copper, nickel and cobalt sulfides was examined using three forms of
these compounds - metal sulfides formed electrochemically (EFMS) under simulated
Caron process leach conditions, synthetic monometallic metal sulfides (SMMS) and real
metal sulfides, naturally found in ore (RMS). In the first instance, electrochemically
formed metal sulfides were studied by techniques which included open circuit potential
and cyclic voltammetry measurements. The dissolution rate and extent of the nickel,
cobalt and copper from the metal sulfide was monitored.
The leaching of the synthetic monometallic metal sulfides was carried out under similar
conditions to those of the Caron process. The effects of key process parameters such as
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concentration of ammonia, concentration of ammonium carbonate and temperature
were investigated. The pH and Eh of the studied systems were monitored and solution
samples were analysed for Ni, Co and Cu. It was observed that the highest extraction of
nickel and copper from their respective metal sulfides was at 3M [NH3]T + 1M [CO2]T at
60 °C, whereas the maximum extraction of cobalt from cobalt sulfide was observed at
5M [NH3]T + 1M [CO2]T at 45 °C.
The kinetic data shows that leaching of nickel follows the ash layer diffusion model, with
the activation energy for the process reported as ‘different’ at the different tested
temperatures (69.6 kJ/mol at 25 °C and 14.7 kJ/mol at 60 °C). An attempt was made to
derive the reaction orders with respect to ammonia (0.18) and ammonium carbonate
(0.09). The available data is possibly not very reliable, however.
The rate of copper leaching shows that the surface reaction model applies best to this
system. The activation energy was 11.5 kJ/mol at 25 °C and 57.6 kJ/mol at 60 °C. The
reaction order with respect to ammonia was 1.9 and for ammonium carbonate it was 4.0.
The leaching kinetic data for cobalt from monometallic cobalt sulfide, showed that the
process follows the surface reaction model similar to copper, with a steady activation
energy of 6.5 kJ/mol. In contrast to nickel, the leaching of cobalt from cobalt sulfide had
a higher order with respect to ammonium carbonate of 1.8 than with respect to ammonia
of 0.9.
The observed leaching behaviour of the electrochemically formed metal sulfides (EFMS)
and the synthetic monometallic metal sulfides (SMMS) was compared to leaching of real
metal sulfides naturally found in ore (RMS) by testing flotation concentrate under the
conditions which gave the highest extractions for the former. Tested were two types of
flotation concentrate, one containing high nickel sulfide and another containing high
copper sulfide. A sample of cobalt sulfide was not available. In these experiments, the
effect of adding 0.25M sodium sulfite (Na2SO3) was also examined. The results have
shown that the addition of sulfite improved both rate and extent of the extraction of
nickel. It significantly hindered the extraction of copper, however. Namely, the rate of
nickel extraction with sodium sulfite present was approximately 1.31 mg/L/min vs. 0.07
mg/L/min without it. The rate of copper extraction on the other hand, decreased from
4.09 mg/L/min without sodium sulfite, to just 0.89 mg/L/min when it was added. On
the basis of this data, and assuming similar behaviour between copper and cobalt
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sulfides, it does not appear that addition of sodium sulfite could reduce the losses of
copper and cobalt from the system.
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Table of Contents
Abstract .................................................................................................................................................. iv
Table of Contents .............................................................................................................................. vii
List of Figures ..................................................................................................................................... ix
List of Tables .....................................................................................................................................xiv
List of Appendices ............................................................................................................................. xv
Abbreviations ....................................................................................................................................xvi
Acknowledgements......................................................................................................................... xviii
1 INTRODUCTION ............................................................................................................................... 1
2 LITERATURE REVIEW ....................................................................................................................... 2
2.1 ORE DEPOSITS, MINERALOGY AND PROCESSING ................................................................... 2
2.2 AMMONIACAL LEACHING PROCESS ........................................................................................ 5
2.2.1 The Caron Process ........................................................................................................... 7
2.2.2 The Sherritt Gordon Process ........................................................................................... 9
2.3 FACTORS AFFECTING NICKEL AND COBALT EXTRACTION ..................................................... 11
2.4 IRON PASSIVATION LAYER FORMATION ............................................................................... 13
2.5 ELECTROCHEMICAL PRINCIPLES............................................................................................ 16
2.5.1 Metal Electrolyte Interface - The Electrical Double Layer ............................................ 16
2.5.2 Corrosion Potential ....................................................................................................... 18
2.5.3 Mixed Potential Theory ................................................................................................. 20
2.5.4 Cyclic Voltammetry ....................................................................................................... 22
2.5.5 Passivity of Metals ........................................................................................................ 24
2.5.6 In situ XRD Electrochemical Analysis ............................................................................ 25
3 EXPERIMENTAL MATERIALS AND METHODS ................................................................................ 30
3.1 MATERIALS ............................................................................................................................ 30
3.1.1 Electrochemically formed Metal Sulfides (EFMS) ......................................................... 30
3.1.2 Synthetic Monometallic Metal Sulfides (SMMS) .......................................................... 30
3.1.3 Flotation Concentrate Samples (RMS) .......................................................................... 30
3.1.4 Test Solutions ................................................................................................................ 30
3.2 METHODS USED FOR ELECTROCHEMICAL STUDY ................................................................ 31
3.2.1 Electrochemical Apparatus ........................................................................................... 31
3.2.2 OCP Measurements ...................................................................................................... 32
3.2.3 Rotating Disk Cyclic Voltammetry ................................................................................. 32
3.2.4 SEM/EDX Surface Analysis ............................................................................................ 33
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3.2.5 Dissolution Studies ........................................................................................................ 33
3.3 LEACHING METHODS ............................................................................................................ 33
3.3.1 Leaching of Synthetic Monometallic Metal Sulfides (SMMS) ....................................... 33
3.3.2 Kinetic model for Synthetic Monometallic Metal Sulfides ........................................... 34
3.3.3 Leaching of Flotation Concentrate (RMS) ..................................................................... 35
4 RESULTS AND DISCUSSION............................................................................................................ 36
4.1 THE INVESTIGATION OF NICKEL SULFIDE .............................................................................. 36
4.1.1 Electrochemical Testwork ............................................................................................. 36
4.1.2 Leaching of a Synthetic Sample (SMMS) ....................................................................... 40
4.2 THE INVESTIGATION OF COBALT SULFIDE ............................................................................ 57
4.3 THE INVESTIGATION OF COPPER SULFIDE ............................................................................ 76
4.4 COMPARISON OF REACTION RATES AND EXTENTS OF LEACHING ....................................... 98
5 CONCLUSIONS ............................................................................................................................... 99
6 REFERENCES ................................................................................................................................ 102
7 APPENDICES ................................................................................................................................ 110
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List of Figures
FIGURE 1. Nickel production and resources (World resources on land) left, and (Nickel production in
2009) right, of laterite and sulfide ores (Oxley et al., 2016). .................................................................. 2
FIGURE 2. Past and future predictions of nickel production from laterite and sulfide ores (Oxley et al.,
2016). ...................................................................................................................................................... 2
FIGURE 3. Generalised laterite processing flowsheets (Norgate and Jahanshahi, 2011)....................... 4
FIGURE 4. A flowsheet showing the Sherritt Gordon process. ............................................................. 10
FIGURE 5. The electric field consisting of two layers of charge – The Electrical Double Layer
(faculty.kfupm.edu.sa) .......................................................................................................................... 18
FIGURE 6. Polarization curves of corrosion reactions, where ia is the anodic reaction current, ic is the
cathodic reaction current, icorr is the corrosion current, Ea is the equilibrium potential of the cathodic
reaction, Ec is the equilibrium potential of the cathodic reaction and Ecorr is the corrosion potential
(Sato, 2012). .......................................................................................................................................... 19
FIGURE 7. A schematic representation of the Mixed Potential Theory for two redox couples
(Nikoloski, 2002). .................................................................................................................................. 22
FIGURE 8. Potential versus time profile applied to the working electrode (Compton and Banks, 2007).
.............................................................................................................................................................. 23
FIGURE 9.Current versus potential Cyclic Voltammogram (Compton and Banks, 2007). .................... 23
FIGURE 10. A schematic representation of current-potential relationship as metal undergoes
passivation (Bockris and Reddy, 1970). ................................................................................................ 24
FIGURE 11. Different cell configurations in reflection and transmission geometries. Thick black arrow
shows the path of X-ray beam; dashed arrows show the scattered beam (De Marco and Veder,
2010). .................................................................................................................................................... 26
FIGURE 12. Synchrotron radiation X-ray real time images of nickel morphology deposited at pH 10
(a) -1.2V, (b) -1.4V and (c) -1.6V (Song et al., 2016). ............................................................................ 27
FIGURE 13.SEM micrographs showing nickel electrodeposition obtained at different potentials
(deposition time of 400s) (a) -1.2V, (b) -1.4V and (c) -1.6V (Song et al., 2016). ................................... 27
FIGURE 14. Schematic of the electrochemical flow cell (a) exploded view of the cell with its main
components, (b) partial section view of the assembled cell, highlighting the path of the flowing
electrolyte solution, and (c) top view of the cell (Clancy et al., 2015). ................................................ 28
FIGURE 15. Schematic diagram of an electrochemical cell used for in-situ X-ray analyses. Upper
diagram shows a side profile of the cell; lower diagram shows a top profile (Veder et al., 2011). ..... 29
FIGURE 16. Electrochemical set-up, showing working electrode (WE), counter electrode (CE),
reference electrode (RE), Luggin capillary(LC) (D’Aloya, 2015). ........................................................... 32
FIGURE 17. Schematics of the leaching set up. .................................................................................... 34
FIGURE 18. OCP of iron in a deoxygenated ammoniacal-carbonate solution containing 0.15M nickel
(II) and 0.022M thiosulfate ions. ........................................................................................................... 36
FIGURE 19. CV of iron following different times of immersion in a deoxygenated Ni (II) thiosulfate
ammoniacal-carbonate solution. .......................................................................................................... 37
FIGURE 20. SEM image of iron RDE following 3 hour immersion in a 3M [NH3]T and 1M [CO2]T
containing 0.15M Ni(II) and 0.022M S2O32-. ......................................................................................... 39
FIGURE 21. Nickel dissolution from iron RDE in 5M [NH3]T + 1M [CO2]T following pre-treatment in 3M
[NH3]T + 1M [CO2]T + 0.15M Ni(II) + 0.022M S2O32- solution. ................................................................ 40
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FIGURE 22. SEM/EDX analysis of the nickel sulfide sample used in the leaching tests (A) SEM image of
the nickel sulfide particles, (B) corresponding spectra for image (A), and (C) EDX image showing the
spots that were quantitatively analysed............................................................................................... 41
FIGURE 23. The effect of ammonia concentration on the leaching efficiency of nickel from nickel
sulfide. ................................................................................................................................................... 43
FIGURE 24. The effect of ammonium carbonate concentration on the leaching efficiency of nickel
from nickel sulfide................................................................................................................................. 45
FIGURE 25. The effect of temperature on the leaching efficiency of nickel from nickel sulfide. ........ 47
FIGURE 26. The effect of sodium sulfite addition on the leaching efficiency of nickel from nickel
sulfide. ................................................................................................................................................... 48
FIGURE 27. Plot of surface reaction model vs time for the leaching of nickel from nickel sulfide at
different temperatures. ........................................................................................................................ 49
FIGURE 28. Plot of ash layer diffusion model vs time for the leaching of nickel from nickel sulfide at
FIGURE 29. Plot of the mixed model vs time for the leaching of nickel from nickel sulfide at different
temperatures. ....................................................................................................................................... 50
FIGURE 30. Arrhenius plot for nickel leaching from nickel sulfide. ...................................................... 52
FIGURE 31. Plot of –log k vs log [NH3] for reaction order estimation................................................... 52
FIGURE 32. Plot of – log k vs log [CO2] for reaction order estimation. ................................................. 53
FIGURE 33. The effect of sodium sulfite addition on the leaching of nickel from nickel flotation
concentrate. .......................................................................................................................................... 54
FIGURE 34. SEM images of (A) nickel feed, (B) Leach Residue A, and (C) Leach Residue B. ................ 56
FIGURE 35. OCP of iron immersed in a deoxygenated ammoniacal-carbonate solution containing
cobalt (II) and thiosulfate ions. ............................................................................................................. 57
FIGURE 36. CV of iron following different immersion times in a deoxygenated Co (II) thiosulfate
ammoniacal solution............................................................................................................................. 58
FIGURE 37. SEM image of the iron RDE following 3 hour immersion in 5M[NH3]T and 1M[CO2]T
containing 0.012M Co(II) and 0.022M S2O32- a) image of a larger area, b) close up on spot marked
with an arrow. ....................................................................................................................................... 60
FIGURE 38. Cobalt dissolution from iron RDE in a 5M [NH3]T + 1M [CO2]T following pre-treatment in
5M [NH3]T + 1M [CO2]T + 0.012M Co(II) + 0.022M S2O32- solution. ....................................................... 61
FIGURE 39. SEM/EDX analysis of the cobalt sulfide sample used in the leaching tests (A) SEM image
of the cobalt sulfide particles, (B) corresponding spectra for image (A), and (C) EDX image showing
the spots that were quantitatively analysed. ....................................................................................... 62
FIGURE 40. The effect of ammonia concentration on the leaching efficiency of cobalt from cobalt
sulfide. ................................................................................................................................................... 64
FIGURE 41. The effect of ammonium carbonate concentration on the leaching efficiency of cobalt
from cobalt sulfide. ............................................................................................................................... 67
FIGURE 42. The effect of temperature on the leaching efficiency of cobalt from cobalt sulfide........ 68
FIGURE 43. The effect of sodium sulfite addition on the leaching efficiency of cobalt from cobalt
sulfide. ................................................................................................................................................... 70
FIGURE 44. Plot of surface reaction model vs time for the leaching of cobalt from cobalt sulfide at
FIGURE 45. Plot of ash layer diffusion model vs time for the leaching of cobalt from cobalt sulfide at
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FIGURE 46. Plot of the mixed model vs time for the leaching of cobalt from cobalt sulfide at
FIGURE 47. Arrhenius plot for cobalt leaching from cobalt sulfide. ..................................................... 74
FIGURE 49. Plot of –log k vs log [CO2] for reaction order estimation. .................................................. 75
copper (II) and thiosulfate ions. ............................................................................................................ 76
FIGURE 51. CV of iron following different immersion times in a deoxygenated Cu (II) thiosulfate
ammoniacal solution............................................................................................................................. 77
FIGURE 52. SEM images of the different areas on the surface of the iron RDE following 3 hour
immersion in 5M [NH3]T and 1M [CO2]T containing 0.008M Cu (II) and 0.022M S2O32-. ...................... 79
FIGURE 53. Copper dissolution from iron RDE in 5M[NH3]T + 1M[CO2]T following pre-treatment in
5M[NH3]T + 1M[CO2]T + 0.008M Cu(II) + 0.022M S2O32- solution. ........................................................ 80
FIGURE 54. SEM/EDX analysis of the copper sulfide sample used in the leaching tests. (A) SEM image
of the copper sulfide particles, (B) corresponding spectra for image (A), and (C) EDX image showing
spots that were quantitatively analysed............................................................................................... 81
FIGURE 55. The effect of ammonia concentration on the leaching efficiency of copper from copper
sulfide. ................................................................................................................................................... 84
FIGURE 56. Stability limits of Cu2+ in ammoniacal solution (Ek et al., 1982). ...................................... 85
FIGURE 57. The effect of ammonium carbonate concentration on the leaching efficiency of copper
from copper sulfide............................................................................................................................... 86
FIGURE 58. The effect of temperature on the leaching efficiency of copper from copper sulfide. ..... 88
FIGURE 59. The effect of sodium sulfite addition on the leaching efficiency of copper from copper
sulfide. ................................................................................................................................................... 89
FIGURE 60. Plot of surface reaction model vs time for leaching of copper from copper sulfide at
FIGURE 61. Plot of ash layer diffusion model vs time leaching of copper from copper sulfide at
FIGURE 62. Plot of the mixed model vs time for leaching of copper from copper sulfide at different
temperatures. ....................................................................................................................................... 91
FIGURE 63. Arrhenius plot for copper leaching from copper sulfide. .................................................. 93
FIGURE 65. Plot of –log k vs log [CO2] for reaction order estimation. .................................................. 94
FIGURE 66. The effect of sodium sulfite addition on the leaching efficiency of copper from
chalcopyrite flotation concentrate. ...................................................................................................... 95
FIGURE 67. SEM image of (A) copper feed, (B) leach residue A and (C) leach residue B. .................... 97
FIGURE 68. Electrochemical set-up. ................................................................................................... 110
FIGURE 69. Electrochemical cell used in this project ......................................................................... 111
FIGURE 70. Iron RDE used in this project............................................................................................ 112
FIGURE 71. Leaching set up. ............................................................................................................... 113
FIGURE 72. Leaching data 1. ............................................................................................................... 114
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FIGURE 81. Leaching data 11. ............................................................................................................. 123
FIGURE 90. Dissolution of nickel sulfide. ........................................................................................... 132
FIGURE 91. Dissolution of cobalt sulfide. ........................................................................................... 132
FIGURE 92. Dissolution of copper sulfide. .......................................................................................... 132
FIGURE 93. XRD analysis of nickel sulfide. .......................................................................................... 133
FIGURE 94. XRD analysis of cobalt sulfide. ......................................................................................... 133
FIGURE 95. XRD analysis of copper sulfide. ........................................................................................ 133
FIGURE 96. Plot of surface reaction model vs time for leaching nickel from nickel sulfide at different
ammonia concentrations. ................................................................................................................... 134
FIGURE 97. Plot of ash layer diffusion model vs time for leaching nickel from nickel sulfide at
different ammonia concentrations. .................................................................................................... 134
FIGURE 98. Plot of the mixed model vs time for leaching nickel from nickel sulfide at different
FIGURE 99. Plot of surface reaction model vs time for leaching nickel from nickel sulfide at different
ammonium carbonate concentrations. .............................................................................................. 135
different ammonium carbonate concentrations. ............................................................................... 136
FIGURE 102. Plot of surface reaction model vs time for leaching cobalt from cobalt sulfide at
FIGURE 103. Plot of ash layer diffusion model vs time for leaching cobalt from cobalt sulfide at
FIGURE 104. Plot of the mixed model vs time for leaching cobalt from cobalt sulfide at different
FIGURE 108. Plot of surface reaction model vs time for leaching copper from copper sulfide at
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FIGURE 109. Plot of ash layer diffusion model vs time for leaching copper from copper sulfide at
FIGURE 110. Plot of the mixed model vs time for leaching copper from copper sulfide at different
FIGURE 111 . Plot of surface reaction model vs time for leaching copper from copper sulfide at
FIGURE 112. Plot of ash layer diffusion vs time for leaching copper from copper sulfide at different
FIGURE 114. Reagent amounts calculations. ...................................................................................... 143
FIGURE 115. XRD analysis of Nickel Sulfide flotation concentrate feed............................................. 144
FIGURE 116. XRD analysis of Nickel Leach Residue A. ........................................................................ 144
FIGURE 117. XRD analysis of Nickel Leach Residue B. ........................................................................ 145
FIGURE 118. XRD analysis of Copper Sulfide flotation concentrate feed. .......................................... 145
FIGURE 119. XRD analysis of Copper Leach Residue A. ...................................................................... 146
FIGURE 120. XRD analysis of Copper Leach Residue B. ...................................................................... 146
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List of Tables
TABLE 1. Solution compositions used in the electrochemical portion of this project. ........................ 31
TABLE 2. Elemental composition of the nickel sulfide feed (Figure 22 (A)) and the elemental
composition of the feed at certain spots from Figure 22 (C)................................................................ 42
TABLE 3. Nickel leaching summary. ..................................................................................................... 43
TABLE 4. Correlation coefficients for the different models at various leaching conditions of nickel
sulfide. ................................................................................................................................................... 51
TABLE 5. Elemental composition of the Nickel Sulfide flotation feed and both leach residues. ......... 55
TABLE 6. Mass (%) composition of cobalt sulfide feed sample used and mineral composition at
certain spots from Figure 39 (C). .......................................................................................................... 62
TABLE 7. Cobalt leaching summary. ..................................................................................................... 63
TABLE 8. Correlation coefficients for the different models at various leaching conditions of cobalt
sulfide. ................................................................................................................................................... 73
TABLE 9. Mass (%) composition of the copper sulfide feed sample used and the mineral composition
at certain spots from Figure 54 (C). ...................................................................................................... 81
TABLE 10. Copper leaching summary. .................................................................................................. 83
TABLE 11. Correlation coefficients for the different models at various leaching conditions of copper
sulfide. ................................................................................................................................................... 92
TABLE 12. Elemental composition of the copper sulfide flotation concentrate feed and both leach
residues. ................................................................................................................................................ 96
TABLE 13. Comparison of the reaction rates and efficiencies for the different metal sulfides analysed
in this project. ....................................................................................................................................... 98
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List of Appendices
APPENDIX A. Equipment used in the project ..................................................................................... 110
APPENDIX B. SMMS leaching data and calculations .......................................................................... 114
APPENDIX C. EFMS dissolution data ................................................................................................... 132
APPENDIX D. SMMS XRD data ............................................................................................................ 133
APPENDIX E. SMMS kinetic model plots ............................................................................................ 134
APPENDIX F. Amount of reagents calculations .................................................................................. 143
APPENDIX G. RMS XRD data ............................................................................................................... 144
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Abbreviations
- Total Concentration of Carbonate species
- Total Concentration of Ammonia species
- Concentration of Ammonia added as

- Activation Energy (kJ/mol)
- Equilibrium Potential of Anodic Reaction
- Equilibrium Potential of Cathodic Reaction
- Corrosion Potential
- Partial Reaction Equilibrium Potential
- Steady State Mixed Potential
- Passivation Potential
- Anodic Peak Potential
- Cathodic Peak Potential
- Anodic Half-reaction
- Cathodic Half-reaction
- Exchange Current Density
- Cathodic Current Density
- Anodic Current Density
- Anodic Reaction Current
- Cathodic Reaction Current
- Corrosion Current
- Apparent rate constants
- Atomic Absorption Spectrophotometry
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- Counter Electrode
- Electrode Potential
- Electrical Double Layer
- Electrochemically Formed Metal Sulfides
- Faraday’s Constant
- Grazing Incidence X-ray Diffraction
- Luggin Capillary
- Mixed Hydroxide Precipitate
- Metal Oxide
- Nitrogen Line
- Universal Molar Gas Constant
- Rotating Disk Electrode
- Reference Electrode
- Real Metal Sulfides
- Saturated Calomel Electrode
- Scanning Electrode Microscopy
- Synthetic Monometallic Metal Sulfides
- Solvent Extraction and Electrowinning
- Soft X-ray Microscopy
- Working Electrode
- X-ray Diffraction
- Fraction Extracted
- Transfer Coefficient
- Electrode Overpotential
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Acknowledgements
First and foremost, I would like to thank my supervisor, Dr. Aleks
Nikoloski for providing me with endless guidance, support and advice.
I am forever grateful for all his time and dedication spent in
mentoring me throughout this challenging journey.
I would like to express my gratitude to Dr. Drew Parsons for always
being willing to help when I needed a question answered.
Special thanks to Rorie Gilligan for his time and assistance in the
laboratory.
I wish to place my sincere thanks to Dr. David Hough for his
invaluable input.
I would also like to take this opportunity to acknowledge the other
faculty in the School of Engineering and Information Technology at
Murdoch University. Their teachings have guided my academic
progress and have changed the ways in which I engage with the
world.
Finally, I would like to thank my friends and family for their
unconditional love, support, advice and encouragement. Without
them, none of this would indeed be possible.
I would like to dedicate this work to the memory of my father –
Marek.
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1 INTRODUCTION
In an ammoniacal carbonate leaching nickel, cobalt and copper sulfides are introduced
as either feed material (Sherritt Gordon process) or as formed intermediate products in
the Caron process. The Caron process is a combined pyro-metallurgical and hydro-
metallurgical process of extracting nickel and cobalt from nickel laterite ores. First, the
ore is heated up to ~700°C in a reducing atmosphere, allowing the nickel and cobalt to
be reduced to their metallic states. There are no free nickel and cobalt minerals in the
nickel laterite ore, the reduced metals will, therefore, be associated with iron (Valix and
Cheung, 2002). After the roasting stage, the calcine is cooled down to stop the nickel and
cobalt from oxidizing. An ammonia-ammonium carbonate solution is used to selectively
leach out these alloys, as both nickel and cobalt form stable ammine complexes (Valix
and Cheung, 2002). Boiling will remove the ammonia and allow the basic nickel
carbonate to precipitate out, resulting in nickel oxide being produced at 1200°C. Under
the atmosphere of hydrogen, this nickel oxide will be converted to nickel metal in
reduction furnaces (Norgate and Jahanshahi, 2011). The main advantages of this process
are its great selectivity towards the metal values, and the fact that ammonia can be
recycled in the leaching circuit.
Due to a low metal recovery of ~80% for nickel and ~60% for cobalt, however, the
Caron process has lacked popularity. Over the years the causes of this poor metal
recovery have been studied, but the observed behaviour is still unclear. A deeper
understanding of these limiting factors could help in optimising the current conditions,
leading to a higher metal recovery.
The main objective of this study is to provide a valuable insight into the leaching of
metal sulfides in a solution containing ammonia, ammonium carbonate and thiosulfate
ions. By studying the effects of the different operating conditions, the limiting factors in
the leaching mechanisms can be determined. This study aims to gain a better
understanding of how the leaching mechanisms respond to various conditions, and how
these conditions can improve the effectiveness of the Caron process.
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2 LITERATURE REVIEW
2.1 ORE DEPOSITS, MINERALOGY AND PROCESSING
Nickel (Ni) is an important metal used in the modern infrastructure and technology
(Wood, 2013). Major uses of nickel include stainless steel (~65%), metal alloys (~20%),
electroplating (~9%) and rechargeable batteries (~5%) (Mudd, 2009 & 2010). From a
metallurgical perspective nickel has a number of benefits, such as a high melting point of
1453°C, ferromagnetic properties as well as catalytic behaviour (Moskalyk and
Alfantazi, 2002).
World’s resources of nickel are present as two ore types - sulfide and laterite ores.
Figure 1 shows the nickel resources and production from laterite and sulfide ores, and
Figure 2 shows predictions for the future.
FIGURE 1. Nickel production and resources (World resources on land) left, and (Nickel production
in 2009) right, of laterite and sulfide ores (Oxley et al., 2016).
FIGURE 2. Past and future predictions of nickel production from laterite and sulfide ores (Oxley et
al., 2016).
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Nickel sulfide ores derived from hydrothermal processes, often involving copper, cobalt
and sometimes platinum group metals (Oxley et al., 2016; Mudd, 2009). The production
of nickel from sulfide ores requires open cut or underground mining, a concentration
technique (flotation), smelting to produce nickel matte, followed by the refining of matte
to produce pure metal (Mudd, 2009).
Nickel laterite ores were formed as a result of extensive weathering over time, in the
tropical climates around the equator (Mudd, 2009). The main areas of nickel laterite
resources in the world are located in New Caledonia, Australia, Indonesia, South
America and the Philippines (Farrokhpay and Filippov, 2016). It has been noted that
because of the complexity of nickel laterite ores, the deposits located at the same regions
can be quite variable in nature (McDonald and Whittington, 2008).
Nickel laterite deposits are usually divided into three different zones: limonite (oxide),
nontronite (clay) and saprolite (silicate) zones (Forrokhpay and Filippov, 2016).
Saprolite, the lowest of these layers reflects the early stages of the weathering process,
and usually contains only around 1.5-3% nickel. The formula for the major mineral is
(Ni,Mg)6Si4O10(OH)8 (Pickles, 2003). The middle layer, nontronite zone, contains mostly
clay and quartz. Limonite, the top zone, consists of goethite and amorphous ferric
hydroxide, and is a result of further weathering (Farrokhpay and Filippav, 2016). The
chemical formula of limonitic type ore is (Fe,Ni)O(OH).n H2O (Pickles, 2003).
Production of nickel from laterite ore is more complex than from sulfide ores (Mudd,
2009; Rice, 2016; Farrokhpay and Filippov, 2016; Norgate and Jahanshahi, 2011). L
The laterite ore mines are all open-cut, due to a large area and shallow nature of this ore.
Figure 3 shows the typical processing routes for the different laterite ores.
3|Page
FIGURE 3. Generalised laterite processing flowsheets (Norgate and Jahanshahi, 2011).
One of the main reasons for the difficulty associated with the processing of nickel from
laterite ores is that these types of ores cannot be significantly upgraded or concentrated
prior to processing (Norgate and Jahanshahi, 2011). Nearly every tonne of the ore mined
needs to be put through the entire process, resulting in very high operating costs. The
complex structure of the laterite ores has prevented the nickel grade from being pre-
concentrated by means of physical beneficiation methods. Some techniques which
include sizing, gravity and magnetic separation either individually or in combinations
have been employed to upgrade/beneficiate the laterite ores. In most cases, however,
these techniques were not able to dramatically improve the quality of the feed (Quast et
al., 2015). Quast et al. (2015), reported that the most commonly used pre-concentration
process was the removal of coarse fraction from the feed, which has been noted to have a
much lower nickel content than the finer material. Lu et al. (2013), reported that nickel in
nickel laterite ore is finely disseminated in the molecular lattice of goethite or hydroxyl
silicate. In this study, Lu et al. (2013), have documented that pyro-metallurgical
techniques are well suited to treating saprolite ore, where the garnierite content is high
and iron content is low.
Another problem arising from the present treatment of laterite ores is the fact that nickel
oxide ores may contain around 45% of water, both as free moisture and also as water
4|Page
chemically combined in hydrated minerals, which means that thermal reduction of the
laterite ore is required prior to processing (Moskalyk and Alfantazi, 2002).
2.2 AMMONIACAL LEACHING PROCESS

Leaching has been described as a primary extractive operation in hydrometallurgy. The
process involves the dissolution of a valuable mineral as the ore comes in contact with an
active chemical solution, known as the leach liquor. This dissolution process is selective,
affecting only the chosen component, with the unwanted (gangue) components
remaining in the solid state. The valuable metal can then be extracted, as the solids are
separated from the leach liquor at the end of the process (Gupta, 2003).
For the efficient leaching of a metal from its ore, the appropriate chemical reactions must
take place, and these reactions are governed by the thermodynamic characteristics of the
particular reaction system, as well as the solubility of the species in the aqueous solution
(Mathobi, 2012).
According to Woollacott and Eric (1994), the following mechanisms will be involved in
a single stage leaching process:
1) There must be a diffusion of the reagents to the mineral surface, as well as

adsorption of the reagents on the surface, while an active chemical reaction is
taking place on the surface, and
2) There must be desorption and diffusion of the reaction products from the surface
into the bulk of the solution.
The rate of the extraction will be controlled by the slowest of these mechanisms. There
are a number of parameters affecting the efficiency of the metal extraction. The size of
the particles, (in other words, the degree of exposure), will affect the rate of leaching,
generally increasing the rate as the particle size decreases. The diffusion rate of reactants
and products will also influence the rate of leaching. This can be improved by an
increase in the degree of agitation of the leach solution. When the rate of chemical
reaction influences the rate of leaching, this can be improved by increasing the degree of
exposure of the valuable metal, or increasing the temperature or pressure of the leaching
system. The rate of leaching will increase with the increase in the concentration of the
leaching agent, and with decreasing pulp density. The rate will also be influenced by a
5|Page
possible insoluble reaction product formed during leaching, with the rate of leaching
dependent on the nature of this product (Woollacott and Eric, 1994).
Metal sulfides are insoluble in water. In the presence of oxygen, however, they will be
solubilised as sulfates. According to Habashi (1970), the desired residue product from the
oxidation of sulfides will be not only sulfates, but elemental sulfur as well. When
leaching sulfides, the temperature and the pH at which the leaching will take place need
to considered. Depending on these two factors, there is a possibility of obtaining both
metal and sulfur in soluble form, with sulfur recovered as ammonium sulfate (Habashi,
1970).
The electrochemical mechanism of leaching sulfides can be represented by the following

reactions:
Cathodic Reaction: [Eq.1]
Anodic Reaction: [Eq.2]
An ammonia-ammonium carbonate system was first used to recover non-ferrous metals

such as copper from oxide ores (Radmehr et al., 2014), but gradually this method was
developed to extract nickel and cobalt as well as other traditional elements. Aqueous
ammonia has been an effective lixiviant, forming stable metal ion ammine complexes
with base metal cations, while rejecting iron (Moyo and Petersen, 2016). Ammonia in
the complex ligands binds to the metal ions through the reactive nitrogen-containing
group, which in turn leads to a higher solubility (Nabizadeh and Aghazadeh, 2015).
According to Meng and Han (1995), there are three main methods of ammonia leaching:
neutral, oxide and the reduction method. During the neutral method, metals will be
leached without the presence of any oxidizing or reducing agents. Most copper and zinc
oxides are leached under this method. The oxide method, is a method which requires the
use of an oxidizer in order to oxidize the solids, such as sulfide minerals. The last type of
method is the reduction method, where a reducing agent is used for dissolving metals
from highly oxidized ores.
Ammonia leaching has a number of advantages over other leaching methods (Radmehr
et al., 2014; Meng and Han, 1995; Wei Wei, 2016; Wetham et al., 2015 and Katsiapi et
al., 2010), which include low toxicity, low cost and the ease of regeneration.
6|Page
The chemistry of the oxidative ammonia leaching is quite complex, and involves a
number of steps. The sulfide component is oxidized to soluble species, mostly sulfate
(SO42-) together with the thiosulfate (S2O32-) and sulfamate (NH4SO3NH2). The iron
component will be oxidized to the +3 state, and later precipitated as hydrated ferric
oxide (Fe2O3.H2O). The metal ion will be released in its +2 oxidation state, and
stabilized by the formation of ammine complexes with NH3 ligands (Nabizadeh and
Aghazadeh, 2015).
Katsiapi et al. 2010 presented the dissolution of divalent metal oxide (MeO) in an
ammonia solution by following:
[Eq.3]
There are two main types of ammoniacal leaching processes currently used around the
world, the Caron process and the Sherrit Gordon process.
2.2.1 The Caron Process

The Caron process (Caron, 1955) was first used in the 1950s for the extraction of nickel
and cobalt in the ammoniacal solution (Zuniga et al., 2010). Since then, this process has
been applied in Cuba (Nicaro), Australia (Townsville), the Philippines (Mavinduque)
and China (Qinghai) as well as in Brazil (Niquelandia), where nickel has mainly been
associated with copper rather than cobalt (Ma et al., 2013).
The Caron process has been successfully used for processing nickel laterite ores. It
provides a combined pyro/hydro-metallurgical approach to nickel and cobalt recovery
(Lu et al., 2013; Mudd, 2009; Rice, 2016; Valix and Cheung, 2002; Norgate and
Jahanshahi, 2011). This process consists of drying and grinding laterite ore, reduction
roasting, leaching with ammoniacal-ammonium carbonate solution to dissolve nickel
and cobalt as ammine complexes, and the recovery of base metal from solution to
produce a nickel oxide product (Moskalyk and Alfantazi, 2002).
The Caron process has proved successful for application to processing of low-grade
nickel laterite oxides (~1.5% Ni, ~0.1% Co) (Valix and Cheung, 2002), in particular has
7|Page
been successfully applied to ores with high goethite (FeOOH) or limonite ores, and ores
with low silicate content (Norgate and Jahanshahi, 2011). Norgate and Jahanshahi
(2011) noted that with the increase of saprolite, the recovery of nickel and cobalt will be
reduced, because nickel and cobalt are locked in a silicate matrix and become difficult to
reduce at 700°C.
Rice (2016) reported that limonite ores with a lower magnesia content responded better
to the hydro-metallurgical techniques of the Caron process, and it has also been noted
that this process can tolerate higher amounts of magnesium than any other process
currently used. When the Caron process was studied in the extraction of nickel from
high silicate ores, it was documented that the control of the reduction conditions was
critical for the recovery of nickel from these ores as well as for better iron separation
(Rice, 2016).
Results from Valix and Cheung (2002) study showed that the temperature of the
reduction had a significant effect on the recovery of both nickel and cobalt. The authors
of this report presented the optimum nickel and cobalt recovery conditions from
limonite, with increasing the temperature up to 600°C as recommended, while the
weathered saprolite reduction was favoured at ~800°C. It was noted that at this
temperature, an association with a complete dehydration is achieved, but if the
temperature is being increased further, the recovery will in fact be reduced (Valix and
Cheung, 2002). The phases which form at 800°C will not be reversed upon cooling the
laterite ore (Valix and Cheung, 2002).
Ma et al. (2013), described the Caron process as particularly effective in the treatment of
high goethite containing limonitic laterite ores. This is because silicate-rich minerals tend
to undergo phase transformation during the reduction roasting stage, which impedes the
extraction of nickel (Ma et al., 2013).
There have been a number of problems associated with the current Caron process,
however, reported in the literature (Norgate and Jaharshahi, 2011; Senanayake et al.,
2010; Zuniga et al., 2010; Dyer et al., 2012). The processes involved in the pyro-
metallurgical stage of the Caron process (drying, calcining and reduction) are all energy
intensive and costly (Norgate and Jahanshahi, 2011; Senanayake et al., 2010). The
leaching kinetics of the process are still slow and limited to ~80-86% Ni and ~50-60% Co
8|Page
extractions (Dyer et al., 2012). These require various reagents, high temperature,
ammonia and metallic iron concentrations (Zuniga et al., 2010), and there is still a high
nickel and cobalt content waste in the tailings (Senanayake et al., 2010).
2.2.2 The Sherritt Gordon Process

The developments of ammonia leaching processes gained popularity from their initial
applications to the developments of the base metals recovery. In 1947, Sherritt Gordon
invented a process of ammonia leaching of nickel, cobalt and copper sulfides, conducted
at 105°C with air pressure of 0.8 MPa (Radmehr et al., 2014). Under these conditions
copper, nickel and cobalt could be dissolved with iron precipitating in its hydroxide
form. The pregnant solution was heated to evaporate the excess ammonia, later allowed
to react with air to oxidize its thiosulfates. Reduction continued till the precipitation of
nickel with little effect on the cobalt ions in solution (Radmehr et al. 2014). The Sherritt
Gordon process was the first successful commercial ammonia leaching of nickel sulfide
concentrates (Wei, 2016). It was later developed for nickel matte from smelting and
nickel-containing alloy scraps. Figure 4 shows the Sherritt Gordon process flowsheet
which is currently being used by the Kwinana Nickel Refinery in WA.
9|Page
MATTE GRIND LEACH
• Contains: Nickel, copper, • Nickel, copper and cobalt
cobalt, sulfur and iron dissolved; sulfide oxidised
to sulfate; iron converted to
insoluble iron oxide
COPPER BOIL SOLID / LIQUID

• Copper seperates as copper • Iron residue
sulfide
OXYDROLYSIS NICKEL REDUCTION

• Unwanted sulfur • Nickel powder precipitated
compounds changed to
sulfate
CRYSTALLISATION METAL STRIPPING

• Ammonium sulfate • Mixed nickel / cobalt sulfide
precipitated precipitated
FIGURE 4. A flowsheet showing the Sherritt Gordon process.
10 | P a g e
2.3 FACTORS AFFECTING NICKEL AND COBALT EXTRACTION
There are a number of studies in which higher nickel extraction was attributed to pH
and temperature increases (Kumbasar and Kasap, 2009; Muharok and Lieberto, 2013;
Zuniga et al., 2010; Sarma and Nathsarona, 1996; Hu et al., 2012; Li et al., 2010). Hu et
al. (2012), described various techniques for nickel recovery from ammoniacal leach
solutions. These included precipitation and solvent extraction. In their study Hu et al.
(2012), tested the β-diketones as an alternative for nickel extraction. They presented β-
diketones as a versatile class chelating agents, which had been recommended for nickel
extraction. In this study the authors found that the extraction efficiency of nickel
increased with increased pH, ammonia concentration and temperature. The maximum
extraction was achieved at pH~8.5, and decreased at higher pH.
Hu et al. (2012), reported that the inert electrolyte (Na2SO4) did not affect the distribution
coefficient of nickel (II). The increase of the total ammonia concentration, however, was
seen to depress the extraction of nickel (Hu et al., 2012). The authors attributed the
decrease in the extraction efficiency mainly to the formation of nickel ammine
complexes, because the replacement of H2O in the [Ni(H2O)6]2+ by NH3 ligand increases
in their stability in the aqueous phase (Hu et al., 2012). It was also noted nickel
extraction will increase in temperature at pH~7.5, but will be reduced with the increase
in temperature at pH~8.5 (Hu et al., 2012).
A similar study was presented by Sarma and Nathsarona (1996), who reported that the
influence of pH on the extraction efficiency was found to be more pronounced in the
range 9.5-10.0, compared to 8.6-9.5. They suggested that the ammonium carbonate
concentration had very little influence on the nickel extraction, at the concentration
range of 45-75 kg/m3. It was also noted that extraction of nickel was reduced by 20% at a
salt concentration in solution of 150 kg/m3 (Sarma and Nathsarona, 1996).
Zuniga et al. (2010), reported the kinetics of nickel extraction as slow, and requiring high
temperatures, ammonia and metallic iron concentrations. They suggested that cobalt
concentrations decrease due to precipitation with or on Fe3+ oxide/hydroxides. The
losses of cobalt are affected by increasing ammonia concentrations and temperature,
because these will enhance the formation of Fe3+ oxides/hydroxides. It was found,
however, that if the ammonium sulfate concentration is increased, this will in fact
decrease cobalt losses (Zuniga et al., 2010).
11 | P a g e
In another study led by Kumbasar and Kasap (2009), the increases in nickel extraction
were attributed to ammonia concentrations increases to 6M at a fixed pH.
Senanayake et al. (2010), described the rate of iron dissolution as slow, with low
extraction of <2%, associated with the precipitation after the leaching stage. The
incomplete dissolution of nickel has been linked to the passivation by M(OH)3, MOOH
or MFe2O4 and these findings have been supported by the measured current-potential
positions, shrinking core kinetic model as well as the thermodynamic predictions
(Senanayake et al., 2010). The authors also reported that sulfide causes precipitation and
lowers the dissolution rate of both iron (~1%) and nickel (<2%).
Muharok and Lieberto (2013) presented a study with a conclusion that precipitation of
nickel hydroxide from nickel laterite ore leaching is dependent on both the pH and
temperature. The mixed hydroxide precipitate (MHP) described in this article, is one of
the intermediate products of nickel laterite ore processing through a hydro-metallurgical
route. It is treated further in the Caron process, to produce separate pure nickel and
cobalt. Muharok and Lieberto (2013) used the SEM to analyse the particle distribution of
the precipitate. Their analysis suggested that nickel hydroxide obtained from the
precipitation at 50°C and pH 9, contains fine particle size in which the main impurity
elements were iron and magnesium.
Lu et al. (2013), studied the effect of sodium sulfate on the H2 reduction process of nickel
laterite ore. The results obtained showed that the addition of sodium sulfate can improve
the reduction kinetics and that the nickel laterite ore’s catalytic activity strongly depends
on sodium sulfate dosage, as well as the reduction temperature. It was also mentioned
that the reducing time, and to some extent, the H2 content influenced the reduction of
iron oxides. As the reaction time and H2 partial pressure were increased, there was an
increase in the reduction rate of iron oxides to metallic iron (Lu et al., 2013).
DeGraaf (1979) studied the reduction conditions and possible improvements of the
Caron process. One of the observations which he noted was, that high-iron ores should
be reduced in the “magnetite” zone and not in the metal zone. This should happen in
order to avoid nickel losses on ferric hydroxide formed by the action of dissolved oxygen
on the products during the leaching stage. The reductions with H2 required longer
leaching times for ores reduced at higher temperatures, increasing the amounts of iron
12 | P a g e
dissolved (DeGraaf, 1979). It was noticed that smaller particle size increased the
recovery of nickel but had no effect on the dissolution rate. For the reduction of silicate
ore with CO, fine grinding was necessary for high nickel extraction, regardless of
reducing conditions (DeGraaf, 1979).
In 1980 DeGraaf presented his second study of the leaching reactions of the Caron
process. This study suggested the addition of sulfur as pyrite during the reduction stage
as beneficial to the nickel extraction and beneficial in decreasing the sensitivity to the
reduction conditions. It was also reported that finer grinding and repeated reduction of
leach residue resulted in some increases in the extraction (DeGraaf, 1980).
2.4 IRON PASSIVATION LAYER FORMATION

The passivation of iron has been identified as a major factor limiting the efficiency of the
Caron process and the recovery of nickel and cobalt from laterite ores (D’Aloya and
Nikoloski, 2012). D’Aloya and Nikoloski (2012) studied the passivation of iron in
ammoniacal solutions containing Cu2+ ions, and reported that the presence of these ions
in solutions will in fact promote the passivation of iron. As the concentrations of copper
are increased, and the concentration of ammonia-ammonium bicarbonate is lowered, the
passivation of iron will occur more readily (D’Aloya and Nikoloski, 2012). An open
circuit measurement was performed, which was found to increase from -0.7 V to -0.6 V
after 3 hours in aqueous ammonia and ammonium bicarbonate-ammonium carbamate
double salt and 0.2mM copper sulfate. The experiment was repeated at a 12mM
concentration of Cu2+, with the OCP increasing to around -0.5 V, before a further
increase to a high potential region of 0.1-0.2 V, where it stayed for the remainder of the
test.
The rotating disk cyclic voltammetry studies were also carried out on solution containing
ammonia-ammonium bicarbonate with 6mM Cu2+ ions. The RDE was immersed in a
solution under the OCP conditions for 2 minutes, with the potential scanned in the
positive direction at a rate of 10 mV/s from the OCP to +0.24 V, then reversed back to
-0.56 V. Peak (A) was observed close to -0.43 V during the anodic sweep, which has
been attributed to the anodic dissolution of metallic iron, with a second peak (B) noticed
at around -0.13 V, assigned to the re-dissolution of cemented copper. During the
cathodic scan, the anodic dissolution of iron was noticed at around -0.4 V, peaking at
-0.47 V (D’Aloya and Nikoloski, 2012).
13 | P a g e
The mechanism of passivation, as described by D’Aloya and Nikoloski (2012), involved
cementation of copper onto the actively dissolving iron surface. During this process of
copper cementation, the insoluble oxide compound will become the preferred product of
iron oxidation. A thin, passive layer will form as a result of the re-dissolution of the
cemented copper, when the copper is no longer cathodically protected by metallic iron
(D’Aloya and Nikoloski, 2012).
Dyer et al. (2012), have studied cobalt loss due to iron precipitation in ammoniacal
carbonate solutions. The slow and limited leaching kinetics and poor recovery were
linked to the possible fuel oil containing sulfur, and the formation of nickel sulfide during
the reduction stage, which is less reactive than elemental nickel or alloys, a formation of
iron as oxide/hydroxide and a formation of iron passive layer by precipitated iron
species (Dyer et al., 2012). It was found that because of the sensitivity of iron oxide
formation under conditions such as pH, temperature, residence time or the solution
potential, it is difficult to predict the exact phase produced. The authors of this study
reported that the initial iron concentration was unlikely to influence the adsorption of
cobalt. It was reported that higher iron levels produced greater mass of precipitate,
however, with greater surface area and, therefore, more binding sites for cobalt (Dyer et
al., 2012). It was found that cobalt loss peaks at pH 7, lower at pH 6, and all values
above pH 7, with a sharp decrease observed at pH 10. The presence of cobalt during iron
precipitation resulted in greater cobalt losses at a number of different iron
concentrations. It was noted that the mechanism of cobalt loss during iron precipitation
is adsorption, not the precipitation of a secondary phase (Dyer et al., 2012). The
increases in ammonia concentrations were seen as beneficial, limiting the proportion of
cobalt being removed. No indications that the temperature between 25-45°C has any
influence over cobalt adsorption was reported.
The majority of iron dissolution is thought to take place under oxygen-free conditions,
resulting in the dissolved iron precipitating as ferric hydroxide. The rejection of iron at
the leaching stage is desirable. The passivation of the metallic iron has had a negative
effect on the extraction efficiency, however (D’Aloya and Nikoloski, 2013). The
formation of CoSx and its effects on the anodic dissolution of iron in ammoniacal-
carbonate solutions were studied by D’Aloya and Nikoloski (2013). This study showed
that during the dissolution of iron in ammoniacal-carbonate solutions in the presence of
14 | P a g e
Co2+ and thiosulfate ions, the CoSx species are formed on the iron surface. It has been
reported that the formation of these species is influenced by the passivation of iron, and
that these species produce negative effect in the leaching stage of the Caron process,
causing the loss of the dissolved cobalt from the leach solution and reducing the
efficiency of the extraction (D’Aloya and Nikoloski, 2013). The authors noted that this
passivation layer can be prevented if the concentration of ammonia is maintained higher
than 4M.
In another study D’Aloya and Nikoloski (2014) studied the anodic dissolution of iron in
ammoniacal-carbonate-thiosulfate-copper solutions. It has been shown that the
behaviour of iron strongly influences the dissolution of alloys and the recovery of metals.
The solutions containing both the dissolved cobalt and thiosulfate ions show a tendency
to significantly suppress the passivation and the dissolution of iron (D’Aloya and
Nikoloski, 2014). It was also reported that if both Cu2+ and thiosulfate ions are present in
the leach solutions, they will also suppress the passivation of iron.
D’Aloya and Nikoloski (2014) observed that in solutions which contained cobalt and
thiosulfate ions, even small additions of copper ions were seen to delay the onset of
passivation. The passivation of the RDE at a concentration of copper ions as low as
0.1mM in an ammoniacal-carbonate solution containing 12mM Co2+ and 24mM S2O32-
took place after 2 hours of immersion, compared to 30-40 minutes with no copper
addition.
The rotating disk cyclic voltammetry measurements were performed for 15 minute
immersions in 6M[NH3]T , 2M[CO2]T solutions at different Cu2+ and S2O32-
concentrations. The potential was scanned from the OCP, resulting in an anodic peak
(A) around -0.6 to -0.2 V, followed by a second anodic peak (B) at around -0.1 to 0 V
and a third peak (C) above 0.1 V. The increase in Cu2+ concentration from 1mM to
4mM at a constant S2O32- resulted in a 7-fold increase in peak (C) (D’Aloya and
Nikoloski, 2014). It was found, however, that the increase of S2O32- concentration at a
constant Cu2+ results in a 10% decrease in the current density peak (C). The authors
attributed this peak (C) to the oxidation of copper-containing species forming during the
anodic dissolution of iron, and possibly as a result of copper (II) reduction to copper (I)
on the surface of the iron electrode. During the reverse scan, the anodic dissolution of
15 | P a g e
metallic iron resumed around -0.4 V with reported higher current densities reached at
lower Cu2+ and higher S2O32- (D’Aloya and Nikoloski, 2014).
D’Aloya and Nikoloski (2014) observed a black solid layer forming on the iron surface
during the dissolution, a layer which contained Cu2S and dendritic copper. It was
suggested that this layer formation is possibly due to the effect of copper cementation. It
was noted that this layer remained in electrical contact with the iron RDE surface
(D’Aloya and Nikoloski, 2014). The authors commented that the formation of the
deposit on the iron surface did not suppress the dissolution of iron, as was the case with
(D’Aloya and Nikoloski, 2013), nor was it found to promote passivation (D’Aloya
and Nikoloski, 2014).
In another study this iron passivation was linked to the oxide layer being in the presence
of high concentrations of dissolved oxygen and/or other oxidants (Nikoloski and Nicol,
2010). Nikoloski and Nicol (2010) studied the cathodic processes involved in the
leaching reactions in the Caron process. It was found that Co3+ ions were the main
oxidizing agents involved in the dissolution of nickel, cobalt and iron in ammonia-
ammonium carbonate solutions. The authors reported that a sulfide layer will be formed
from a reaction involving the reduction of thiosulfate in the presence of nickel and cobalt
metal ions, and that this additional cathodic reaction could enhance the overall rate of
dissolution of iron alloys in an ammoniacal-carbonate solutions (Nikoloski and Nicol,
2010).
2.5 ELECTROCHEMICAL PRINCIPLES

2.5.1 Metal Electrolyte Interface - The Electrical Double Layer
As the metal is immersed in an electrolyte, the electrons from the metal ions will
separate and remain in the metal. Surrounded by the water molecules, these metal ions
will start to diffuse away from the metal. The excess number of electrons on the metal
surface will attract the positively charged metal ions, so instead of diffusing into the bulk
electrolyte, these metal ions will in fact remain near the metal surface. The water layer
around the metal ions, however, will prevent them from making direct contact with the
electrons on the surface, so stopping them from being reduced to metal atoms. This
electrolyte layer adjacent to the electrode, containing water molecules and ions from
both metal and bulk electrolyte, will possess its own unique chemical composition,
16 | P a g e
significantly different from the bulk electrolyte. An electrical double layer (EDL) is a
term used to describe the combination of this negatively charged surface of the metal and
the adjacent electrolyte layer.
The first concept of the ‘electrical double layer’ was developed by Helmholtz in the 19th
century (Helmholtz, 1853). The model proposed a theory of electron transfer occurring
at the electrode with the solution composed only by electrolyte. A good basis for the
understanding of the solid-liquid interface was provided, but, this model failed to
account for the diffusion and mixing in solution, as well as the possible surface
adsorption.
Guoy (1910) and later Chapman (1913) proposed a more advanced theory of a ‘diffused
electrical double layer’. This model described the electrolyte in terms of a number of
oppositely charged ions, whose concentration decreases as the distance from the surface
is increased. This theory was not entirely accurate, however, as the anions and cations
already existed in the solution. There was the probability that with the increased distance
from the surface, the ions of the same charge as the surface will be found within this
double layer would also increase. Stern (1924) worked on developing this ‘diffused
electrical double layer’ theory further and combined the Helmholtz layer with the Guoy-
Chapman theory. His theory described the ‘electrical double layer’ in terms of two
separate layers- the inner Stern layer consisting of adsorbed and immobile ions right on
the solid, and the diffuse outer layer of mobile charge carriers, passing into the bulk
solution. The nature of the interactions between the electrode surface and the ions in
solution was assumed to be electrostatic, caused by either the excess or a deficiency of
electrons at the electrode surface (Stern, 1924). For the interface to remain neutral, ions
close to the electrode surface must have been constantly redistributed. The attracted ions
approaching the surface would need to form a layer, which balances the electrode
charge. This would result in two layers of charge - hence the double layer - and a
potential drop when these two are separated (Wang and Pilon, 2011). Figure 5 shows the
schematics of the double layer theory.
17 | P a g e
FIGURE 5. The electric field consisting of two layers of charge – The Electrical Double Layer
(faculty.kfupm.edu.sa)
2.5.2 Corrosion Potential

Corrosion potential is described as the potential of an electrode of metal corroding in an
aqueous solution (Sato, 2012). It represents the point where the anodic oxidation current
of metal dissolution will be equal to the cathodic reduction current of the oxidant. Figure
6 schematically describes the electrode potential versus reaction current curves of anodic
oxidation and cathodic reduction.
18 | P a g e
FIGURE 6. Polarization curves of corrosion reactions, where i a is the anodic reaction current, ic is
the cathodic reaction current, icorr is the corrosion current, Ea is the equilibrium potential of the
cathodic reaction, Ec is the equilibrium potential of the cathodic reaction and Ecorr is the corrosion
potential (Sato, 2012).
It is possible to control the rate of corrosion of metals by controlling either the anodic or
the cathodic reactions.
The anodic metal dissolution can be represented as an exponential function of the

electrode potential (E), as follows:
[Eq.4]
where and are parameters.
The cathodic current (ic) of the oxidation reaction is also an exponential function of
electrode potential (E), as follows:
[Eq.5]
The cathodic current will increase exponentially with increasing cathodic electrode
potential in the more negative direction (Sato, 2012).
19 | P a g e
2.5.3 Mixed Potential Theory
When a catalystic surface is introduced to an electrolyte containing Mn+ ions and a
reducing agent, the partial oxidation and reduction reactions will occur simultaneously.
A steady-state mixed potential (Emix) will be established as these two partial reactions
strive to establish their own equilibriums (Eeq). It has been noted, that the value of the
mixed potential is not a determination of the two individual thermodynamic equilibrium
potentials, but in fact is determined by their reaction kinetics being closer to the
equilibrium potentials of the faster reacting species (D’Aloya, 2015). As the redox couple
raises anodically from Eeq.Red, the potential of the metal electrode M/Mn+ is reduced
cathodically from the value Eeq.M, down to the value of the mixed potential (Emix).
According to Paunovic and Schlesinger (2006), there are four characteristic aspects of the
mixed potential theory:
1) The characteristic equilibrium potentials of both redox systems will be shifted by

the amount of over-potential , as shown in Eq.6 and Eq.7,
[Eq.6]
[Eq.7]
2) An electrochemical reaction will take place at each redox system, as the mixed
potential shifts their equilibrium potential.
3) During the reduction of Mn+, the cathodic current density (iM), and the anodic
current density (iRed) will be equal, according to Eq. 8, since an isolated system
has no net current,
[Eq.8]
4) The free energy change is not zero, since the system is not in equilibrium.
The Butler-Volmer equation describes the current density at an electrode in terms of the
over-potential and has been used to calculate the rate of electrochemical reaction,
according to the formula:
[Eq.9]
20 | P a g e
where:
= current density as a result of imposed potential (A/cm2)
= exchange current density (A/cm2)
= transfer coefficient
= electrode over-potential
F = Faraday’s constant (C/mol)
n = number of electrons in the half-reaction
R = universal molar gas constant (kJ/mol)
T = temperature (°K)
The Butler-Volmer equation represents the sum of the total anodic half-reaction (IA) and
the total cathodic half-reaction (IC), according to these two equations:
[Eq.10]
[Eq.11]
A higher exchange current will results when the anodic half-reaction is paired with
cathodic half-reaction, according to the following:
[Eq.12]
Figure 7 shows the mixed potential (Emix) as the point in the middle of two redox
coupled equilibrium potentials.
21 | P a g e
FIGURE 7. A schematic representation of the Mixed Potential Theory for two redox couples
(Nikoloski, 2002).
2.5.4 Cyclic Voltammetry

Cyclic Voltammetry is a technique used for analysing electrochemical reactions. It helps
in analysing the thermodynamics of redox processes as well as understanding the
kinetics of the electron-transfer reactions. By applying a voltage to an electrode
immersed in an electrolyte solution, the system’s responses can be analysed. Cyclic
Voltammetry uses the three electrode system, which consists of a working electrode, a
reference electrode and a counter electrode. By varying the magnitude of the applied
potential to the working electrode, the electrode itself will become a stronger oxidant or
reductant, depending on whether the potential is being increased or decreased with time
(Kissinger and Heineman, 1984). The potential is measured between the working and
the reference electrodes, and the current is measured between the working and the
counter electrodes. The role of the counter electrode is to prevent any current running
through the reference electrode, as this would have a negative impact on the potential of
this reference electrode.
During Cyclic Voltammetry, the potential of the working electrode is scanned rapidly
over a wide potential range, returning back to its initial value with an applied potential
22 | P a g e
signal, which varies linearly with time (Compton and Banks, 2007). The working
electrode is subjected to a triangular potential sweep, as the potential rises at a constant
rate from the start value (Epa) to the final value (Epc), then returns back to the starting
potential. The current measured during this process is referred to as current density, and
will depend on the surface area of the electrode (Compton and Banks, 2007). A cyclic
voltammogram will represent the current density plotted against the applied potential. A
typical potential versus time profile applied to the working electrode and the resulting
cyclic voltammogram are shown in Figures 8 and 9, respectively.
FIGURE 8. Potential versus time profile applied to the working electrode (Compton and Banks,
2007).
FIGURE 9.Current versus potential Cyclic Voltammogram (Compton and Banks, 2007).
23 | P a g e
2.5.5 Passivity of Metals
Metallic corrosion has been one of the problems encountered, and hence studied, since
the industrial revolution. Keir (1790) first studied metallic passivity and presented a
theory of metallic iron in an active state corroding in a concentrated nitric acid solution,
to the point where the corrosion was suddenly stopped, turning into a passive state of no
corrosion observed. This corrosion theory was confirmed much later, with the discovery
of an oxide film, called the passive film, several nanometers thick, on the surface of the
metal (Sato and Okamoto, 1981). Anodic metal passivation occurs at the passivation
potential (Ep), a point from which the anodic current of metal dissolution will decrease
drastically. As Sato (2012) states, the passivation potential will depend on the acidity of
the solution, and will shift linearly to more positive direction with decreasing pH. It is
both the anodic metal dissolution and the cathodic oxidant reduction current which
determine the corrosion potential. If this corrosion potential of the metallic electrode is
held in the potential range of passivity, the electrode then may be made passive. As long
as the cathodic current is less than the maximum current of the anodic metal dissolution,
corrosion potential will remain active (Sato, 2012). An unstable passive state will begin
when the cathodic and anodic potential current curves cross. Figure 10 shows the
relationship between the current and potential as metal undergoes passivation.
FIGURE 10. A schematic representation of current-potential relationship as metal undergoes

passivation (Bockris and Reddy, 1970).
24 | P a g e
2.5.6 In situ XRD Electrochemical Analysis
There have been a number of different surface characterisation techniques (XRD, SEM,
Raman Spectroscopy) applied to investigate the kinetics of solid phases in
hydrometallurgical aqueous media. Most of these techniques involved ex-situ
measurements, needing the analysed samples to be removed from the reaction
environment and/or its surface before the characterisation process (Majuste et al., 2013;
De Marco and Veder, 2010).
Recently, there has been an increased interest in characterisation techniques specific to

electrochemical analysis, involving in-situ measurements. A number of publications have
demonstrated that in-situ characterisation techniques, which allow the analysis under a
more realistic conditions, have lead to significant advances in research areas in
hydrometallurgy (Majuste et al., 2010; De Marco and Veder, 2010; Veder et al., 2011;
Clancy et al., 2015; Song et al., 2016).
Majuste et al. (2013), describe the use of synchrotron radiation XRD measurements
being performed with high spatial and time resolution, using intense high energy X-rays,
capable of penetrating a wide range of in-situ sample environments. This synchrotron
radiation has become increasingly popular for analysing the electrochemical reactions
taking place under controlled conditions.
In order to use synchrotron radiation in the characterisation of electrochemical systems

in-situ, a specifically designed flow cell is required, one that will allow for the
electrochemical reactions to take place whilst the appropriate X-ray measurements are
being made. According to De Marco and Veder (2010), there are two specific in-situ cell
designs, corresponding to two different modes of measurements geometries- reflection
and transmission. Figure 11 shows the two types of in-situ electrochemical cell
configurations.
Reflection cells contain an X-ray transparent window, situated parallel or perpendicular

to the working electrode interface, while in the transmission cells, the X-ray beam passes
through the entire cell.
25 | P a g e
FIGURE 11. Different cell configurations in reflection and transmission geometries. Thick black
arrow shows the path of X-ray beam; dashed arrows show the scattered beam (De Marco and
Veder, 2010).
A significant innovation in studies of electrochemical interface systems in-situ has been

presented by Bozzini et al. (2009). This study tested the use of in-situ soft X-ray
microscopy (SXM) in the nickel electrodeposition from ammonium and chloride
solutions being monitored as a function of applied potential.
Song et al. (2016), applied the in-situ X-ray real time imaging technology in order to
analyse the interfacial behaviours of nickel electrodeposition in the NH4Cl solutions.
Figures 12 and 13 show the X-ray images of nickel morphology and SEM micrographs
of the nickel electrodeposition, respectively.
26 | P a g e
FIGURE 12. Synchrotron radiation X-ray real time images of nickel morphology deposited at pH 10
(a) -1.2V, (b) -1.4V and (c) -1.6V (Song et al., 2016).
FIGURE 13.SEM micrographs showing nickel electrodeposition obtained at different potentials

(deposition time of 400s) (a) -1.2V, (b) -1.4V and (c) -1.6V (Song et al., 2016).
The in-situ synchrotron radiation X-ray imaging showed that the evolution of nickel
morphology is dependent on the potential (Song et al., 2016).
In another study Clancy et al. (2015), designed an electrochemical cell which was used to
characterise the evolution of the surface layers formed on the Pb anode under
electrochemical conditions in the industrial copper electrowinning. Figure 14 shows the
schematic of their design.
27 | P a g e
FIGURE 14. Schematic of the electrochemical flow cell (a) exploded view of the cell with its main
components, (b) partial section view of the assembled cell, highlighting the path of the flowing
electrolyte solution, and (c) top view of the cell (Clancy et al., 2015).
This flow cell in conjunction with the synchrotron radiation analysis proved successful in
assessing in real time how the surface layers are evolving. This study presented valuable
insights, particularly for the electrowinning industry (Clancy et al., 2015).
In their study, Veder et al. (2011), emphasised the need for a versatile electrochemical
cell, one that is applicable to a number of different electrochemical techniques, following
by in-situ surface studies, using a variety of X-ray characterisation methods. They were
able to develop an electrochemical cell design (shown in Figure 15), capable of in-situ
electrochemical and surface characterisation measurements in a variety of media.
28 | P a g e
FIGURE 15. Schematic diagram of an electrochemical cell used for in-situ X-ray analyses. Upper
diagram shows a side profile of the cell; lower diagram shows a top profile (Veder et al., 2011).
As described by Brant et al. (2013), in-situ electrochemical cells cannot be converged to

one single design. Many of these flow cells will have complex designs. The aim is to
maximise the electrochemical properties while maintaining a high quality diffraction
pattern, allowing for every phase observed to be identified. This ability to combine the
electrode structure measurements with the electrochemical techniques has since become
one of the more compelling surface characterisation techniques in modern
electrochemistry.
29 | P a g e
3 EXPERIMENTAL MATERIALS AND METHODS
3.1 MATERIALS
The investigation will focus on the leaching rate and extent of three different types of
materials, including electrochemically formed metal sulfides (EFMS), synthetic
monometallic metal sulfides (SMMS) and real metal sulfides (RMS) present in a
flotation concentrate. Throughout the rest of this thesis these materials will be referred to
according to their abbreviations.
3.1.1 Electrochemically formed Metal Sulfides (EFMS)

The first group of samples studied are electrochemically formed metal sulfides (EFMS).
These metal sulfides have been observed to form on the surface of dissolving iron-based
material under processing conditions. The method of preparation of these materials will
be described under the section covering the methods used in the electrochemical study.
3.1.2 Synthetic Monometallic Metal Sulfides (SMMS)

Prior to conducting the leaching studies, samples of nickel sulfide (Ni3S2) , cobalt sulfide
(CoS2) and copper sulfide (Cu2S) were scanned by the SEM/EDX as well as the XRD
instruments for sample characterisation analysis. A sizing test using a laser-sizer was
performed on a sub-sample from each feed material.
3.1.3 Flotation Concentrate Samples (RMS)

Prior to conducting the leaching studies on the flotation concentrate feed samples, an
analysis using the SEM and XRD was performed, from which the elemental
composition of both feeds as well as the leach residues was obtained.
3.1.4 Test Solutions

All solutions used in the electrochemical study were prepared using deionised water and
AR grade reagents. Each solution contained total concentration of ammonia [NH3]T and
carbonate [CO2]T, similar to the composition of the barren liquor used in the Caron
process. The barren solution was prepared using 28% w/w concentrated aqueous
ammonia solution with ammonium carbonate.
30 | P a g e
For the electrochemical portion of this project, the chosen concentrations of [NH3]T and
[CO2]T were 5M (90 g/L) and 1M (45 g/L) respectively, this being consistent with the
previous studies by D’Aloya (2015), except for the Ni(II) + S2O32- solution, where 3M
[NH3]T (54 g/L) and 1M [CO2]T (45 g/L) were used to make up the barren solution.
TABLE 1 shows the composition of the solutions used.
TABLE 1. Solution compositions used in the electrochemical portion of this project.
mol/L mol/L x 10-3

SOLUTION
[NH3]T [CO2]T Ni(II) Co(II) Cu(II) S2O32-
1 Barren 5 1
2 Ni(II) + S2O32- 3 1 150 22
3 Co(II) + S2O32- 5 1 12 22
4 Cu(II) + S2O32- 5 1 8 22
3.2 METHODS USED FOR ELECTROCHEMICAL STUDY

3.2.1 Electrochemical Apparatus
The electrochemical set-up used in this project consisted of a three-electrode
electrochemical cell, which was connected to a potentiostat (Model Wave Form). A
jacketed vessel, containing 100 ml of the prepared solution was connected to a
thermostat-controlled water bath set to 45°C.
The working electrode used in all experiments was the rotating disk electrode (RDE)
constructed from iron (99.9% Fe) with a diameter of 9.8 mm. The electrode was fitted to
a rotator, through which it was connected to a potentiostat and rotated at 200 rpm.
Before each test the surface of the working electrode was polished with 800 and 4000 grit
silicon carbide paper wetted with deionised water. The counter electrode was made of
platinum wire, 0.5 mm in diameter and 100 mm long. A Calomel electrode (SCE) placed
within a salt bridge containing potassium sulfate solution was used as a reference
electrode. The reference electrode was connected to a Luggin capillary fitted at the
bottom of the cell, with the tip only a few millimetres away from the surface of the
31 | P a g e
working electrode. This distance was kept to the minimum to minimise the iR drop in
potential. All potentials were reported vs SHE (+0.0V). Each experiment was conducted
under deoxygenated conditions, with nitrogen sparged into the solution throughout the
test. A schematic representation of the experimental set up is shown in Figure 16.
FIGURE 16. Electrochemical set-up, showing working electrode (WE), counter electrode (CE),
reference electrode (RE), Luggin capillary(LC) (D’Aloya, 2015).
3.2.2 OCP Measurements

The behaviour of iron RDE was monitored during the 3 hour immersions in a 3M
[NH3]T and 1M [CO2]T (Solution 2) and 5M [NH3]T and 1M [CO2]T (Solution 3 and 4)
with a combination of dissolved species according to Table 1. The RDE was rotated at
200 rpm, with the temperature of the leach solution kept at 45°C. For all the OCP
experiments nitrogen gas was sparged into the solutions.
3.2.3 Rotating Disk Cyclic Voltammetry

Cyclic voltammetry tests performed involved the working electrode being immersed in a
combination of solutions (Table 1) for 2 hours and rotated at 200 rpm. The
measurements were taken by scanning the potential in the positive direction from the
OCP to ~+1.2 V and back, at a rate of 10 mV/s. A typical cyclic voltammogram was
constructed for each solution tested, showing the anodic peak potentials and current
densities which were further analysed.
32 | P a g e
3.2.4 SEM/EDX Surface Analysis
Following each OCP test, the working electrode was rinsed with deionised water, and its
surface was analysed by SEM/EDX spectroscopy, for full characterisation of the layers
which formed on the surface of the electrode.
3.2.5 Dissolution Studies

In order to monitor the dissolution of the layers formed on the surface of the working
electrode, two cells were used simultaneously, both heated to 45°C. The first cell
contained 100 ml of the appropriate solution (Table 1), and was used to form the sulfide
layer on the surface of the electrode. The second cell, containing 100 ml of barren
solution, was used to monitor the dissolution of the freshly formed layers from the first
cell.
As the OCP measurement indicated passivation, the working electrode was removed
from the first cell, rinsed with deionised water, and re-immersed in the second cell.
During the dissolution stage, solution samples were taken out at different time intervals.
These samples were analysed for the total concentrations of metal for each test (Ni, Co
or Cu) by the AAS.
3.3 LEACHING METHODS

3.3.1 Leaching of Synthetic Monometallic Metal Sulfides (SMMS)
The leaching of nickel sulfide (Ni3S2) cobalt sulfide (CoS2) and copper sulfide (Cu2S) in
a thiosulfate ammoniacal-carbonate solution under various conditions was carried out in
a 500 ml sealed glass vessel for the duration of 5 hours. Unlike the electrochemical tests,
the leaching tests were performed with air. A schematic representation of the leaching
set-up is represented in Figure 17. The leach solution was mixed continuously using an
agitator and a plastic stirrer. At each sampling stage, 10 ml of the leach liquor was
removed, with the bulk of the solution monitored for pH and Eh variations. These
solutions removed were sufficiently diluted and analysed by the AAS. From the results
obtained, the dissolution kinetics behaviour of nickel, cobalt and copper was determined
and fitted in the reaction rate models based on either ash diffusion control, surface
reaction control or the mixed model.
33 | P a g e
FIGURE 17. Schematics of the leaching set up.
3.3.2 Kinetic model for Synthetic Monometallic Metal Sulfides

The results from the leaching tests were analysed with different kinetic models. The three
kinetic model equations were:
Surface Reaction: [Eq.13]
Ash Layer Diffusion: [Eq.14]
Mixed Model: [Eq.15]
where , and are apparent rate constants.
Linear plots representing the experimental data were drawn, and an attempt to fit the
data with the kinetic models was made. The relationship between the apparent rate
constant and the temperature was expressed by the Arrhenius equation:
[Eq.16]
where is the apparent rate constant, A is the frequency factor, E a is the activation
energy and R is the gas constant. Activation energy was estimated for nickel, cobalt and
copper leaching reactions.
34 | P a g e
3.3.3 Leaching of Flotation Concentrate (RMS)
The leaching of flotation concentrate feed samples in a thiosulfate ammoniacal-
carbonate solution under various conditions was carried out in 500 ml sealed glass vessel
for the duration of 30 hours, at 45°C and under atmospheric conditions. A schematic
representation of the leaching set-up is represented in Figure 17. The slurry was mixed
continuously using an agitator and a plastic stirrer. At each sampling stage, 10 ml of the
leach liquor was removed, with the bulk of the solution monitored for pH and Eh
variations. The solution samples removed were analysed for either nickel or copper
concentrations by the AAS. From the results obtained, the dissolution kinetics behaviour
of nickel and copper was determined. The obtained results were also compared to the
kinetic behaviour of the synthetic monometallic nickel and copper sulfides.
35 | P a g e
4 RESULTS AND DISCUSSION
4.1 THE INVESTIGATION OF NICKEL SULFIDE
The results and discussion of nickel sulfide tests are presented in this section. The
investigations of the electrochemically formed, the synthetic monometallic and the real
nickel sulfide samples are outlined, and a comparison of the rate and the extent of each is
presented at the end.
4.1.1 Electrochemical Testwork

This section includes the analysis of electrochemically formed nickel sulfide. The results
from OCP and CV tests are presented, as well as the sulfide layer characterisation
studies. The rate and extent of the sulfide layer dissolution back into the leach solution is
also investigated.
4.1.1.1 OCP Measurement

The open circuit potential (OCP) of the iron electrode was measured for 3 hours in a
deoxygenated 3M [NH3]T + 1M [CO2]T solution containing 0.15M Nickel (II) and
0.022M thiosulfate ions. The electrode was rotated at 200 rpm, and the solution was
maintained at a temperature of 45°C. Figure 18 shows the obtained result.
-0.1
-0.2
E (V vs SHE)
-0.3
-0.4
-0.5
-0.6
0 30 60 90 120 150 180
TIME (mins)
FIGURE 18. OCP of iron in a deoxygenated ammoniacal-carbonate solution containing 0.15M

nickel (II) and 0.022M thiosulfate ions.
36 | P a g e
The open circuit potential was found to be around -0.35 V within the 3 hour immersion.
It can be seen from Figure 18, however, that the spontaneous passivation of iron in
ammoniacal-carbonate solution containing 0.15M nickel (II) and 0.022M thiosulfate
ions could not be achieved during the 3 hour immersion.
4.1.1.2 Rotating Disk Voltammetry

The cyclic voltammetry tests were carried out, with the iron electrode immersed in a
deoxygenated 3M [NH3]T + 1M [CO2]T solution containing 0.15M nickel (II) and
0.022M thiosulfate ions. The potentials were scanned in the positive direction from an
initial potential of -0.56 V, with the vertex potential at +1.24 V, and the final potential at
-0.70 V. The sweep rate was kept at 10 mV/s. The electrode was rotated at 200 rpm and
the solution was maintained at 45°C. The cyclic voltammograms were constructed at 0
hours (initial immersion) and 2 hours after immersion, and are represented in Figure 19.
150
100
A
C
i (mA/cm2)
50
B D
E
0
INITIAL
-50
2Hrs
-100
-1.0 -0.5 0.0 0.5 1.0 1.5
E (V vs SHE)
FIGURE 19. CV of iron following different times of immersion in a deoxygenated Ni (II)

thiosulfate ammoniacal-carbonate solution.
Upon the immersion of the iron RDE, as the potential was scanned anodically from
-0.56 V, a peak at around -0.50 V was recorded (Figure 19). The current density at this
point was at around 80 mA/cm2. This peak (A) was attributed to the anodic dissolution
of iron, according to the following half-reaction:
37 | P a g e
[Eq.17]
As the potential continued to be applied, there was a steep drop of the current recorded
at around -0.40 V, and following this drop no significant currents were recorded, till the
reversed scan approached -0.40 V, where another peak (B) was noticed (with the current
density of around 25 mA/cm2). This peak resulted from the reactivation of the iron
dissolution. During the positive scan of the iron RDE following 2 hour immersion, peak
(C) was recorded at around -0.20 V, with the current density at this point of less than 50
mA/cm2. This anodic peak represented the dissolution of iron, and was followed by a
steep decline at around -0.10 V. A second peak (D) was recorded during the anodic scan
following the 2 hour immersion at around +0.45 V. This peak is most probably
attributed to the oxidation of the nickel sulfide layer which has formed on the surface of
the electrode. The magnitude of peak (C) was smaller than for peak (A), possibly due to
the formation of species on the surface of the electrode, which reduce the number of sites
for the anodic dissolution of iron.
During the reverse scan, another peak (E) was observed at around -0.40 V. This peak
corresponded to the cathodic reactivation of iron dissolution, but because the nickel
sulfide layer was already formed on the surface of the electrode, recorded a current
density around five times smaller than peak (B) from the initial immersion test.
4.1.1.3 SEM/EDX Analysis

Following the OCP measurement, the iron electrode was removed from the solution,
gently rinsed with deionised water and its surface was analysed by the SEM/EDX
spectroscopy in order to gain more information about the composition of the layers
formed on its surface. As it can be seen from Figure 20, small particles were detected on
the surface. The EDX analysis of the surface resulted in the detection of ~20% of nickel
and ~15% of sulfur. Previous surface characterisation studies using GIXRD by D’Aloya
(2015) revealed the presence of crystalline nickel sulfide (Ni3S2) on the surface of the
electrode.
38 | P a g e
FIGURE 20. SEM image of iron RDE following 3 hour immersion in a 3M [NH3]T and 1M [CO2]T
containing 0.15M Ni(II) and 0.022M S2O32-.
4.1.1.4 Metal Dissolution Analysis

The surface of the iron electrode was pre-treated in 100 ml of deoxygenated 3M [NH3]T
+ 1M [CO2]T + 0.15M Ni(II) + 0.022M S2O32- solution for 2 hours at 45°C. After the 2
hours, the iron electrode was immersed in 100 ml of deoxygenated barren solution (5M
[NH3]T + 1M [CO2]T) heated up to 45°C. The metal dissolution was carried out for 5
hours, with the iron electrode rotated at 200 rpm. Solution samples were taken at
different time intervals, and were analysed for total nickel concentration by the AAS.
The results of nickel dissolution are presented in Figure 21.
39 | P a g e
0.25
0.2
Ni CONCENTRATION (mM/L)
0.15
0.1
0.05
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 21. Nickel dissolution from iron RDE in 5M [NH3]T + 1M [CO2]T following pre-treatment
in 3M [NH3]T + 1M [CO2]T + 0.15M Ni(II) + 0.022M S2O32- solution.
Based on the results presented in Figure 21, with the assumption that the sulfide layer
was uniformly distributed on the surface of the iron electrode, the initial dissolution of
nickel took place at a rate of around 1.64 mg/L/min/ cm2.
As it can be seen in Figure 21, the dissolution of nickel was rapid in the first 5 minutes
following re-immersion of the electrode in the barren solution, reporting a concentration
of 0.1mM/L. During the next 4 hours it was seen to level off, with the concentration of
dissolved nickel at ~0.16mM/L at the 4 hour mark. According to the previous studies
done by D’Aloya (2015), this levelling off of nickel in solution rate possibly correlates to
the reported decrease in mixed potential, which is influenced mainly by the underlying
iron oxide. A steep increase in the rate of nickel dissolution was noticed during the last
hour, with a final dissolved nickel concentration in solution at 0.2mM/L at the end of
the test.
4.1.2 Leaching of a Synthetic Sample (SMMS)

Before conducting the leaching studies, the nickel sulfide (Ni3S2) feed sample was laser
sized and characterised by the SEM/EDX, XRD. The results from the SEM/EDX
analysis are presented in Figure 22. A quantitative analysis of this feed material was
40 | P a g e
performed, with the results of mass (%) compositions presented in Table 2. The XRD
analysis is shown as Figure 93 (p.133).
A B
FIGURE 22. SEM/EDX analysis of the nickel sulfide sample used in the leaching tests (A) SEM
image of the nickel sulfide particles, (B) corresponding spectra for image (A), and (C) EDX image
showing the spots that were quantitatively analysed.
41 | P a g e
TABLE 2. Elemental composition of the nickel sulfide feed (FIGURE 22 (A)) and the elemental
composition of the feed at certain spots from FIGURE 22 (C).
MASS (%)
Ni S O
COMPOSITION
FEED 49.13 15.01 35.86
SPOT 002 60.53 9.20 30.27
SPOT 003 53.29 12.89 33.82
SPOT 004 70.61 4.06 25.33
SPOT 005 66.74 6.03 27.22
A detailed characterisation study of the feed sample was carried out, and it was found
that the nickel sulfide sample contained higher amounts of oxygen than initially
expected. The quantitative data presented in Table 2, shows that nickel and oxygen were
uniformly distributed throughout the feed sample, while sulfur was not. The increased
oxygen content in this sample suggests that the Ni3S2 feed possibly oxidized to NiSO4,
which would explain the differences in theoretical and calculated mass balances of the
leaching tests. After performing the sizing analysis, the P80 of the nickel sulfide feed was
reported to be 19.14 µm.
The leaching of nickel from nickel sulfide was carried out under various leaching
conditions, which included different ammonia and ammonium carbonate concentrations
as well as different temperatures in order to analyse the kinetic behaviour of nickel. All
leaching experiments were performed with air. The tests were conducted using 0.5 g of
99.97% nickel sulfide (Ni3S2) powder in a 500 ml solution, containing particular
ammonia and ammonium carbonate concentrations mixed with thiosulfate ions, and an
addition of sodium sulfite, where appropriate. The nickel sulfide powder used in the
experiments contained no moisture. The assumption that this nickel sulfide feed has
undergone oxidation, however, is supported by the solid characterisation analysis,
presented in Table 2, and leach mass balance calculations from Appendix B (p.114-118).
A summary of the nickel leaching data is presented in Table 3.
42 | P a g e
TABLE 3. Nickel leaching summary (SMMS)
TEMP (°C) [NH3]T (M) [CO2]T (M) [Na2SO3] (M) % Ni EXTRACTION

45 7 1 - 67.9
45 5 1 - 47.9
45 3 1 - 99.2
45 3 0.5 - 64.7
45 3 1.5 - 76.6
25 3 1 - 49.2
60 3 1 - 99.5
45 3 1 0.25 88.4
45 3 1 0.50 74.2
4.1.2.1 The effect of ammonia concentration on nickel leaching from nickel

sulfide.
The leaching of nickel from nickel sulfide was carried out at three different ammonia
concentrations in order to investigate how ammonia affects the leaching rate of nickel.
The chosen concentrations of ammonia were 3M, 5M and 7M, mixed with 1M [CO2]T
and 0.022M S2O32-. The results are summarised in Figure 23.
100
90
80
70
% Ni EXTRACTION
60
50
40
30 7M
20 5M
10 3M
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 23. The effect of ammonia concentration on the leaching efficiency of nickel from nickel
sulfide.
Based on the results presented in Figure 23, it can be seen that the highest nickel
extraction (~99.5%), was achieved in a leach solution containing 3M ammonia, with the
43 | P a g e
7M ammonia leach test achieving ~65% after 5 hours of leaching, and 5M ammonia
leach with ~ 45% nickel extracted into the solution. The dissolution of nickel in the 3M
leach test has shown a significant increase from the first hour to the second, increasing
from ~45% to ~75% within that single hour. A smaller increase was also recorded
between the 3rd and the 4th hour in the same test, from ~75% to ~95%. The 7M leach test
showed overall slower kinetics when compared to the other 2 tests, however the
extraction of nickel was the same (at ~45%) as in the 3M leach test at the end of the first
hour. For the remainder of the 7M leach test, the amount of nickel extracted into the
solution only slightly increased, and plateaued at ~50%, with an increase to ~65%
recorded during the last hour of leaching. During the first 5 minutes of leaching, the 5M
test reported an extraction of ~25%, which was slightly higher than those recorded for
the other 2 test. The extraction increased to ~35% at the 30 minute mark, but showed a
flatter recovery profile after that, with very little change recorded for the remaining 4.5
hours.
In the Caron process, ammonia is the main reagent reacting with nickel during leaching.
Its concentration as well as how the ammine complexes are formed in the solution will
be important when determining the overall leaching kinetics. When nickel is leached in
ammonia-ammonium carbonate solution, it will form ammines with ammonia,
according to the following:
[Eq.18]
Zhong and Hepworth (1995) have shown that increasing the ammonia concentration,
increases the pH of the leach solution, and with it, the chemical driving force is also
increased. The increasing pH trend as the concentration of ammonia increases was also
observed during this study, reporting that the highest ammonia concentration test at 7M
reached the highest pH values (~10.4), the 5M test ~9.9, and 3M test ~9.5. The
increased chemical driving force of the leach at higher ammonia concentration, however,
was not observed, as the results from this study show that at a lower ammonia
concentration of 3M the extraction of nickel from nickel sulfide is more efficient. Lower
recovery of nickel when the concentration of ammonia is increased has also been
reported by Hu et al. (2012). One of the possible explanations for this lower extraction
might be the fact that as the ammonia concentration is increased, the concentration of
44 | P a g e
OH- in solution also increases, leading to the formation of nickel oxide or hydroxide, and
resulting in a decreased leaching rate.
In a Ni-NH3-H2O system, as the pH ranges between 8.5-10.5, the main soluble species
will be Ni(NH3)52+. If the pH is increased to ~11, Ni(NH3)62+ will also be present.
According to Meng and Han (1995), unlike cobalt or copper, nickel amine complexes
cannot serve as an oxidant in an aqueous solution, as no higher or lower oxidation state
can be paired under these conditions.
4.1.2.2 The effect of ammonium carbonate concentration on nickel leaching

from nickel sulfide.
The leaching of nickel from nickel sulfide was carried out at three different ammonium
carbonate concentrations, in order to investigate the relationship between ammonium
carbonate and the leaching kinetics of nickel. The chosen concentrations of ammonium
carbonate were 0.5M, 1M and 1.5M, mixed with 3M [NH3]T and 0.022M S2O32-. The
results are presented in Figure 24.
100
90
80
70
% Ni EXTRACTION
60
50
40
30 0.5M
20 1M
10 1.5M
0
0 1 2 TIME (Hrs) 3 4 5
FIGURE 24. The effect of ammonium carbonate concentration on the leaching efficiency of nickel
from nickel sulfide.
From the results presented in Figure 24, it can be seen that the highest nickel extraction
was achieved with 1M ammonium carbonate, ~98% after 5 hours of leaching, the
45 | P a g e
second highest (~75%) extraction of nickel was reported during the 1.5M ammonium
carbonate test, with the least (~60%) nickel extracted into the solution reported during
the 0.5M ammonium carbonate leach test. During the first 5 minutes of leaching, the test
with the highest ammonium carbonate concentration showed the fastest leaching
kinetics, with ~40% of nickel dissolved in solution within 5 minutes. The 1M leach test
recorded ~25% nickel extraction during the first 5 minutes, with the 0.5M test reporting
just under 20% nickel extraction. The 1.5M test continued to show the highest nickel
extraction till around the 1.5 hour mark, at which point the 1M leach test showed a
significant increase, continuing till the end of the process. The 0.5M ammonium
carbonate test showed a steady increase in nickel extraction throughout the 5 hours of
leaching. The percentage of nickel extracted into the solution at each sampling stage,
however, was always significantly lower than amounts of nickel dissolved in the same
time frame for the other 2 tests. As it can be seen from the leach data in Appendix B,
there were significant differences between the pH values recorded during the 0.5M leach
test, ranging from 10.0-10.1, compared to the pH values recorded for the 1M test (9.5-
9.6), and the 1.5M test (9.4-9.5).
The main role of ammonium carbonate in ammoniacal leaching is to supply anions to

the ammine complexes, compensating with the hydroxide anion generation during
ammine complex formation (Sun et al., 2015). According to Sun et al. (2015), one of the
possible reasons for the drop of nickel extraction as the concentration of ammonium
carbonate increases (also seen in Figure 24), is related to the thermodynamic interaction
between ammonia and ammonium carbonate. The dissociation of ammonia and
ammonium carbonate in an aqueous solution is at equilibrium with temperatures, when
K1 and K2 are constant, as represented in the following equations:
[Eq.19]
[Eq.20]
An increase in the concentration of ammonium carbonate, will lower the overall

concentration of [NH4+], allowing K2 to be kept constant, but as a result producing a
lower overall recovery of nickel, as its concentration increases.
46 | P a g e
4.1.2.3 The effect of temperature on nickel leaching from nickel sulfide.
The leaching of nickel from nickel sulfide was carried out at three different temperatures,
in order to establish how temperature will influence the leaching kinetics of nickel. The
chosen temperatures were 25°C, 45°C and 60°C. All three experiments were carried out
in a leach solution made up of 3M [NH3]T mixed with 1M [CO2]T and 0.022M S2O32-.
The results are summarised in Figure 25.
100
90
80
% Ni EXTRACTION
70
60
50
40
30 25°C
20 45°C
10 60°C
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 25. The effect of temperature on the leaching efficiency of nickel from nickel sulfide.
Based on the results presented in Figure 25, it can be seen that the highest nickel
extraction was achieved when the leaching temperature was at 60°C, with the second
highest extraction at 45°C. The leach test with the lowest nickel extraction was the one
at 25°C. The leach test carried out at 45°C showed the fastest leaching kinetics during
the first 4 hours, slightly dropping in the last hour, at which point the test performed at
60°C reported more nickel extracted into the solution. The leach test at 45°C extracted
~40% of nickel within the first 5 minutes of leaching, the test at 60°C, ~25%, and the test
at 25°C, just over 35%. At the 1 hour mark the 25°C test continued at ~35% nickel
extracted, the 45°C test at just over 65%, with the 60°C test at ~45% of nickel
extraction. Seen from Figure 25, the 25°C leach showed very little change in the amount
of nickel dissolved into the solution, with only ~40% of nickel extracted at the end of the
5 hours. According to Sun et al. (2010), when the leaching profile becomes flatter, as is
the case seen during the 25°C test in Figure 25, it suggests that the leaching mechanism
47 | P a g e
has become different from the early stage, and the leaching kinetics are now influenced
by mass transfer or diffusion, with the reactivity of the leach solution becoming lower,
possibly due to the lower free ammonia concentration in the leach solution.
4.1.2.4 The effect of sodium sulfite addition on nickel leaching from nickel
sulfide.
The leaching of nickel from nickel sulfide was carried out both with, and without, the
addition of sodium sulfite (Na2SO4) in order to investigate how the addition would
influence the leaching kinetics of nickel. The two chosen sodium sulfite concentrations
were 0.25M and 0.5M, and were compared to the test carried out under the same
conditions, but with no sodium sulfite addition. The 500 ml leach liquor contained 3M
[NH3]T mixed with 1M [CO2]T and 0.022M S2O32-. The results are summarised in Figure
26.
100
90
80
70
% Ni EXTRACTION
60
50
40
30 0M
20 0.25M
10 0.50M
0
0 1 2 TIME (Hrs) 3 4 5
FIGURE 26. The effect of sodium sulfite addition on the leaching efficiency of nickel from nickel
sulfide.
The results presented in Figure 26 imply that the leaching efficiency of nickel from nickel
sulfide does not improve with the addition of sodium sulfite. In fact, the higher the
addition, the lower the extraction. The leach test containing no sodium sulfite achieved
~96% of nickel in solution at the end of the 5 hours, compared to ~88% with 0.25M
sodium sulfite addition and ~74% with 0.5M addition. The pH values recoded for each
test were ~9.3 with no addition, ~9.7 with 0.25M and ~10.1 with 0.5M.
48 | P a g e
The addition of a reducing agent in the extraction of nickel was studied by Meshram et
al. (2015). It was found that unlike cobalt, nickel hardly undergoes the reduction process.
The addition of sodium sulfite will, therefore, play a limited role in the leaching of nickel
containing non-stoichiometric phases (Meshram et al., 2015). Another possible reason
for lower nickel extraction with the addition of a reductant could be the fact that when
added, sodium sulfite will react with oxygen, reducing the amount of dissolved oxygen
available for the leaching reaction, so causing the leaching rate to decline.
4.1.2.5 Kinetic Model for Synthetic Nickel Sulfide

In three separate studies by Bhuntumkomol et al. (1982), Mizokuchi et al. (1978), and
Mothobi (2012), the dissolution of nickel was shown to follow the ash layer diffusion
model. The initial rate of nickel dissolution is now believed to be influenced by the
concentration of oxygen, the density and radius of the particles as well as the mass
transfer coefficient.
0.9
25°C R² = 0.97
0.8
45°C R² = 0.95
0.7 R² = 0.95
60°C
0.6
1-(1-x)1/3
0.5
0.4
0.3
0.2
0.1
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 27. Plot of surface reaction model vs time for the leaching of nickel from nickel sulfide at
different temperatures.
49 | P a g e
1
25°C R² = 0.97
0.9
45°C R² = 0.96
0.8
60°C R² = 0.94
0.7
1-3(1-x)2/3 + 2(1-x)
0.6
0.5
0.4
0.3
0.2
0.1
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 28. Plot of ash layer diffusion model vs time for the leaching of nickel from nickel
sulfide at different temperatures.
0.8
25°C R² = 0.95
0.7 45°C R² = 0.92
1-2(1-x)1/3 + (1-x)2/3
0.6 60°C R² = 0.87
0.5
0.4
0.3
0.2
0.1
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 29. Plot of the mixed model vs time for the leaching of nickel from nickel sulfide at
50 | P a g e
TABLE 4. Correlation coefficients for the different models at various leaching conditions of nickel
sulfide.
Surface
R2 values Ash Diffusion Mixed Model
Reaction
TEMP (°C)
25 0.97 0.97 0.95
45 0.95 0.96 0.92
60 0.95 0.94 0.87
[NH3]T (M)
3 0.95 0.94 0.87
5 0.96 0.97 0.97
7 0.88 0.90 0.90
[CO2]T (M)
0.5 0.99 0.96 0.94
1 0.95 0.94 0.87
1.5 0.97 0.97 0.96
The analysis of the kinetics data for nickel shown in Figure 25, indicate that between 20-
60% of nickel can be extracted within the first 30 minutes of leaching, with the
extractions slowing down after that. This might suggest that the leaching of nickel takes
place in two separate stages, the first stage being controlled by a surface reaction because
it is more rapid, and the second stage of leaching controlled by ash diffusion, as the rate
slows down. The data was fitted into the models from 30 minutes to 5 hours, in order to
determine the correlation coefficients of the second stage of leaching from the regression
analysis. Calculations from the data in Table 4 show that it was the ash diffusion model
that gave the best fit, evident from the relatively high correlation coefficient values. From
the data presented in Table 4, it can be seen that the correlation coefficient for surface
reaction is higher than for the mixed model. From the slopes of
vs time plots the K values were calculated, and the Arrhenius plot for nickel
leaching was constructed (Figure 30).
51 | P a g e
0
-0.5
-1
y = -1.76x + 3.64
-1.5
ln k
-2
-2.5 y = -8.37x + 24.39
-3
-3.5
-4
2.9 3 3.1 3.2 3.3 3.4
1000/T (K)
FIGURE 30. Arrhenius plot for nickel leaching from nickel sulfide.
The results presented in Figure 30 suggest that the reaction mechanisms are in fact
different at different temperatures. The activation energy for the lower temperatures
(25°C - 45°C) was calculated to be 69.6 kJ/mol, while the activation energy for the
higher temperature (>45°C) was 14.7 kJ/mol. The significantly high activation energy
calculated for the lower temperature range indicates that the leaching reactions will be
slower and will require more additional energy in order to proceed. As the temperature
of leaching is increased, the reaction will require less energy in order to proceed.
1
0.9
0.8
0.7
0.6 y = 0.18x + 0.43
- log (k)
0.5
0.4
0.3
0.2
0.1
0
0 0.5 1 1.5 2 2.5 3
log [NH3]
FIGURE 31. Plot of –log k vs log [NH3] for reaction order estimation.
52 | P a g e
0.3
0.2
0.1
0
-log (k)
-0.1
-0.2 y = -0.09x + 0.06
-0.3
-0.4
0 0.5 1 1.5 2
log [CO2]
FIGURE 32. Plot of – log k vs log [CO2] for reaction order estimation.
From the slopes of the lines in Appendix E (Figure 97 p.134), the apparent rate constants
(k) were calculated. The plot in Figure 31 shows -log (k) vs log [NH3] which was
constructed to determine the order of dependency with respect to ammonia
concentration. The empirical reaction order with respect to ammonia concentration was
determined to be 0.18 (Figure 31). Similarly, -log of the apparent rate constants from
Figure 100 (p.136) were plotted vs log [CO2] to determine the dependency with respect to
ammonium carbonate concentration. Figure 32 shows that the reaction order with
respect to ammonium carbonate concentration was calculated to be 0.09. These results
indicate that the leaching of nickel from nickel sulfide under these sets of conditions has
a higher dependency on the ammonia concentration than on the ammonium carbonate
concentration.

The leaching of nickel from sulfide flotation concentrate was conducted under optimum
conditions (based on the leaching studies of synthetic nickel sulfide), with and without
the addition of sodium sulfite. The aim of these tests was to compare the experimental
results from the leaching studies of SMMS to RMS through the analysis of their leaching
behaviours under the same conditions. The leach liquor was made up of 3M [NH3]T +
1M [CO2]T with 0.25M Na2SO3, where appropriate. The leach tests were performed in a
53 | P a g e
500 ml glass reactor, at 45°C with air. 10 g of the feed concentrate was used in each test.
The results are summarised in Figure 33.
60
NO SODIUM SULFITE
50
0.25M SODIUM
SULFITE
40
% Ni EXTRACTED
30
20
10
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
TIME (Hrs)
FIGURE 33. The effect of sodium sulfite addition on the leaching of nickel from nickel flotation
concentrate.
From the results presented in Figure 33, it can be seen that the addition of sodium sulfite
has improved the leaching efficiency of nickel. During the first 3 hours, the leaching rates
were identical in both tests, at ~5% extraction. At the 4 hour mark the test without
sodium sulfite addition recorded ~10% of nickel in solution compared to still ~5% in the
test with the addition. The profile of the leach without the sodium sulfite addition did
not change for the remainder of the test and finished at an overall nickel extraction of
~15%. The rate of the extraction was calculated to be 0.07 mg/L/min. The leach test
with the addition of sodium sulfite was seen to increase significantly from the 6th hour till
the 30th hour of leaching, finishing at ~48% extraction. The rate of extraction for this test
was calculated to be 1.31 mg/L/min.
Similar results were presented by Chong et al. (2013), where nickel was leached with and
without the addition of a reductant (sulfite). Their results show that nickel extraction can
be increased with an addition of a reductant. As a possible explanation they have
suggested that nickel was oxidised, or possibly associated with manganese solids, since
these respond well to a reducing agent.
54 | P a g e
Prior to conducting the leaching studies, an elemental analysis was performed on the
feed, with the results presented in Table 5, together with the elemental analysis of both
leach residues. Residue A represents the residue from leaching without the addition of
sodium sulfite, while Residue B is from the test with the addition of sodium sulfite. A
SEM micrograph was taken of the feed sample as well as the residue samples, and is
presented in Figure 34.
The XRD analysis of Leach Residue A (Figure 116 p.144) shows pyrrhotite (Fe(1-x)S) and
goethite (FeOOH) as the major constituents. In the XRD analysis of Leach Residue B
(Figure 117 p.145), the major constituents are pyrrhotite and valleriite
(Fe2+,Cu)4(Mg,Al)3S4(OH,O)6, with only a minor phase of goethite. According to Luo et
al. (2015), nickel in limonitic laterite becomes substituted in goethite, making a complete
dissolution of goethite necessary for good nickel extraction. The addition of a reductant
will lower the potential, which will help to convert FeOOH to Fe 2+, so releasing the
nickel. The leaching efficiency of nickel will be improved (Luo et al., 2015).
TABLE 5. Elemental composition of the Nickel Sulfide flotation feed and both leach residues.
FEED RESIDUE A RESIDUE B

ELEMENT
% (g) % (g) % (g)
Ni 0.95 0.10 0.40 0.04 1.16 0.11
Fe 56.70 5.67 23.31 2.06 60.96 5.52
S 36.80 3.68 7.17 0.63 8.05 0.73
Cu 0.07 0.01 0.47 0.04 0.00 0.00
Other 0.53 0.05 68.65 6.08 29.83 2.97
Based on the results presented in Table 5, it can be seen that leaching with the addition
of sodium sulfite (Residue B) has resulted in significantly more Fe and Ni precipitating
out, compared to the leaching without the addition of sodium sulfite (Residue A). It is
possible that higher amount of Ni in the residue could be associated with a limited Ni
dissolution as it becomes trapped within the iron matrix. On the other hand, the amount
of sulfur in both residues was relatively similar.
55 | P a g e
A
B C
FIGURE 34. SEM images of (A) nickel feed, (B) Leach Residue A, and (C) Leach Residue B.
56 | P a g e
4.2 THE INVESTIGATION OF COBALT SULFIDE
This section presents the results and discussion of cobalt sulfide. The investigations of
the electrochemically formed, and the synthetic monometallic cobalt sulfide, are
outlined, and a comparison of the rate and extent of each is presented at the end.

This section includes the analysis of the electrochemically formed cobalt sulfide. The
results from the OCP and CV tests are presented, as well as the characterisation studies
of the formed sulfide layer. The rate and extent of the dissolution of this sulfide layer is
also presented.

The open circuit potential of the iron electrode was measured for 3 hours in a
deoxygenated 5M [NH3]T + 1M [CO2]T solution containing 0.012M Co(II) and 0.022M
thiosulfate ions. The electrode was rotated at 200 rpm, and the solution was maintained
at 45°C. Figure 35 shows the obtained result.
0.04
0.02
0
E (V vs SHE)
-0.02
-0.04
-0.06
-0.08
-0.1
-0.12
0 30 60 90 120 150 180
TIME (mins)

cobalt (II) and thiosulfate ions.
As it can be seen from Figure 35, the spontaneous passivation of the iron electrode took
place after 128 minutes of immersion in a deoxygenated ammoniacal-carbonate solution
containing cobalt (II) and thiosulfate ions.
57 | P a g e
The rotating disk voltammetry tests were conducted on the iron electrode immersed in a
deoxygenated 5M [NH3]T + 1M [CO2]T solution containing 0.012M Co(II) and 0.022M
thiosulfate ions. The potentials were scanned in the positive direction from an initial
potential of -0.60 V, with the vertex potential of +1.20 V, and the final potential at -0.56
V. The sweep rate was kept at 10 mV/s. The iron electrode was rotated at 200 rpm and
the solution was maintained at 45°C. Cyclic voltammograms were constructed at 0 hours
(initial immersion) and 2 hours after immersion, and are represented in Figure 36.
160 INITIAL
A 2Hrs
120
i (mA/cm2)
80
B
40
C D
E
0
-40
-1.0 -0.5 0.0 0.5 1.0 1.5
E (V vs SHE)
FIGURE 36. CV of iron following different immersion times in a deoxygenated Co (II) thiosulfate
ammoniacal solution.
Cyclic voltammetry measurements conducted following different immersion times in a

deoxygenated cobalt (II) thiosulfate ammoniacal solution resulted in a significant
reduction of the iron oxidation peaks. As the potential was scanned in the positive
direction from -0.60 V, a peak (A), assigned to the anodic oxidation of iron was observed
around -0.25 V. This peak was followed by a steep reduction, where no significant
currents were recorded. As the scan was reversed, a second peak (B) was recorded at
around -0.50 V. This peak was attributed to the reactivation of the metallic iron. After
the iron electrode has been immersed in the solution for 2 hours, another cyclic
voltammetry measurement was conducted. As the potential was scanned in the positive
direction from -0.60 V, an iron oxidation peak (C) was observed, but was significantly
58 | P a g e
smaller than the oxidation peak (A) from the initial immersion test. This is most
probably because the surface of the iron electrode has gradually become covered with
some solid species, which have a negative effect on the anodic dissolution of iron. As the
scanned potential continued towards more positive values, another anodic peak (D) was
recorded at +0.5 V. This peak was of the same magnitude as peak (C), and most
probably because of the solid species deposited on the surface of the electrode
undergoing the dissolution processes. With the potential scanned from above +0.55 V to
+1.2 V, no currents were recorded. With the reversal of the scan, no currents were
observed till around -0.4 V, where a smaller peak (E) was noticed. This peak represented
the reactivation of metallic iron. It was noticed that this reactivation seemed to be
significantly reduced, however, with the longer immersion times. From these results, it
can be said that, as the time of the iron electrode’s exposure to the solid species present
in the solution increases, its reactivation becomes increasingly limited.

The surface of the iron electrode was studied following its immersion and passivation in
a solution containing 5M [NH3]T + 1M [CO2]T + 0.012M Co(II) + 0.022M S2O32- by the
SEM/EDX spectroscopy. The surface of the electrode after the 3 hour immersion is
shown in Figure 37. According to D’Aloya (2015) the species responsible for passivation
of iron have been cobalt and thiosulfate ions, but only when these were both present in
the solution. As it can be seen in Figure 37, there are a number of small particles visible.
These particles could possibly indicate localised corrosions, resulting in the precipitation
of a product containing iron oxide/hydroxide or carbonate, also observed in previous
studies by D’Aloya (2015). Figure 37 (b) shows a close up of one of these particles. The
layer formed on the surface of the electrode was believed to consist of cobalt sulfide or
polysulfide (CoSx), but this was not investigated any further during this study. The EDX
quantitative analysis revealed that the layer consisted of ~10% Co and ~15% S.
59 | P a g e
a) b)
FIGURE 37. SEM image of the iron RDE following 3 hour immersion in 5M[NH3]T and 1M[CO2]T
containing 0.012M Co(II) and 0.022M S2O32- a) image of a larger area, b) close up on spot marked
with an arrow.

+ 1M [CO2]T + 0.012M Co(II) + 0.022M S2O32- solution for 2 hours at 45°C. After the 2
hours, the iron electrode was immersed in 100 ml of deoxygenated Barren solution (5M
[NH3]T + 1M [CO2]T), heated up to 45°C. The metal dissolution was carried out for 5
hours, while the iron electrode was being rotated at 200 rpm. Solution samples were
taken out at different time intervals, and were analysed for the total cobalt concentration
by the AAS. The results of cobalt dissolution are presented in Figure 38.
60 | P a g e
0.04
Co CONCENTRATION (mM/L) 0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 38. Cobalt dissolution from iron RDE in a 5M [NH3]T + 1M [CO2]T following pre-
treatment in 5M [NH3]T + 1M [CO2]T + 0.012M Co(II) + 0.022M S2O32- solution.
Based on the results presented in Figure 38, with the assumption that the layer was
uniformly distributed on the iron electrode, the initial dissolution of cobalt took place at
a rate of around 0.17 mg/L/min/ cm2.
The dissolution of cobalt was very rapid during the first 5 minutes, then it levelled off at
around 0.015mM/L for the next 4 hours. This period of no significant increase in
dissolved cobalt concentration might be the result of the sulfide layer becoming more
cobalt-deficient, more sulfur-rich and therefore non-conductive. A suggestion that this
surface layer does not undergo further oxidation even when higher potentials are being
applied has been reported by D’Aloya (2015).

Prior to conducting the leaching studies, the cobalt sulfide (CoS2) feed sample was laser
sized and analysed by the SEM/EDX and XRD instruments. The results from the
SEM/EDX analysis are presented in Figure 39. The feed material was quantitatively
analysed at different spots, with the mass (%) composition results presented in Table 6.
The XRD analysis is shown in Figure 94 (p.133).
61 | P a g e
A
B
FIGURE 39. SEM/EDX analysis of the cobalt sulfide sample used in the leaching tests (A) SEM
image of the cobalt sulfide particles, (B) corresponding spectra for image (A), and (C) EDX image
showing the spots that were quantitatively analysed.
TABLE 6. Mass (%) composition of cobalt sulfide feed sample used and mineral composition at
certain spots from FIGURE 39 (C).
MASS (%)
Co S O
COMPOSITION
FEED 38.55 20.42 41.03
SPOT 001 34.63 22.42 42.96
SPOT 002 61.70 8.63 29.67
SPOT 003 51.42 13.86 34.71
SPOT 004 30.77 24.38 44.85
SPOT 005 27.18 26.21 46.61
62 | P a g e
Based on the elemental composition analysis of the cobalt sulfide (CoS2) feed presented
in Table 6, it can be seen that this sample has undergone oxidation to cobalt sulfate
(CoSO4). The higher than expected levels of oxygen in the feed, as well as the mass
balance calculations of the leaching data (Appendix B p.118-122) support this finding.
A sub-sample of the feed material has been analysed for the average size of the particles,
and it was found that 80% are < 32.20 µm.
The leaching of cobalt from cobalt sulfide was carried out under various conditions
which included different ammonia and ammonium carbonate concentrations as well as
different temperatures, in order to analyse the leaching kinetics of cobalt. All leaching
tests were performed with air, and were carried out using 0.5 g of 99.98% cobalt sulfide
(CoS2) powder in a 500 ml solution containing particular ammonia concentration mixed
ammonium carbonate and thiosulfate ions. The cobalt sulfide powder used in the
experiments was found to contain 17% moisture, and the actual pure cobalt content in
the powder was calculated to be between 20-30%, as opposed to ~47% expected from the
stoichiometric ratio. This lower cobalt content in the feed sample is most probably a
result of the sample becoming oxidised to CoSO4, an earlier assumption confirmed by
the EDX quantitative analysis presented in Table 6. The leaching results are summarised
in Table 7.
TABLE 7. Cobalt leaching summary (SMMS).
% Co
TEMP (°C) [NH3]T (M) [CO2]T (M) [Na2SO3] (M)
EXTRACTION
45 7 1 - 48.8
45 5 1 - 74.2
45 3 1 - 46.4
45 5 2 - 69.2
45 5 3 - 71.4
25 5 1 - 68.1
60 5 1 - 71.1
60 5 1 0.50 86.7
63 | P a g e
4.2.2.1 The effect of ammonia concentration on cobalt leaching from cobalt
sulfide.
The leaching of cobalt from cobalt sulfide was carried out at three different ammonia
concentrations in order to investigate how ammonia affects the leaching kinetics of
cobalt. The chosen concentrations of ammonia were 3M, 5M and 7M. All leaching
experiments were performed at 45°C . The results are summarised in Figure 40.
100
90
80
% Co EXTRACTION
70
60
50
40
30 7M
20 5M
10 3M
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 40. The effect of ammonia concentration on the leaching efficiency of cobalt from cobalt
sulfide.
Based on the results from Figure 40, it can be seen that the 5M ammonia concentration
achieved the highest cobalt extraction, with over 70% of total cobalt extracted within the
5 hours of leaching duration. Fast leaching kinetics were noticed in the first 30 minutes
of the leaching process, with around 60% of total cobalt extracted in that time frame.
Only an additional 10% was recovered into solution in the remaining 4.5 hours. During
the leaching of cobalt in the 3M ammonia solution, only ~25% of total cobalt was
extracted within the first 30 minutes of leach, with the total of ~ 40% of cobalt extracted
after the 5 hours. This ammonia concentration showed a significant decrease in the
leaching efficiency when compared to the 5M ammonia leach, and this can be easily
seen in Figure 40. The leach test in the 7M ammonia solution was only able to extract
~10% of total cobalt in the first 30 minutes to 1 hour, but showed a significant increase
in the leaching rate from the second hour right till the end, to the point where, after the 5
64 | P a g e
hours of leaching, the 7M ammonia leach achieved slightly higher cobalt extraction than
the 3M ammonia leach. Based on these observations, it can be said that the optimum
ammonia concentration for the most efficient cobalt extraction from cobalt sulfide is 5M,
where both higher and lower variation from this have a negative effect on the overall
extraction. A similar trend was reported by Zuniga et al. (2010), who suggested that
increasing the ammonia concentration will lead to a formation of Fe3+
oxides/hydroxides, resulting in more losses of cobalt.
As it can be seen from the leach data in the Appendix B (p.118-122), the pH was at
around 10.4 during the 7M leach, 10.2 during the 5M leach and around 9.7 during the
3M leach. Nabizadeh and Aghazadeh (2015) have shown that the pH of the leach
solution will have a tendency to remain constant or to slowly increase during leaching,
promoting the formation of stable cobalt-ammonia complexes. The pH values will
readjust due to the equilibration with the Co(NH3)62+ complex (Nabizadeh and
Aghazadeh, 2015). According to Ku et al. (2016), once cobalt forms low valence ions, it
will exist as a complex ion with NH3 in ammoniacal solution, given by the following
reaction:
+ [Eq.21]
The region where the Co(NH3)62+ complex can be stable is defined as a function of
temperature, total ammonia concentration ([NH3] + [NH4+]) and pH (Nabizadeh and
Aghazadeh, 2015). From the data presented in the Appendix B, the optimum pH range
for stable cobalt complex formation is found to be around 10.2. Cobalt extraction was
lower when the pH dropped to around 9.7, or when the pH of the leach solution
increased to 10.4. According to Nabizadeh and Aghazadeh (2015), the following
equilibrium exists in ammoniacal solution:
, = , [Eq.22]
And from this, a following relationship can be obtained:
[Eq.23]
At lower pH, the ratio of [NH3] to [NH4+] will be insufficient to form stable cobalt
complexes. Most of the total ammonia ([NH3] + [NH4+]) will be present as ammonium
65 | P a g e
ion, with not enough free ammonia [NH3] available for leaching cobalt. When the pH of
the leach solution is greater than 10.4, the concentration of the free ammonia as well as
OH- are still increasing. Based on the leaching data for the 7M ammonia concentration
presented in Figure 40, however, and the pH variations reported during this leach, there
is a strong possibility that cobalt oxide or hydroxide is forming, which would explain the
decrease in the leaching rate.
According to Meng and Han (1995), in the Co-NH3-H2O system and the pH/Eh
diagram, the major soluble species between pH 9-11 will be Co(NH3)63+, Co(NH3)52+ and
Co(NH3)42+. The ratios can be determined by the potential of the system, and is
represented as:
[Eq.24]
[Eq.25]
[Eq.26]
[Eq.27]
4.2.2.2 The effect of ammonium carbonate concentration on cobalt leaching

from cobalt sulfide
The leaching of cobalt from cobalt sulfide was carried out at three different ammonium
carbonate concentrations in order to investigate the relationship between ammonium
carbonate and the leaching kinetics of cobalt. The tested concentrations of ammonium
carbonate were 1M, 2M and 3M mixed with 5M [NH3]T .The results are summarised in
Figure 41.
66 | P a g e
100
90
80
70
% Co EXTRACTION
60
50
40
30 1M
20 2M
10 3M
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 41. The effect of ammonium carbonate concentration on the leaching efficiency of cobalt
from cobalt sulfide.
Based on the results in Figure 41, it can be said that the 1M ammonium carbonate
concentration leach achieved the best cobalt extraction of ~ 71% after 5 hours of
leaching. Within the first 30 minutes of leaching, ~ 60% of total cobalt was extracted.
With the 2M ammonium carbonate concentration leach test, ~ 50% of cobalt was
extracted into the solution within the first 30 minutes, with ~ 60% of cobalt in solution at
the end of the 5 hours. The 3M ammonium carbonate leach extracted ~ 45% of total
cobalt within the first 30 minutes of the test, with ~ 50% of cobalt in solution by the end
of the fourth hour. It was noticed that ~ 10% of cobalt became extracted during the last
hour of the leach test. This result poses a question of whether more cobalt could have
been extracted under these conditions, if the duration of the leach was extended. In their
findings, Nabizadeh and Aghazadeh (2015) reported that as the concentration of
ammonium carbonate (at a constant ammonia concentration) decreases, the leaching
kinetics of cobalt will increase. The results from this study, presented in Figure 41,
confirm these findings.
There are two main reasons for the increased rate of cobalt leaching, which are directly
influenced by the amount of ammonium carbonate present. According to Bingöl et al.
(2005), ammonium carbonate will form a buffer solution with ammonia, which allows
for the pH of the solution to be maintained at a constant value. The second reason
involves the buffering of OH-, formed from the reduction of oxygen by NH4+, which
67 | P a g e
produces more NH3, increases the concentration of the reactant, and in turn improves
the rate of cobalt extraction (Bingöl et al., 2005). This can be represented by the
following reaction:
[Eq.28]
The leach data in Appendix B (p.117-121) contains the pH values recorded at each
sampling time for the 3 ammonium carbonate variation leaching tests. The pH values
recorded for the 1M ammonium carbonate test were at ~10.2, which is consistent with
the results presented in the previous section and the literature, which state that the
optimum pH for the formation of stable cobalt-ammonia complexes will be ~10.2. Both
the 2M and the 3M ammonium carbonate leaches had lower pH values, of ~ 9.3 to 9.8.
4.2.2.3 The effect of temperature on cobalt leaching from cobalt sulfide

The leaching of cobalt from cobalt sulfide was carried out at three different temperatures,
in order to analyse how temperature will influence the leaching kinetics of cobalt. The
chosen temperatures were 25°C, 45°C and 60°C. The leach solution was made up of 5M
[NH3]T , 1M [CO2]T and 0.022M S2O32- . The results are summarised in Figure 42.
100
90
80
% Co EXTRACTION
70
60
50
40
30 60°C
20 45°C
10 25°C
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 42. The effect of temperature on the leaching efficiency of cobalt from cobalt sulfide.
Based on the results presented in Figure 42, it can be seen that the highest cobalt
extraction of ~71% occurred during the 45°C leaching test. Cobalt has shown fast
68 | P a g e
leaching kinetics during the first 5 minutes of the 25°C and 60°C tests, with ~45% of
total cobalt extracted. It can be said that with the increase in temperature, the rate of
leaching also increases. In an ammonia-ammonium system, however, the increase in
temperature of the solution leads to a greater loss of free ammonia due to evaporation.
As mentioned previously, this free ammonia is needed in the formation of stable cobalt
ammine complexes. Increased temperatures will make these complexes unstable, leading
to a rather decreased leaching efficiency. From Figure 42, it can be seen that cobalt
extraction reached a plateau after the first 30 minutes in all three leaching tests.
At temperatures above 45°C, ammonia loss from solution becomes significant, because
of its high vapour pressure. Ammonium carbonate will also be affected at temperatures
above 35°C (Sun et al. 2010), as it will start to decompose according to the following
reaction:
[Eq.29]
The vaporisation of ammonia and the decomposition of ammonium carbonate will affect
the overall dissolution of cobalt.
It has been stated previously, that the region where the Co(NH3)42+ complex is stable, is
defined as a function of total ammonia concentration and the pH, which is dependent on
the temperature. At a room temperature, the pH of ammonia-ammonium system is given
by:
[Eq.30]
According to the study by Ku et al. (2016), the pH of the leach solution will be shifted to
a lower value as the temperature increases, and to a higher value, as the temperature is
decreased. This shift in the pH values will affect the leaching rate of cobalt. The
pH trends for the 3 leaching tests are presented in the Appendix B (p.118-122), and these
results confirm the findings by Ku et al. (2016). The 45°C leach test recorded pH values
of ~10.2 (the optimum pH for cobalt-ammonia complexes formation), the 60°C test had
pH values of ~9.7, and the 25°C test recorded pH values of
~10.8.
69 | P a g e
4.2.2.4 The effect of sodium sulfite on cobalt leaching from cobalt sulfide
The leaching of cobalt from cobalt sulfide was carried out with and without the addition
of sodium sulfite (Na2SO3) in order to investigate if this addition will influence in any
way the leaching kinetics of cobalt. Leaching experiments were performed at 60°C in a
solution containing 5M [NH3]T , 1M [CO2]T and 0.022M S2O32-, with one solution mixed
with 0.5M Na2SO3. The results are presented in Figure 43.
100
90
80
70
%Co EXTRACTION
60
50
40
30
NO SODIUM SULFITE
20
10 0.5M SODIUM SULFITE
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 43. The effect of sodium sulfite addition on the leaching efficiency of cobalt from cobalt
sulfide.
The leaching of sulfides in an ammonia-ammonium carbonate solution with the addition

of ammonium sulfite was investigated by Ku et al. (2016). In this study, the authors
analysed the leaching behaviour of nickel, cobalt and copper from treated cathode active
materials, separated from a commercial lithium ion batteries (LIBs) in hybrid electric
vehicles. The results presented showed that the addition of ammonium sulfite was able
to enhance the leaching kinetics of nickel, cobalt as well as copper. In this study, the
hypothesis tested by Ku et al. (2016) was applied to the extraction of cobalt from cobalt
sulfide, and investigated for possible improvements of the leaching rate of cobalt. For the
purpose of this investigation, ammonium sulfite was replaced by sodium sulfite, so that
no additional ammonia/ammonium species were introduced to the system. From the
results presented in Figure 43, it can be seen that during the leach test with the addition
of sodium sulfite, more cobalt was extracted into the solution (~80%), compared to ~
70% with no sodium sulfite, after the 5 hours of leaching. It can also be seen, that the
70 | P a g e
leaching rate of the sodium sulfite test was faster, with ~50% of total cobalt extracted
within the first 5 minutes, compared to ~40% of cobalt extracted without the addition.
The leach test which had no sodium sulfite added showed little increase in cobalt
extraction from 30 minutes till the remainder of the leach test. The extraction of cobalt in
the test with the addition of sodium sulfite kept increasing at a faster rate between the 30
minutes and 5 hours. It is quite possible that even higher cobalt extraction was
achievable, if the duration of the leach test was extended. The results presented in Figure
43 are consistent with the results presented by Ku et al. (2016), confirming that the
addition of a sulfite can lead to higher efficiency in the extraction of cobalt from cobalt
sulfide.
Zheng et al. (2017) suggested that even though the dissolution of Co3+ in ammonia
solution is thermodynamically favourable, the leaching kinetics are reported as slow.
They have suggested that by adding sodium sulfite, the reduction of Co3+ to Co2+ will
allow for the metal to be readily dissolved in solution, while the electrochemical
potential of the leach solution is kept in the stable range of cobalt amine complexes.
4.2.2.5 Kinetic Model for Synthetic Cobalt Sulfide
In order to determine which kinetic model fits best, the correlation coefficients were
calculated from the leaching data collected from 30 minutes to 5 hours. From these
correlation coefficient values, presented in Table 8, it can be seen that the best fit is given
by the reaction controlled model, as the values calculated are larger than in the other two
models. The Arrhenius plot for cobalt leaching was constructed from the slopes of
vs time plots, and is presented in Figure 47.
71 | P a g e
0.4
0.35
0.3
0.25
1-(1-x)1/3
0.2
0.15
25°C R² = 0.99
0.1
45°C R² = 1.00
0.05
60°C R² = 1.00
0
0 1 2 TIME (Hrs) 3 4 5
FIGURE 44. Plot of surface reaction model vs time for the leaching of cobalt from cobalt sulfide at
0.35
0.3
0.25
1-3(1-x)2/3 +2(1-x)
0.2
0.15
0.1 25°C R² = 0.99

45°C R² = 1.00
0.05
60°C R² = 0.99
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 45. Plot of ash layer diffusion model vs time for the leaching of cobalt from cobalt sulfide
at different temperatures.
72 | P a g e
0.14
0.12
0.1
1-2(1-x)1/3 + (1-x)2/3
0.08
0.06
0.04 25°C R² = 0.99

45°C R² = 1.00
0.02
60°C R² = 0.98
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 46. Plot of the mixed model vs time for the leaching of cobalt from cobalt sulfide at
TABLE 8. Correlation coefficients for the different models at various leaching conditions of cobalt
sulfide.
Surface
Reaction
TEMP (°C)
25 0.99 0.99 0.99
45 1.00 1.00 1.00
60 1.00 0.99 0.98
[NH3]T (M)
3 0.98 0.96 0.96
5 1.00 1.00 1.00
7 0.97 0.91 0.90
[CO2]T (M)
1 1.00 1.00 1.00
2 0.98 0.99 0.99
3 0.94 0.92 0.91
73 | P a g e
-3.65
-3.7
-3.75
-3.8 y = -0.78x - 1.33

ln (k)
R² = 0.99
-3.85
-3.9
-3.95
-4
2.9 3 3.1 3.2 3.3 3.4
1000/T (K-1)
FIGURE 47. Arrhenius plot for cobalt leaching from cobalt sulfide.
From the slope of the line in Figure 47, the activation energy for cobalt leaching from
cobalt sulfide was calculated to be 6.5 kJ/mol.
1.4
1.2
0.8
- log (k)
y = -0.87x + 2.06
0.6
0.4
0.2
0
0 0.5 1 1.5 2 2.5
log [NH3]
74 | P a g e
0.7
0.6
0.5
0.4
- log (k)
y = -1.83x + 3.27
0.3
0.2
0.1
-0.1
0 0.5 1 1.5 2
log [CO2]
FIGURE 49. Plot of –log k vs log [CO2] for reaction order estimation.
From the slopes of the straight lines in Figure 102 (p.137), the apparent rate constant (k)
values were obtained. Figure 48 shows the plot of -log (k) vs log [NH3] which was
constructed to determine the order of dependency with respect to ammonia
concentration. The empirical reaction order with respect to ammonia concentration was
determined to be 0.9 (Figure 48). Similarly, -log of the apparent rate constants obtained
from the slopes of the lines in Figure 105 (p.138) were plotted vs log [CO2] to determine
the dependency with respect to ammonium carbonate concentration. Figure 49 shows
that the reaction order with respect to ammonium carbonate was calculated to be 1.8.
These results indicate that the leaching of cobalt from cobalt sulfide under these
conditions has a higher dependency on ammonium carbonate concentration than
ammonia concentration.
75 | P a g e
4.3 THE INVESTIGATION OF COPPER SULFIDE
The results and discussion of copper sulfide are presented in this section. The
investigations of the electrochemically formed, the synthetic monometallic and the real
copper sulfide samples are outlined, and a comparison of the rate and extent of each is
presented at the end.

This section includes the analysis of the electrochemically formed copper sulfide. The
results of the OCP and CV tests are presented, as well as the characterisation studies of
the formed sulfide layer. The rate and extent of dissolution of this sulfide layer back into
the leach liquor is also presented.

The open circuit potential of the iron electrode was measured for 3 hours in a
deoxygenated 5M [NH3]T + 1M [CO2]T solution containing 0.008M copper (II) and
0.022M thiosulfate ions. The electrode was rotated at 200 rpm and the solution was
maintained at 45°C. Figure 50 shows the obtained result.
0.25
0.20
E (Vvs SHE)
0.15
0.10
0.05
0.00
0 30 60 90 120 150 180
TIME (mins)

copper (II) and thiosulfate ions.
76 | P a g e
As it can be seen from Figure 50, the passivation of the iron electrode took place as soon
as the surface of the electrode was immersed in the Cu (II) thiosulfate ammoniacal
solution.

The rotating disk voltammetry tests were measured on the iron electrode immersed in a
deoxygenated 5M [NH3]T + 1M [CO2]T containing 0.008M Cu(II) and 0.022M
thiosulfate ions. The potential were scanned in a positive direction from an initial
potential of -0.66 V, with the vertex potential at +1.44 V and the final potential at -0.56
V. The sweep rate was kept at 10 mV/s. The iron electrode was rotated at 200 rpm and
the solution was maintained at 45°C. Cyclic voltammograms were constructed at 0 Hrs
(initial immersion) and 2 hours after immersion, and are represented in Figure 51.
140
INITIAL E
120
2Hrs
100
A
80
i (mA/cm2)
60
F
40
D
20 C B
0
-20
-40
-1.0 -0.5 0.0 0.5 1.0 1.5
E (V vs SHE)
FIGURE 51. CV of iron following different immersion times in a deoxygenated Cu (II) thiosulfate
ammoniacal solution.
Cyclic voltammetry tests were conducted on the iron electrode following different
immersion times in a deoxygenated Cu (II) thiosulfate ammoniacal solution. As the
77 | P a g e
potential was scanned in the positive direction from -0.66 V, peak (A), representing the
oxidation of iron was recorded at around -0.25 V. Following this peak there was a steep
drop in current, until peak (B) was observed at around +0.10 V. This anodic peak (B)
was probably due to the solid species that had already deposited on the surface of the
electrode, that were undergoing the dissolution processes. After peak (B), no significant
currents were observed, till the scan was reversed and peak (C) at around -0.50 V was
recorded. This point represented the reactivation of metallic iron. After 2 hours of
immersion, a second voltammetry test was conducted. Peak (D) was recorded at ~ -0.50
V, and represented the anodic dissolution of iron. It was noticed that this peak (D) was
at least 3 times larger than peak (A) from initial test, and this was probably caused by the
fact that after the 2 hour exposure, most of the iron surface was covered by the solid
species, which in turn had negative effects on the oxidation processes. Following peak
(D), a large peak (E) was observed at around +0.45 V. As it was noticed that the surface
of the iron electrode was entirely covered by the solid species, this peak (E) represented
the anodic dissolution of these solid species. When the scan was reversed, peak (F) was
recorded at around -0.50 V, representing the reactivation of the metallic iron. This peak
(F) was observed to be slightly larger than peak (C) from the initial scan, and this is
because with the higher oxidation rate of the solid species on the surface, more sites
became available for the metallic iron re-activation.

After OCP of the iron RDE was measured for 3 hours in a solution made up of 5M
[NH3]T + 1M [CO2]T + 0.008M Cu(II) + 0.022M S2O32-, the electrode was removed,
rinsed with deionised water and analysed by the SEM/EDX spectroscopy. Figure 52
shows the SEM images of the surface of the iron electrode after passivation. The analysis
revealed a thin oxide layer on the surface, which consisted mostly of iron, ~20% copper
and ~10% sulfur. A more detailed SEM/EDX analysis was presented by D’Aloya
(2015), where it was reported that the morphology of the copper deposit is sensitive to
variables such as temperature, rotation speed or pH. The variations in the ratios of the
species present will be the likely cause of the changes to the morphology of the copper
deposit (D’Aloya, 2015).
78 | P a g e
FIGURE 52. SEM images of the different areas on the surface of the iron RDE following 3 hour
immersion in 5M [NH3]T and 1M [CO2]T containing 0.008M Cu (II) and 0.022M S2O32-.
+ 1M [CO2]T + 0.008M Cu(II) + 0.022M S2O32- solution for 2 hours at 45°C. After the 2
hours the iron RDE was immersed in 100 ml of the deoxygenated barren solution (5M
[NH3]T + 1M [CO2]T) heated up to 45°C. The metal dissolution was carried out for the
duration of 5 hours, with the iron electrode being rotated at 200 rpm. Solution samples
were taken out at different time intervals and were analysed for total copper
concentration by the AAS. The results of the copper dissolution are presented in Figure
53.
79 | P a g e
0.025
Cu CONCENTRATION (mM/L) 0.020
0.015
0.010
0.005
0.000
0 1 2 3 4 5
TIME (Hrs)
FIGURE 53. Copper dissolution from iron RDE in 5M[NH3]T + 1M[CO2]T following pre-treatment
in 5M[NH3]T + 1M[CO2]T + 0.008M Cu(II) + 0.022M S2O32- solution.
Based on the results presented in Figure 53, with the assumption that the layer was
uniformly distributed on the iron electrode, the initial dissolution of copper took place at
a rate of around 0.10 mg/L/min/cm2.
At the end of the 5 hour experiment, the amount of the dissolved copper in solution was
double the amount of dissolved cobalt in solution from the CoSx layer under the same
conditions, as discussed in section 4.2.4. The dissolution of copper continued to increase
uniformly throughout the test, unlike the dissolution of cobalt where there was no
significant changes during the first 4 hours, only increasing during the last hour of the
experiment.

Prior to conducting the leaching, the copper sulfide (Cu2S) feed sample underwent some
solid characterisation, which included SEM/EDX, XRD and laser-sizing. The results
from the SEM/EDX analysis are presented in Figure 54. This feed material was
quantitatively analysed at different spots, with the mass (%) composition presented in
Table 9. The XRD analysis is shown as Figure 95 (p.133).
80 | P a g e
A
B
FIGURE 54. SEM/EDX analysis of the copper sulfide sample used in the leaching tests. (A) SEM
image of the copper sulfide particles, (B) corresponding spectra for image (A), and (C) EDX image
showing spots that were quantitatively analysed.
TABLE 9. Mass (%) composition of the copper sulfide feed sample used and the mineral
composition at certain spots from FIGURE 54 (C).
MASS (%)
Cu S O
COMPOSITION
FEED 74.89 2.51 22.61
SPOT 001 73.47 3.22 23.32
SPOT 002 76.09 1.80 22.01
SPOT 003 72.72 3.59 23.69
SPOT 004 76.02 1.94 22.04
SPOT 005 47.86 16.05 36.08
81 | P a g e
An elemental analysis of the copper sulfide (Cu2S) feed is presented in Table 9, and from
these results it can be seen that this sample has in fact been oxidised to cuprous sulphate
(Cu2SO4). The mass balance calculations of the leaching data (Appendix B p.123-127), as
well as significantly high levels of oxygen present in the sample support this finding.
Based on the results presented in Table 9, it can be said that copper, sulfur and oxygen
were all uniformly distributed throughout the feed sample. A sub-sample of the feed was
analysed for particle size, and it was found that 80% of the feed < 68.86 µm.
The process of copper extraction in ammonia leaching has been described as a complex
gas-liquid-solid process (Niinea et al., 1994). It involves the oxidation of copper at the
surface of the copper metal, according to the equation:
[Eq. 31]
followed by the dissolution of this freshly formed copper oxide by ammonia solution:
[Eq. 32]
According to Sun et al. (2015), the total reaction for the dissolution of copper in
ammonia leach solution can be expressed as:
[Eq. 33]
Sun et al. (2015) described the stages of copper leaching as:
(i) diffusion of ammonia/ammonium carbonate and oxygen from the bulk

solution to the copper metal surface,
(ii) chemical reaction taking place at the surface, and
(iii) diffusion of ammine complex from bulk solution to the metal surface.
The copper extraction will be influenced by one or a combination of the stages above.
The leaching of copper from copper sulfide was conducted under various conditions,
including different ammonia and ammonium carbonate concentrations as well as
varying temperatures in order to analyse the leaching behaviour of copper. All
experiments were carried out using 0.5 g of 99.99% copper sulfide (Cu2S) powder in a
500 ml solution containing a particular ammonia concentration mixed with ammonium
carbonate and thiosulfate ions. The copper sulfide powder used in the experiments
82 | P a g e
contained no moisture. An elemental analysis was performed on the feed sample, and it
was found that the sample contained ~67% pure copper. Based on the stoichiometric
relationship, a sample of Cu2S should contain ~ 80% of copper. One of the possible
reasons for the lower copper content in the feed sample might be the fact that the sample
has been exposed to air, and as a result has been oxidised. The following assumption has
been confirmed by the results from the EDX quantitative analysis presented in Table 9.
The results of copper leaching experiments are summarised in Table 10.
TABLE 10. Copper leaching summary (SMMS).
% Cu
TEMP (°C) [NH3]T (M) [CO2]T (M) [Na2SO3] (M)
EXTRACTION
45 7 1 - 80.9
45 5 1 - 76.3
45 3 1 - 85.1
45 3 0.5 - 84.2
45 3 1.5 - 86.0
25 3 1 - 48.9
60 3 1 - 85.7
45 3 1 0.25 99.4
45 3 1 0.50 99.4
4.3.2.1 The effect of ammonia concentration on copper leaching from copper

sulfide.
The leaching of copper from copper sulfide was carried out at three different ammonia
concentrations, in order to investigate how ammonia affects the leaching kinetics of
copper. The chosen concentrations of ammonia were 3M, 5M and 7M. All experiments
were performed at 45°C with air. The results are summarised in Figure 55.
83 | P a g e
100
90
80
% Cu EXTRACTION
70
60
50
40
30 7M
20 5M
10 3M
0
0 1 2 TIME (Hrs) 3 4 5
FIGURE 55. The effect of ammonia concentration on the leaching efficiency of copper from copper
sulfide.
It can be seen from the results in Figure 55, that during the first 3 hours of leaching, the
5M ammonia produces the highest copper extraction (~35% at 5 minutes, ~50% at 1
hour and over 60% at 3 hours). During the last 2 hours of leaching, however, copper
extraction was only increased to ~70%, with the profile becoming flatter during these last
2 hours. The 3M ammonia concentration test was able to extract ~25% of copper within
the first 5 minutes, ~45% at the 1 hour mark, showing a gradual increase in copper
extraction for the remainder of the leaching test, with a final copper extraction of ~80%
at the end of the 5 hours. The 7M ammonia concentration leach test showed a steady
increase in copper extraction during the first 2 hours of leaching, with ~25% extracted
during the first 5 minutes, ~45% copper extracted at the 1 hour mark, and ~50%
extraction at 2 hours. There was no significant increase in the copper extraction noticed
between the 2nd and 4th hour of this test. An increase was reported during the last hour,
however, from ~50% to 75% copper extracted at the end of the leaching test.
Based on the previous investigations by Sun et al. (2015), Nabizadeh and Aghazaden
(2015) and Baba et al. (2014) copper recovery increases with the increased starting
ammonia concentration. The results reported in this study and presented in Figure 55,
do not support this trend, however. One of the possible reasons for the differences could
be the fact that these previous studies were performed at ambient temperature, not at
45°C, as was the case with this study.
84 | P a g e
FIGURE 56. Stability limits of Cu2+ in ammoniacal solution (Ek et al., 1982).
Ek et al. (1982), studied the stability limits of copper in ammoniacal solutions. Figure 56
represents their findings, and shows that in order to increase the dissolution of copper,
the pH being buffered by the NH4+/NH3 acid-base couple, needs to be decreased to
~10.3. The pH values recorded during the tests (Appendix B p.123-127) are consistent
with the results calculated by Ek et al. (1982). It can be seen that the pH values recorded
for the 3M and 5M ammonia concentration leach tests (~9.6 and ~10.2, respectively),
correspond to higher copper extraction, when compared to the 7M test (pH ~10.4).
According to Sun et al. (2015), it was found that pH values ranging from 8.7 to 10.6 are
within the stable region of ammonia complex. Baba et al. (2014), reported that as the
oxidation of copper is taking place, the pH values will gradually decrease, and this
decrease is attributed to the generation of SO42- and H+ through oxidation reaction as
well as H+ ion neutralisation. The generation of NH4+ ion will decrease the pH of the
leach solution, and help with maintaining the pH within the stable region of copper
ammine complex as shown below:
[Eq. 34]
Baba et al. (2014), explained that this decrease in the pH is related to the initial
concentration of ammonia and the amount of S to SO42- oxidation reaction. This is
consistent with the pH values recorded, where these values for the leach test at the
85 | P a g e
highest (7M) ammonia concentration were ~10.4, 5M ammonia concentration test at
~10.2, and the lowest (3M) ammonia concentration test at ~9.6.
According to the pH/Eh diagram, the dominant species at pH ~9 in ammonia solution

are Cu(NH3)42+ and Cu(NH3)2+. The ratio of the two will be influenced by the oxidation
potential in the system (Meng and Han, 1995). This relation can be represented by:
[Eq. 35]
[Eq. 36]
4.3.2.2 The effect of ammonium carbonate on copper leaching from copper

sulfide.
The leaching of copper from copper sulfide was carried out at three different ammonium
carbonate concentrations in order to investigate the relationship between ammonium
carbonate and the leaching kinetics of copper. The tested concentrations of ammonium
carbonate were 0.5M, 1M and 1.5M mixed with 3M [NH3]T and 0.022M S2O32-. The
results are summarised in Figure 57.
100
90
80
70
% Cu EXTRACTION
60
50
40
30 0.5M
20 1M
10 1.5M
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 57. The effect of ammonium carbonate concentration on the leaching efficiency of copper
from copper sulfide.
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As it can be seen from Figure 57, the recovery of copper from copper sulfide, increases as
the concentration of ammonium carbonate at a constant NH3 concentration is decreased.
A similar trend was observed by Nabizadeh and Aghazadeh (2015), and Sun et al.
(2015). Nabizadeh and Aghazadeh (2015), tested copper recovery at a constant ammonia
concentration of 5M, varying the ammonium carbonate concentrations between 0.3M to
2M, for the duration of 6 hours. Their findings show that more copper was being
recovered at lower ammonium carbonate concentrations. One of the possible reasons for
this is the fact that ammonium carbonate will form a buffer solution with ammonia,
giving rise to constant pH values (seen in the leach data in Appendix B p.123-127), as
well as the increase in NH3 generation during the buffering of OH-, as oxygen becomes
reduced by NH4+. Another possible explanation as to why the recovery of copper
decreases as the concentration of ammonium carbonate increases, may be related to the
thermodynamic interaction between ammonia and ammonium carbonate, and this
relationship was shown previously by Eq.19 and Eq.20.
From the results presented in Figure 57, during the first 15 minutes of leaching, the
0.5M leach test produced the highest copper recovery, while the 1.5M ammonium
carbonate test reported the least amount of recovered copper. At the 30 minute mark,
however, the leach solution which contained 1M ammonium carbonate concentration
increased copper recovery to ~40%, while the 1.5M test only extracted ~25% of copper
in the same time frame. The 1M ammonium carbonate leach test showed a steady
increase in copper extraction, achieving ~80% of copper dissolved in the solution after 5
hours of leaching. The 0.5M ammonium carbonate test plateaus after the first hour (seen
in Figure 57), at ~45% copper extracted at the end of the 4th hour. A significant increase
in the copper extraction was visible in the last hour of the leaching test, however, with
~80% copper extracted at the end.
An addition of ammonium carbonate has been known to help in preventing the build-up
of the oxidized phase, by providing more acidic conditions, which help in maintaining
copper within its stable complex region, illustrated in Figure 56 (Ek et al., 1982). The
conditions necessary for the complete dissolution of Cu2S as soluble Cu complexes are
based on the following equilibrium:
[Eq. 37]
87 | P a g e
According to Ek et al. (1982), the above equilibrium helps in defining the stability limits
of these copper complexes.
4.3.2.3 The effect of temperature on copper leaching from copper sulfide.

The leaching of copper from copper sulfide was conducted at three different
temperatures in order to establish how temperature affects the leaching kinetics of
copper. The tested temperatures were 25°C, 45°C and 60°C. The leach solutions
contained 3M [NH3]T , 1M [CO2]T and 0.022M S2O32-. The results are presented in
Figure 58.
100
25°C
90
45°C
80
60°C
70
% Cu EXTRACTION
60
50
40
30
20
10
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 58. The effect of temperature on the leaching efficiency of copper from copper sulfide.
It can be seen from Figure 58, that the highest copper extraction was achieved at 60°C.
In this 60°C leach test, the copper extraction reached ~50% during the first hour,
compared to ~25% during the 25°C and 45°C leach tests. The 60°C test performed
significantly better than the other 2 tests, throughout the 5 hours of leaching, with a final
copper extraction of ~80% at the end of the leach, compared to ~40% for both the 25°C
and the 45°C tests.
88 | P a g e
4.3.2.4 The effect of sodium sulfite addition on copper leaching from copper
sulfide.
The leaching of copper from copper sulfide was carried out with and without the
addition of sodium sulfite (Na2SO3) in order to investigate how this addition influences
the leaching kinetics of copper. The obtained results are presented in Figure 59.
100
90
80
% Cu EXTRACTION
70
60
50
40
30 0M
20 0.25M
10 0.50M
0
0 1 2 TIME (Hrs) 3 4 5
FIGURE 59. The effect of sodium sulfite addition on the leaching efficiency of copper from copper
sulfide.
As it can be seen from Figure 59, the addition of sodium sulfite has increased the
recovery of copper from copper sulfide. During the first 30 minutes the leach test
containing no Na2SO3 addition recorded the fastest leaching rate, with ~40% of copper
in solution, compared to the two tests with the addition of Na2SO3, at ~30% of copper
extracted. At the 1 hour mark, however, the leach test with 0.25M Na2SO3 recorded
~70% of copper, ~45% of copper was extracted in the no addition leach test, while the
0.5M test reported 40% copper extraction. At the end of the 5 hours, both tests
containing Na2SO3 finished with ~90% of copper in solution, compared to ~70% in the
test with no Na2SO3 addition. The exact leaching mechanisms are unclear, as not enough
research has been done on copper sulfide leaching reactions with the addition of sodium
sulfite. Based on the results of the effects of sodium sulfite on the leaching of nickel and
copper from this project, a possible explanation of the improved leaching efficiency
89 | P a g e
might be related to the reduction of high valence state copper oxides in ammonia
solution, which have been reported for increasing the rate of metal dissolution (Ku et al.,
2016; Zheng et al., 2017).
4.3.2.5 Kinetic Model for Synthetic Copper Sulfide

The process of copper dissolution involves the formation of copper oxide, followed by
the dissolution of the oxide. Xia and Hu (1980), described the dissolution of copper in an
ammoniacal solution in the presence of oxygen as electrochemical. At a higher oxygen
pressure, the surface reaction will control the dissolution process. Sun et al. (2015), have
studied the effect of temperature on the leaching kinetics of copper, presenting the
apparent activation energy for copper in ammoniacal solution at higher temperature as
18.96 kJ/mol, and 11.86 kJ/mol at lower temperature. Their results suggest that the
reaction mechanisms must be different at different temperature ranges.
Bingöl et al. (2005), also studied the dissolution kinetics of copper and reported that it is
possibly controlled by mixed kinetics. The rate of leaching was faster at the beginning,
and slowed down as the reaction proceeded. The following kinetic model was presented:
[Eq.38]
with the activation energy of 15 kJ/mol.
0.6
25°C R² = 0.86
0.5 45°C R² = 0.91
60°C R² = 0.97
0.4
1-(1-x)1/3
0.3
0.2
0.1
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 60. Plot of surface reaction model vs time for leaching of copper from copper sulfide at
90 | P a g e
0.5
25°C R² = 0.83
0.45
45°C R² = 0.87
0.4
60°C R² = 0.95
0.35
1-3(1-x)2/3 + 2(1-x)
0.3
0.25
0.2
0.15
0.1
0.05
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 61. Plot of ash layer diffusion model vs time leaching of copper from copper sulfide at
0.25
25°C R² = 0.82
45°C R² = 0.85
0.2
1-2(1-x)1/3 +(1-x)2/3
60°C R² = 0.92
0.15
0.1
0.05
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 62. Plot of the mixed model vs time for leaching of copper from copper sulfide at
91 | P a g e
TABLE 11. Correlation coefficients for the different models at various leaching conditions of
copper sulfide.
Surface
Reaction
Temperature (°C)
25 0.86 0.82 0.82
45 0.91 0.87 0.85
60 0.97 0.95 0.92
[NH3]T (M)
3 0.97 0.95 0.92
5 0.93 0.95 0.97
7 0.82 0.76 0.72
[CO2]T (M)
0.5 0.80 0.74 0.70
1 0.97 0.95 0.92
1.5 0.93 0.87 0.83
The analysis of the kinetics reaction data show that around 40% of copper is extracted
within the first 30 minutes of leaching. In order to determine the correlation coefficients
of copper leaching from the regression analysis, the data was fitted to the each model
from 30 minutes to 5 hours. The reaction rate gradually slowed down after the initial 30
minutes, which explains the possibility that between those times the leaching is
controlled by a mixed reaction and ash diffusion model, supporting the results presented
by Bingöl et al. (2005).
From the analysed data in Table 11, it can be seen that the reaction controlled model
gives the largest correlation coefficient values, and therefore gives the best fit. The k
values were calculated from the slopes of vs time plots, and the Arrhenius
plot for copper leaching from copper sulfide was constructed, and is presented in Figure
63.
92 | P a g e
0
-0.5
-1
-1.5
-2
ln k
y = -6.93x + 18.10
-2.5
-3
y = -1.39x + 0.69
-3.5
-4
-4.5
2.9 3 3.1 3.2 3.3 3.4
1000/T (K)
FIGURE 63. Arrhenius plot for copper leaching from copper sulfide.
The results presented in Figure 63 indicate that the rate constants of the copper leaching
reaction change as the temperature increases. The activation energy (EA) for the leaching
reactions at lower temperatures (25°C - 45°C) was calculated to be 11.5 kJ/mol, while
the activation energy for leaching at higher temperatures (>45°C) was 57.6 kJ/mol. This
result is consistent with the trend reported by Sun et al. (2015).
1.2
0.8
-log (k)
y = 1.97x - 1.78
0.6
0.4
0.2
0
0 0.5 1 1.5
log [NH3]
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0.3
0.2
0.1
y = -4.02x + 4.61
0
- log (k)
-0.1
-0.2
-0.3
-0.4
1.08 1.1 1.12 1.14 1.16 1.18 1.2 1.22 1.24
log [CO2]
FIGURE 65. Plot of –log k vs log [CO2] for reaction order estimation.
The apparent rate constants (k) were obtained from the slopes of the lines in Figure 108
(p.140). The plot of –log of k vs log [NH3] (Figure 64) was constructed to determine the
order of dependency with respect to ammonia concentration. The empirical reaction
order with respect to ammonia was determined to be 1.9. The dependency in relation to
ammonium carbonate concentration was determined from the plot of –log of apparent
rate constant values (from the slopes of the lines in Figure 111 p.141) vs log [CO2].
Figure 65 shows that the reaction order with respect to ammonium carbonate
concentration was determined to be 4.0. These results indicate that the leaching reaction
of copper from copper sulfide has a significantly higher dependency on the ammonium
carbonate concentration than the concentration of ammonia.

The leaching of copper from copper sulfide flotation concentrate (chalcopyrite) was
conducted under optimum conditions (based on the previously performed leaching tests
of synthetic copper sulfide), with and without the addition of sodium sulfite. The aim of
these tests was to compare the results from the leaching of SMMS to the leaching of
RMS, by analysing the leaching behaviour of the two under similar conditions. The
leach liquor used for all tests was made up of 3M [NH3]T + 1M [CO2]T + 0.022M S2O32-,
with 0.25M Na2SO3, where appropriate. All tests were performed in a 500 ml reactor, at
94 | P a g e
45°C with air. 10 g of the copper flotation concentrate was used for each test. The results
are summarised in Figure 66.
50
45 NO SODIUM SULFITE
40
0.25M SODIUM
35
SULFITE
30
% Cu EXTRACTED
25
20
15
10
5
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
TIME (Hrs)
FIGURE 66. The effect of sodium sulfite addition on the leaching efficiency of copper from
chalcopyrite flotation concentrate.
The results in Figure 66 show that the addition of sodium sulfite suppresses the leaching
of copper from copper flotation concentrate. The profile of the 0.25M Na2SO3 test
remains at ~2.5% of copper extracted for the duration of the test. The leach test with no
Na2SO3 addition is seen to increase linearly with time, however, finishing at ~45% of
copper in solution at the end of the 30 hours.
According to Qiu et al. (2007), leaching of chalcopyrite depends on the Fe ion

concentration. During the initial stage, chalcopyrite will be oxidised by Fe3+, whose
concentration in solution is much higher. As the Fe3+ starts to precipitate out, the
dissolution of chalcopyrite will decrease. The concentration of dissolved oxygen will be
reduced, as a result of Fe2+ to Fe3+ oxidation taking place. During the oxidating stage, Fe
ions will have a lesser effect on the leaching of chalcopyrite, as the Fe3+ concentration in
solution is very low (Qiu et al., 2007).
Prior to conducting the leaching studies, an elemental analysis was performed on the
feed and the results are presented in Table 12, together with the elemental analysis of
both leach residues. Leach Residue A represents the solids recovered from the leach with
no addition of sodium sulfite, while the solids from the leach with the addition of sodium
95 | P a g e
sulfite are represented by Residue B. The sub-samples of copper sulfide feed as well as
the leach residues were also analysed by the SEM/EDX, and are represented in Figure
67.
TABLE 12. Elemental composition of the copper sulfide flotation concentrate feed and both leach
residues.
FEED RESIDUE A RESIDUE B

ELEMENT
% (g) % (g) % (g)
Ni 0.22 0.02 1.47 0.11 0.62 0.05
Fe 29.80 2.98 45.26 3.54 29.75 2.28
S 33.40 3.34 10.85 0.85 12.59 0.97
Cu 32.00 3.20 10.19 0.80 23.57 1.81
Other 0.36 0.04 27.77 2.17 33.47 2.57
Based on the results in Table 12, it can be seen that Residue A contained significantly
higher amounts of Fe, compared with Residue B. The amount of sulfur was similar in
both residues. Residue B, however, contained more than double the amount of Cu seen
in Residue A. Based on this residue analysis, it can be said that the addition of sodium
sulfite to chalcopyrite concentrate leaching is undesirable, as it results in an increased
amounts of Cu precipitating out and higher impurities (Fe) remaining in solution.
96 | P a g e
A
B C
FIGURE 67. SEM image of (A) copper feed, (B) leach residue A and (C) leach residue B.
97 | P a g e
4.4 COMPARISON OF REACTION RATES AND EXTENTS OF LEACHING
The reaction rates and extents of nickel, cobalt and copper sulfides leaching were
investigated. The results are summarised in Table 13.
TABLE 13. Dissolution rate and extent of Ni, Co and Cu from the different metal sulfides.
Dissolution NICKEL COBALT COPPER

Rate Extent Rate Extent Rate Extent
(mg/L/min) (%) (mg/L/min) (%) (mg/L/min) (%)
EFMS 1.64 - 0.17 - 0.10 -
SMMS 9.18 99.50 19.06 74.20 36.02 85.70
RMS 0.07 14.94 - - 4.09 45.20
SMMS
10.04 88.40 22.20 86.70 44.21 99.40
(with Na2SO3)
RMS
1.31 48.24 - - 0.89 2.00
(with Na2SO3)
Based on the results presented in Table 13, it can be seen that in all three SMMS samples
the highest rate and extent was reported, when compared to the EFMS and RMS
samples tested. These results could be related to the effect of secondary phases present in
feed material that may reduce the leaching; hence considering that the SMMS samples
contained no impurities, could be a positive factor. The leaching of RMS, on the other
hand, was slowest of the three types of material and reached relatively low extractions
overall. The RMS also involved significant amount of gangue minerals, so the other
elements in the system may have decreased the rate and extent of dissolution of the
target metals.
The dissolution of nickel from the EFMS layer formed on the surface of the iron
electrode was much faster (1.64 mg/L/min), than that of cobalt (0.17 mg/L/min) or
copper (0.10 mg/L/min). The extent of EFMS dissolutions could not be calculated
because of technical difficulties. The faster rate of nickel dissolution could be attributed
to the fact that iron RDE did not reach passivation in a solution containing nickel (II). In
addition, this may have allowed the formation of a more substantial nickel but looser
sulfide layer on the surface, delaying passivation. On the other hand, the passivation of
the iron RDE immersed in a solution containing copper (II) was rapid (very soon after
the electrode was introduced), which is assumed to have led to the formation of a thinner
but more compact sulfide layer on the surface of the electrode, which could be slower to
re-dissolve.
98 | P a g e
During the leaching of the synthetic monometallic sulfides (SMMS) the rate of copper
leaching was the fastest at 36.02 mg/L/min, followed by cobalt (19.06 mg/L/min) and
lastly nickel (9.18 mg/L/min). The extent of nickel (SMMS) leaching was the highest
(99.5%), compared to copper (85.7%) then cobalt (74.2%). In addition, the leaching data
shows that the addition of Na2SO3 improved the rates of leaching for all three SMMS
materials. The biggest improvement was recorded in copper, where the rate increased to
44.21 mg/L/min and the extent to 99.4%. It is possible that this improvement is
attributed to the fact that these tested sulfides were to some extent oxidised prior to use
in the experiments. Therefore, the addition of a reducing agent in the form of Na2SO3,
would have been beneficial in reducing the oxide surface and promoting the dissolution
of the metals.
The rate of nickel leaching from the RMS feed was significantly slower (0.07
mg/L/min), than the leaching rate of copper (4.09 mg/L/min). The extent of nickel
recovery was also reported as lower (14.94%) compared to copper (45.2%). The addition
of Na2SO3 had a positive effect on the rate of nickel leaching, showing an improvement
to 1.31 mg/L/min, and the extent increasing to 48.24%. However, the addition of
Na2SO3 has been observed to have an undesirable effect on the rate and extent of copper
leaching (RMS), which were reduced to 0.89 mg/L/min and 2.0%, respectively.
5 CONCLUSIONS
The dissolution of metal sulfides in an ammoniacal carbonate solution under similar

conditions to the Caron process, has been known to be strongly influenced by the
behaviour of metallic iron as it passivates. This passivation of iron results in an
incomplete metal dissolution, as metal values precipitate into the newly formed sulfide
layer on the iron surface, thus affecting the efficiency of metal extraction.
In this study, the behaviour of iron in solutions containing nickel (II), cobalt (II) and
copper (II) was conducted through the use of electrochemical techniques. The nature and
composition of the sulfide layer on iron surface was investigated by SEM/EDX
characterisation studies. The dissolution of this layer was also analysed in order to
determine the likelihood of the metal values being redissolved back into the leach
solution.
99 | P a g e
The passivation of iron was found to take place in ammoniacal-carbonate solutions
containing cobalt (II) and thiosulfate ions as well as copper (II) and thiosulfate ions. The
spontaneous passivation of iron did not take place, however, in the ammoniacal-
carbonate solution containing nickel (II) and thiosulfate ions.
The results from the dissolution of the sulfide layer found that the concentration of the
redissolved metal was highest for nickel (II), than copper (II) and lastly cobalt (II).
The leaching of nickel (SMMS) was found to take place in two separate stages. At first
more rapid then slowing down as the leaching rate became influenced by mass diffusion.
The relative rates of reaction were found to be different at different temperatures, and the
leaching of nickel showed a higher dependency on ammonia concentration than
ammonium carbonate concentration. The addition of sodium sulfite had a negative
effect on nickel recovery during the (SMMS) material leaching. It showed an
improvement in the leaching efficiency of nickel from the flotation concentrate material
(RMS).
Under the leach conditions of this study, the first stage of cobalt (SMMS) leaching was
seen as rapid. Based on the correlation coefficient values it was found the surface
reaction controlled model fits best with the calculated data. The kinetic data also
indicated that the leaching of cobalt had a higher dependency on ammonium carbonate
than ammonia concentration. The addition of sodium sulfite was reported as beneficial
to the efficiency of cobalt leaching from cobalt sulfide (SMMS).
The leaching rate of copper (SMMS) in ammoniacal-carbonate solution containing

thiosulfate ions was also seen as rapid. In fact, under the same conditions, copper
extraction was reported as much higher than the extraction of nickel or cobalt in this
study. The leaching mechanisms for copper followed the surface reaction model. It was
found that, similarly to nickel, the rates of reaction for copper leaching change with
changes in temperature. It was also found that copper leaching has a higher dependency
on ammonium carbonate concentration than ammonia concentration, a trend also
reported in the leaching of cobalt. The addition of sodium sulfite was seen to improve
the leaching efficiency of copper from copper sulfide (SMMS), but was found to restrain
the extraction of copper from the flotation concentrate (RMS).
100 | P a g e
Based on the results of this study and previous investigations, it is believed that the
limited efficiency of the Caron process is mainly affected by the passivation of iron and
the loss of cobalt from the leach solution. Further investigations of the mechanisms
involved in the Caron process are needed, with the aim at optimising metal sulfide
dissolution, once passivation of iron takes place.
101 | P a g e
6 REFERENCES
[1] Baba, A.A., Ghosh, M.K., Pradhan, S.R., Rao, D.S., Baral, A. and Adekola, F.A.
(2014). Characterization and kinetic study of ammonia leaching of complex copper ore.
Transactions of Nonferrous Metals Society of China 24 (5), 1587-1595.
[2] Bhuntumkomol, K., Han, K.N. and Lawson, F. (1982). The leaching behaviour of
nickel laterite in acid and ammoniacal solutions. Hydrometallurgy 35, 147-263.
[3] Bingöl, D., Canbazoğlu, M. and Aydoğan, S. (2005). Dissolution kinetics of

malachite in ammonia/ammonium carbonate leaching. Hydrometallurgy 76, 55-62.
[4] Bockris, J.O.M. and Reddy, A.K.N. (1970). Modern Electrochemistry 2. Plenum
Press, New York.
[5] Bozzini, B., D’Urzo, L., Gianoncelli, A., Kaulich, B., Prasciolu, M., Sgura, I.,
Tondo, E. and Kiskinova, M. (2009). An in-situ synchrotron-based soft X-ray
microscopy investigation of Ni electrodeposition in a thin-layer cell. Journal of Physical
Chemistry C 113(22), 9783-9787.
[6] Brant, W.H., Schmid, S., Du, G., Gu, Q and Sharma, N. (2013). A simple
electrochemical cell in-situ fundamental structural analysis using synchrotron X-ray
powder diffraction. Journal of Power Sources 244, 109-114.
[7] Caron, M.H. (1955). Ammonia Leaching of Nickel Sulfide Ores. Half Century Review.
Trans. Inst. Min. Met. 64, 611-616.
[8] Chapman, D.L. (1913). A contribution to the theory of electrocapillarity.

Philosophical Magazine 25, 475-480.
[9] Chong, S., Hawker, W. and Vaughan, J. (2013). Selective reductive leaching of
oxidised cobalt containing residue. Minerals Engineering 54, 82-87.
[10] Clancy, M., Styles, M.J., Bettles, C.J., Birbilis, N., Chen, M., Zhang, Y., Gu, Q.,
Kimpton, J.A. and Webster, N.A.S. (2015). In-situ synchrotron X-ray diffraction
investigation of the evolution of a PbO2 / PbSO4 surface layer on a copper
102 | P a g e
electrowinning Pb anode in a novel electrochemical cell. Journal of Synchrotron Radiation
22, 366-375.
[11] Compton, R.G. and Banks, C.E. (2007). Understanding Voltammetry. World
Scientific: Hackensack, N.J.
[12] D’Aloya, A. (2015). Heterogeneous electrochemical reactions taking place on

metallic iron in ammonical-carbonate solutions containing dissolved nickel, cobalt,
copper and thiosulfate ions. PhD Thesis, Murdoch University.
[13] D’Aloya, A. and Nikoloski, A.N. (2012). The passivation of iron in ammoniacal
solutions containing copper (II) ions. Hydrometallurgy 111-112, 58-64.
[14] D’Aloya, A. and Nikoloski, A.N. (2013). An electrochemical investigation of the

formation of CoSx and its effect on the anodic dissolution of iron in ammoniacal-
carbonate solutions. Hydrometallurgy 131-132, 99-106.
[15] D’Aloya, A. and Nikoloski, A.N. (2014). The anodic dissolution of iron in
ammoniacal-carbonate-thiosulfate-copper solutions with formation of Cu2S and dendritic
copper. Hydrometallurgy 144-145, 163-169.
[16] De Marco, R. and Veder, J-P. (2010). In-situ structural characterization of

electrochemical systems using synchrotron-radiation techniques. Trends in Analytical
Chemistry 29(6), 528-537.
[17] DeGraaf, J.E. (1979). The treatment of lateritic nickel ores- A further study of the
Caron process and other possible improvements. Part 1: Effect of reduction conditions.
Hydrometallurgy 5, 47-65.
[18] DeGraaf, J.E. (1980). The treatment of lateritic nickel ores-A further study of the
Caron process and other possible improvements. Part 2: Leaching studies.
Hydrometallurgy 5, 255-271.
[19] Dyer, L., Su, B. and Asselin, E. (2012). Cobalt loss due to iron precipitation in
ammoniacal carbonate solutions. Hydrometallurgy 125-126, 144-147.
[20] Ek, C., Frenay, J. and Herman, J-C. (1982). Oxidized copper phase precipitation in
ammoniacal leaching- the influence of ammonium salt addition. Hydrometallurgy 8, 17-26.
103 | P a g e
[21] Forrokhpay, S. and Filippov, L. (2016). Challenges in processing nickel laterite ores
by flotation. International Journal of Mineral Processing 151, 59-67.
[22] Guoy, M. (1910). Concerning the surface electric charge of an electrolyte.

J.Phys.Theor.Appl 9, 457-468.
[23] Gupta, C.K. (2003). Chemical Metallurgy. Wiley-VCH, India.
[24] Habashi, F. (1970). Principles of Extractive Metallurgy, Volume 2.

Hydrometallurgy, Gordon & Breach, New York-London-Paris. (reprinted 1980).
[25] Helmholtz, H. (1853). Ueber einige Gesetze der Vertheilung elektrischer Strome in
korperlichen Leitern mit Anwendug auf die thierich-elektrischen Versuche. Annalen der
Physik und Chemie 165 (6), 211-233.
[26] Hu, J., Chen, Q., Hu, H., Qui, B., Xie, A. and Yin, Z. (2012). Extraction behaviour
of nickel (II) in ammoniacal sulphate solution with sterically hindered ß-diketone.
Separation and Purification Technology 95, 136-143.
[27] Katsiapi, A., Tsakiridis, P.E., Oustadakis, P. and Agatzini-Leonardou, S. (2010).

Cobalt recovery from mixed Co-Mn hydroxide precipitates by ammonia-ammonium
carbonate leaching. Minerals Engineering 23 (8), 643-651.
[28] Keir, J. (1790). Philos.Trans., 80,259.
[29] Kissinger, P.T. and Heineman, W.R. (1984). Laboratory Techniques in

Electroanalytical Chemistry. Marcel Dekker, N.J.
[30] Ku, H., Jung, Y., Jo, M., Park, S., Kim, S., Yang, D., Rhee, K., An, E., Sohn, J.
and Kwon, K. (2016). Recycling of spent lithium-ion battery cathode materials by
ammoniacal leaching. Journal of Hazardous Materials 313, 138-146.
[31] Kumbasar, R.A. and Kasap, S. (2009). Selective separation of nickel from cobalt in
ammoniacal solutions by emulsion type liquid membranes using 8-hydroxyquinoline (8-
HQ) as a mobile carrier. Hydrometallurgy 95, 121-126.
[32] Li, D., Park, K., Wu, Z. and Guo, X. (2010). Response surface design for nickel
recovery from laterite by sulfation- roasting- leaching process. Transactions of Nonferrous
Metals Society of China 20 (Supplement 1), 92-96.
104 | P a g e
[33] Lu, J., Liu, S., Shangguan, J., Du, W., Pan, F. and Yang, S. (2013). The effect of
sodium sulphate on the hydrogen reduction process of nickel laterite ore. Minerals
Engineering 49, 154-164.
[34] Luo, J., Li, G., Rao, M., Peng, Z., Zhang, Y. and Jiang, T. (2015). Atmospheric
leaching characteristics of nickel and iron in limonitic laterite with sulphuric acid in the
presence of sodium sulfite. Minerals Engineering 78, 38-44.
[35] Ma, B., Wang, C., Yang, W., Yin, F. and Chen, Y. (2013). Screening and reduction
roasting of limonitic laterite and ammonia-carbonate leaching of nickel-cobalt to produce
a high-grade iron concentrate. Minerals Engineering 50-51, 106-113.
[36] Majuste, D., Ciminelli, V.S.T., Eng, P.J. and Osseo-Asare, K. (2013). Applications
of in-situ synchrotron XRD in hydrometallurgy: Literature review and investigation of
chalcopyrite dissolution. Hydrometallurgy 131-132, 54-66.
[37] McDonald, R.G. and Whittington, B.I. (2008). Atmospheric acid leaching of nickel
laterites review Part 1: Sulphuric acid technologies. Hydrometallurgy 91, 35-55.
[38] Meng, X. and Han, K.H. (1995). The Principle and Applications of Ammonia
Leaching of Metals: A Review. Miner. Processing Extr. Metallurgy Rev. 16, 23-61.
[39] Meshram, P., Pandey, B.D. and Mankhand, T.R. (2015). Hydrometallurgical
processing of spent lithium batteries (LIBs) in the presence of a reducing agent with
emphasis on kinetics of leaching. Chemical Engineering Journal 281, 418-427.
[40] Mizokuchi, T., Nakamura, J. and Ishii, H. (1978). Oxygen pressurized leaching of
metallic nickel in ammoniacal ammonium carbonate solution. Journal of Chemical Society
6, 23-61.
[41] Moskalyk, R.R. and Alfantazi, A.M. (2002). Nickel laterite processing and
electrowinning practice. Minerals Engineering 15, 593-605.
[42] Mothobi, E. (2012). Leaching of Nickel Laterite with a solution of ammonia and
ammonium carbonate utilizing solids liquid separation under pressure. Master Thesis,
Stellenbosch University.
105 | P a g e
[43] Moyo, T. and Petersen, J. (2016). Study of the dissolution of chalcopyrite in
solutions of different ammonium salts. The Journal of the Southern African Institute of
Mining and Metallurgy 116, 509-516.
[44] Mudd, G.M (2009). Nickel sulphide versus laterite: The hard sustainability
challenge remains. Proc. “48th Annual Conference of Metallurgists”, Canadian
Metallurgical Society, Sudbury, Canada, August 2009.
[45] Mudd, G.M. (2010). Global trends and environmental issues in nickel mining:
Sulfides versus laterites. Ore Geology Reviews 38, 9-26.
[46] Muharok, M.Z. and Lieberto, J. (2013). Precipitation of nickel hydroxide from
simulated and atmospheric – leach solution of nickel laterite ore. Procedia Earth and
Planetary Science 6, 457-464.
[47] Nabizadeh, A. and Aghazadeh, V. (2015). Dissolution study of chalcopyrite

concentrate in oxidative ammonia/ammonium carbonate solutions at moderate
temperature and ambient pressure. Hydrometallurgy 152, 61-68.
[48] Niinae, M., Komatsu, N., Nakahiro, Y., Wakamatsu, T. and Shibata, J. (1994).
Preferential leaching of cobalt, nickel and copper from cobalt-rich ferromanganese crusts
with ammoniacal solutions using ammonium thiosulfate and ammonium sulphite as
reducing agents. Hydrometallurgy 40, 111-121.
[49] Nikoloski, A.N. (2002). The electrochemistry of the leaching of pre-reduced laterites
in ammonia-ammonium carbonate solution. PhD Thesis, Murdoch University.
[50] Nikoloski, A.N. and Nicol, M.J. (2010). The electrochemistry of the leaching
reactions in the Caron process II. Cathodic processes. Hydrometallurgy 105, 54-59.
[51] Norgate, T and Jahanshahi, S. (2011). Assessing the energy and greenhouse gas
footprints of nickel laterite processing. Minerals Engineering 24, 698-707.
[52] Oxley, A., Smith, M.E. and Caceres, O. (2016). Why heap leach nickel laterites?
Minerals Engineering 88, 53-60.
[53] Paunovic, M. and Schlesinger, M. (2006). Fundamentals of Electrochemical

Deposition. 2nd Ed. John Wiley & Sons, New Jersey.
106 | P a g e
[54] Pickles, C.A. (2003). Drying kinetics of nickeliferous limonitic laterite ores. Minerals
[55] Quast, K., Connor, J.N., Skinner, W., Robinson, D.J. and Addai-Mensan, J.
(2015). Pre-concentration strategies in the processing of nickel laterite ores Part 1:
Literature Review. Minerals Engineering 79, 261-268.
[56] Qui, T., Nie, G., Wang, J. and Cui, L. (2007). Kinetic process of oxidative leaching
of chalcopyrite under low oxygen pressure and low temperature. Transactions of
Nonferrous Metals Society of China 17, 418-422.
[57] Radmehr, V., Koleini, S.M.J., Khalesi, M.R. and Mohammadi, M.R.T. (2014).
Ammonia Leaching: A new approach of Copper Industry in Hydrometallurgical
Processes. Journal of the Institution of Engineers (India) 94 (2), 95-104.
[58] Rice, N. M. (2016). A hydrochloric acid process for nickeliferous laterites. Minerals
[59] Sarma, P.V.R. and Nathsarona ,K.C. (1996). Extraction of nickel from ammoniacal
solutions using LIX 87QN. Hydrometallurgy 42, 83-91.
[60] Sato, N. (2012). Green Corrosion Chemistry and Engineering : Opportunities and
Challenges, 1st Ed. (eds. S.K. Sharma). Wiley-VCH Verlag GmbH & Co.KGaA.
[61] Sato, N. and Okamoto, G. (1981). Electrochemical Passivation of Metals in

Comprehensive Treatise of Electrochemistry Vol.4 (eds. J.O.B. Bockris and R.E. White).
Plenum Publishing Corporation, New York.
[62] Senanayake ,G., Senaputra, A. and Nicol, M.J. (2010). Effect of thiosulfate,
sulphide, copper (II)/(III) and iron oxides on the ammoniacal carbonate leaching of
nickel and ferronickel in the Caron process. Hydrometallurgy 105, 60-68.
[63] Song, Y., Tang, J., Hu, J., Liu, S., Fu, Y. and Ji, X. (2016). Insights into
electrodeposition process of nickel from ammonium chloride media with speciation
analysis and in situ synchrotron radiation X-ray imaging. Electrochimica Acta 210, 812-820.
[64] Stern, O. (1924). The theory of the electrolytic double layer. Z. Elektrochem 30, 508-
516.
107 | P a g e
[65] Sun, Z.H.I., Xiao, Y., Sietsma, J., Agterhuis, H., Visser, G. and Yang, Y. (2015).
Selective copper recovery from complex mixtures of end-of-life electronic products with
ammonia-based solution. Hydrometallurgy 152, 91-99.
[66] Valix, M. and Cheung, W.H. (2002). Study of phase transformation of laterite ores
at high temperature. Minerals Engineering 15, 607-612.
[67] Veder, J-P., Nafady, A., Clarke, G., Williams, R.P., De Marco, R. and Bond, A.M.
(2011). A flow cell for transient voltammetry and in situ grazing incidence X-ray
diffraction characterization of electrocrystallized cadmium (II)
tetracyanoquinodimethane. Electrochimica Acta 56, 1546-1553.
[68] Wang, H. and Pilon, L. (2011). Accurate simulation of Electric Double Layer
Capacitance of Ultra-Microelectrodes. The Journal of Physical Chemistry 115 (33), 16711-
16719.
[69] Wei, W. (2016). Applications of Ammonium-Citrate-Thiosulfate Leaching on

Awaruite-bearing Serpentinite Ores. Master Thesis, University of British Columbia.
[70] Wetham, N.J., Johnston, G.M. and Sutcliffe, M.L. (2015). AmmLeach: A new
Paradigm in Copper-Cobalt Processing. Copper Cobalt Africa, incorporating the 8th Southern
African Base Metals Conference, 207-216.
[71] Wood, M. (2013). Metals Cost Service Insights.
[72] Woollacott, L.C. and Eric, R.H. (1994). Mineral and metal extraction: An
overview. South African Institute of Mining and Metallurgy Monograph Series.
Pennsylvania State University.
[73] Xia, G.X. and Hu, Z.W. (1980). Studies on the kinetics of copper dissolution in
aqueous ammoniacal solution. Acta Metallurgical Sinica 6, 442-453.
[74] Zheng, X., Gao, W., Zhang, X., He, M., Lin, X., Cao, H. and Zhang, Y. (2017).
Spent lithium-ion battery recycling-Reductive ammonia leaching of metals from cathode
scrap by sodium sulphite. Waste Management 60, 680-688.
[75] Zhong, S. and Hepworth, M.T. (1995). A calculation method for determining
equilibria in metal-ammonia-water systems. Hydrometallurgy 38, 15-37.
108 | P a g e
[76] Zuniga, M., Parada, F. and Asselin, E. (2010). Leaching of limonitic laterite in
ammoniacal solutions with metallic iron. Hydrometallurgy 104, 260-267.
109 | P a g e
7 APPENDICES
APPENDIX A. Equipment used in the project
FIGURE 68. Electrochemical set-up.
110 | P a g e
FIGURE 69. Electrochemical cell used in this project
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FIGURE 70. Iron RDE used in this project.
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FIGURE 71. Leaching set up.
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APPENDIX B. SMMS leaching data and calculations
PROJECT HONOURS PROJECT
TEST No LEACH TEST 1

SAMPLE NICKEL SULFIDE (Ni3S2)
TEMPERATURE 45
WATER DI WATER
DATE 24th of January 2017
5M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Ni3S2
Additions Solution Data Removed In Sample Ni Ni Ni

Time Ammonium Cumm Leach Extrn. Extrn.
(Hours) Ore Solution Ammonia Carbonate S2O3 pH ORP Ni Vol Ni Ni Vessel Total Total
(g) (mls) (g) (g) (g) (mV) (ppm) (ml) (mg) (mg) (mg) (mg) (%)
0.5 500.0 137.39 40.18 2.75

Moisture (%) 0.0
dry f eed 0.5
0 500.0 10.20 -61.2 0.40 10 4 4 199 203 0.00
0.08 490.0 10.16 -518.0 6.52 10 65 65 3193 3259 8.29
0.25 480.0 10.16 -595.0 7.15 10 72 72 3434 3505 8.91
0.5 470.0 10.15 -497.0 7.87 10 79 144 3700 3844 9.77
1 460.0 10.13 -407.9 9.07 10 91 235 4170 4404 11.20
2 450.0 10.13 -325.4 13.99 10 140 374 6297 6671 16.97
3 440.0 10.13 -273.9 14.87 10 149 523 6541 7064 17.96
4 430.0 10.14 -257.0 16.39 10 164 687 7047 7734 19.67
5 420.0 10.14 -247.8 18.65 10 187 874 7835 8708 22.14
TOTAL 90 949
NICKEL EXTRACTION CALCULATIONS COM M ENTS :
NICKEL
Product Quantity Assay Mass Dist'n
(ppm) (mg) (%)
Solids (g) 0.0535 570841 30540 77.66
Solution (mls) 420.0 18.65 7835 19.92
Solution Samples 949 2.41
Total Extraction 22.34

Total 39324 100.00
Calculated Head 7.9
Assay Head

TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Ni3S2

0.5 500.0 67.91 40.18 2.75

Moisture (%) 0.0
dry feed 0.5
0 500.0 9.64 -29.7 1.11 10 11 11 556 567 0.00
0.08 490.0 9.53 -417.0 45.92 10 459 459 22501 22960 23.11
0.25 480.0 9.60 -388.1 52.38 10 524 524 25142 25666 25.83
0.5 470.0 9.57 -363.8 75.72 10 757 1216 35588 36805 37.04
1 460.0 9.51 -288.0 94.76 10 948 2164 43590 45754 46.04
2 450.0 9.52 -95.4 154.90 10 1549 3713 69705 73418 73.88
3 440.0 9.54 -63.6 158.20 10 1582 5295 69608 74903 75.38
4 430.0 9.60 -53.0 202.62 10 2026 7321 87127 94448 95.05
5 420.0 9.60 -49.6 212.82 10 2128 9449 89384 98834 99.46
TOTAL 90 9984
NICKEL EXTRACTION CALCULATIONS COMMENTS :
NICKEL
(ppm) (mg) (%)
Solids (g) 0 0.00
Solution (mls) 420.0 212.82 89384 89.95

Total 99369 100.00
Calculated Head 19.9
Assay Head
FIGURE 72. Leaching data 1.
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TEMPERATURE 45
WATER DI WATER
DATE 6th of February 2017
7M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Ni3S2

0.5 500.0 189.55 40.18 2.75

Moisture (%) 0.0
dry feed 0.5
0 500.0 10.42 -119.1 0.83 10 8 8 417 425 0.00
0.08 490.0 10.43 -458.0 60.86 10 609 609 29821 30430 17.78
0.25 480.0 10.38 -523.0 72.30 10 723 723 34704 35427 20.70
0.5 470.0 10.37 -559.0 93.32 10 933 1542 43860 45402 26.53
1 460.0 10.41 -487.0 157.60 10 1576 3118 72496 75614 44.18
2 450.0 10.42 -435.0 184.38 10 1844 4962 82971 87933 51.38
3 440.0 10.38 -414.0 187.78 10 1878 6839 82623 89463 52.27
4 430.0 10.33 -393.0 206.04 10 2060 8900 88597 97497 56.97
5 420.0 10.37 -371.9 249.72 10 2497 11397 104882 116279 67.94
TOTAL 90 12128
NICKEL
(ppm) (mg) (%)
Solids (g) 0.1049 516100 54139 31.63
Solution (mls) 420.0 249.72 104882 61.28

Total 171150 100.00
Assay Head

TEMPERATURE 45
WATER DI WATER
3M [NH3] + 0.5M [CO2] + 0.022M S2O3 + 0.5g Ni3S2

0.5 500.0 79.83 19.64 2.75

Moisture (%) 0.0
dry f eed 0.5
0 500.0 10.10 -50.9 6.36 10 64 64 3179 3243 0.00
0.08 490.0 10.02 -424.0 66.56 10 666 666 32614 33280 17.87
0.25 480.0 10.00 -462.0 72.86 10 729 729 34973 35701 19.17
0.5 470.0 10.03 -358.9 86.00 10 860 1589 40420 42009 22.55
1 460.0 10.02 -317.7 100.82 10 1008 2597 46377 48974 26.29
2 450.0 10.03 -256.7 146.64 10 1466 4063 65988 70051 37.61
3 440.0 10.04 -214.6 178.48 10 1785 5848 78531 84379 45.30
4 430.0 10.05 -206.7 218.20 10 2182 8030 93826 101856 54.68
5 420.0 10.06 -203.5 261.36 10 2614 10644 109771 120415 64.65
TOTAL 90 11373
NICKEL
(ppm) (mg) (%)
Solids (g) 0.1161 560900 65120 34.96
Solution (mls) 420.0 261.36 109771 58.93

Total 186264 100.00
Assay Head
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TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1.5M [CO2] + 0.022M S2O3 + 0.5g Ni3S2

0.5 500.0 57.02 58.92 2.75

Moisture (%) 0.0
dry feed 0.5
0 500.0 9.50 -39.4 4.92 10 49 49 2462 2511 0.00
0.08 490.0 9.47 -384.7 116.22 10 1162 1162 56948 58110 42.08
0.25 480.0 9.46 -418.0 131.92 10 1319 1319 63322 64641 46.81
0.5 470.0 9.50 -441.0 152.28 10 1523 2685 71572 74257 53.78
1 460.0 9.40 -365.1 166.26 10 1663 4348 76480 80827 58.54
2 450.0 9.43 -273.3 185.12 10 1851 6199 83304 89503 64.82
3 440.0 9.41 -221.2 187.28 10 1873 8072 82403 90475 65.52
4 430.0 9.40 -200.7 212.70 10 2127 10199 91461 101660 73.62
5 420.0 9.41 -189.8 222.16 10 2222 12420 93307 105727 76.57
TOTAL 90 13789
NICKEL
(ppm) (mg) (%)
Solids (g) 0.1076 287988 30988 22.44
Solution (mls) 420.0 222.16 93307 67.57

Total 138083 100.00
Assay Head

TEMPERATURE 60
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Ni3S2

0.5 500.0 67.91 40.18 2.75

Moisture (%) 0.0
dry feed 0.5
0 500.0 9.64 -29.7 1.11 10 11 11 556 567 0.00
0.08 490.0 9.53 -417.0 45.92 10 459 459 22501 22960 23.11
0.25 480.0 9.60 -388.1 52.38 10 524 524 25142 25666 25.83
0.5 470.0 9.57 -363.8 75.72 10 757 1216 35588 36805 37.04
1 460.0 9.51 -288.0 94.76 10 948 2164 43590 45754 46.04
2 450.0 9.52 -95.4 154.90 10 1549 3713 69705 73418 73.88
3 440.0 9.54 -63.6 158.20 10 1582 5295 69608 74903 75.38
4 430.0 9.60 -53.0 202.62 10 2026 7321 87127 94448 95.05
5 420.0 9.60 -49.6 212.82 10 2128 9449 89384 98834 99.46
TOTAL 90 9984
NICKEL
(ppm) (mg) (%)
Solids (g) 0.0000 0 0 0.00
Solution (mls) 420.0 212.82 89384 89.95

Total 99369 100.00
Assay Head
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TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Ni3S2 + 0.5M Na2SO3

(Hours) Ore Solution Ammonia Carbonate S2O3 Na2SO3 pH ORP Ni Vol Ni Ni Vessel Total Total
(g) (mls) (g) (g) (g) (g) (mV) (ppm) (ml) (mg) (mg) (mg) (mg) (%)
0.5 500.0 67.91 40.18 2.75 63.0

Moisture (%) 0.0
dry feed 0.5
0 500.0 10.19 -288.9 1.67 10 17 17 833 850 0.00
0.08 490.0 10.10 -537.0 35.08 10 351 351 17189 17540 12.08
0.25 480.0 10.16 -572.0 37.86 10 379 379 18173 18551 12.78
0.5 470.0 10.07 -582.0 41.52 10 415 766 19514 20280 13.97
1 460.0 10.08 -578.0 55.66 10 557 1323 25604 26926 18.55
2 450.0 10.06 -582.0 91.90 10 919 2242 41355 43597 30.03
3 440.0 10.10 -555.0 133.72 10 1337 3579 58837 62416 43.00
4 430.0 10.05 -530.0 176.64 10 1766 5345 75955 81300 56.01
5 420.0 10.08 -465.0 238.06 10 2381 7726 99985 107711 74.20
TOTAL 90 8121
NICKEL
(ppm) (mg) (%)
Solids (g) 0.0987 375380 37050 25.52
Solution (mls) 420.0 238.06 99985 68.88

Total 145156 100.00
Assay Head

TEMPERATURE 25
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Ni3S2

0.5 500.0 67.91 40.18 2.75

Moisture (%) 0.0
dry f eed 0.5
0 500.0 9.38 -57.5 2.22 10 22 22 1108 1130 0.00
0.08 490.0 9.39 -479.0 37.64 10 376 376 18444 18820 34.58
0.25 480.0 9.40 -478.0 38.46 10 385 385 18461 18845 34.63
0.5 470.0 9.40 -503.0 38.58 10 386 762 18133 18895 34.72
1 460.0 9.37 -398.5 39.74 10 397 1160 18280 19440 35.72
2 450.0 9.30 -258.4 43.00 10 430 1590 19350 20940 38.47
3 440.0 9.30 -236.2 45.48 10 455 2044 20011 22056 40.52
4 430.0 9.32 -236.8 51.70 10 517 2561 22231 24792 45.55
5 420.0 9.31 -213.1 56.26 10 563 3124 23629 26753 49.16
TOTAL 90 3531
NICKEL
(ppm) (mg) (%)
Solids (g) 0.0944 288824 27265 50.10
Solution (mls) 420.0 56.26 23629 43.42

Total 54425 100.00
Assay Head
117 | P a g e

TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Ni3S2 + 0.25M Na2SO3

0.5 500.0 67.91 40.18 2.75 31.5

Moisture (%) 0.0
dry feed 0.5
0 500.0 9.80 -297.5 2.24 10 22 22 1119 1141 0.00
0.08 490.0 9.77 -524.0 50.22 10 502 502 24608 25110 14.52
0.25 480.0 9.85 -570.0 59.90 10 599 599 28752 29351 16.98
0.5 470.0 9.72 -563.0 73.38 10 734 1236 34489 35725 20.66
1 460.0 9.74 -496.0 113.36 10 1134 2370 52146 54515 31.53
2 450.0 9.73 -423.0 172.90 10 1729 4099 77805 81904 47.38
3 440.0 9.74 -422.0 231.80 10 2318 6417 101992 108409 62.71
4 430.0 9.71 -420.0 290.76 10 2908 9324 125027 134351 77.72
5 420.0 9.72 -401.8 333.56 10 3336 12660 140095 152755 88.36
TOTAL 90 13281
NICKEL
(ppm) (mg) (%)
Solids (g) 0.0890 219101 19500 11.28
Solution (mls) 420.0 333.56 140095 81.04

Total 172876 100.00
Assay Head

SAMPLE COBALT SULFIDE (CoS2)
TEMPERATURE 45
WATER DI WATER
5M [NH3] + 2M [CO2] + 0.022M S2O3 + 0.5g CoS2
Additions Solution Data Removed In Sample Co Co Co

(Hours) Ore Solution Ammonia Carbonate S2O3 pH ORP Co Vol Co Co Vessel Total Total
0.5 500.0 114.17 80.5 2.75

Moisture (%) 17.0
dry f eed 0.415
0 500.0 9.78 -144.9 1.45 10 14 14 725 739 0.00
0.25 490.0 9.88 -210.1 87.80 10 878 878 43022 43900 39.78
0.5 480.0 9.82 -196.3 96.94 10 969 1847 46531 48379 43.84
1 470.0 9.80 -167.8 100.28 10 1003 2850 47132 49982 45.29
2 460.0 9.81 -132.9 110.10 10 1101 3951 50646 54597 49.47
3 450.0 9.84 -111.0 110.18 10 1102 5053 49581 54634 49.51
4 440.0 9.80 -101.0 114.46 10 1145 6198 50362 56560 51.25
5 430.0 9.81 -98.0 117.92 10 1179 7377 50706 58082 52.63
TOTAL 80 7391
COBALT EXTRACTION CALCULATIONS COMMENTS :
COBALT Initial sample of CoS2 used f or the leach contains betw een 24.47 - 26.38 % of pure Co
Product Quantity Assay Mass Dist'n In theory, a sample of CoS2 should contain 47% of Co
(ppm) (mg) (%)
Solids (g) 0.1435 364200 52263 47.36
Solution (mls) 430.0 117.92 50706 45.95

Total 110360 100.00
Assay Head
118 | P a g e

TEMPERATURE 45
WATER DI WATER
5M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g CoS2

0.5 500.0 137.39 40.18 2.75

Moisture (%) 17.0
dry feed 0.415
0 500.0 10.20 -114.3 1.23 10 12 12 615 627 0.00

0.25 490.0 10.15 -200.3 95.32 10 953 953 46707 47660 51.13
0.5 480.0 10.14 -186.9 111.94 10 1119 2073 53731 55804 59.87
1 470.0 10.14 -157.1 116.14 10 1161 3234 54586 57820 62.03
2 460.0 10.15 -117.8 122.40 10 1224 4458 56304 60762 65.18
3 450.0 10.14 -100.4 130.08 10 1301 5759 58536 64295 68.97
4 440.0 10.17 -96.1 136.04 10 1360 7119 59858 66977 71.85
5 430.0 10.12 -88.3 141.00 10 1410 8529 60630 69159 74.19
TOTAL 80 8542
COBALT Initial sample of CoS2 used for the leach contains betw een 24.47 - 26.38 % of pure Co
(ppm) (mg) (%)
Solids (g) 0.0987 243600 24043 25.79
Solution (mls) 430.0 141.00 60630 65.04

Total 93215 100.00
Assay Head 0

TEMPERATURE 45
WATER DI WATER
5M [NH3] + 3M [CO2] + 0.022M S2O3 + 0.5g CoS2

0.5 500.0 90.74 120.53 2.75

Moisture (%) 17.0
dry feed 0.415
0 500.0 9.37 -58.1 2.59 10 26 26 1296 1322 0.00

0.25 490.0 9.32 -73.8 83.24 10 832 832 40788 41620 44.50
0.5 480.0 9.34 -59.1 84.28 10 843 1675 40454 42130 45.05
1 470.0 9.31 -61.6 93.70 10 937 2612 44039 46651 49.88
2 460.0 9.32 -50.9 94.10 10 941 3553 43286 46839 50.08
3 450.0 9.28 -44.2 113.00 10 1130 4683 50850 55533 59.38
4 440.0 9.30 -41.6 119.08 10 1191 5874 52395 58269 62.30
5 430.0 9.29 -50.6 138.50 10 1385 7259 59555 66814 71.44
TOTAL 80 7285
(ppm) (mg) (%)
Solids (g) 0.1415 188600 26687 28.53
Solution (mls) 430.0 138.50 59555 63.68

Total 93527 100.00
Assay Head 0
119 | P a g e

TEMPERATURE 45
WATER DI WATER
7M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g CoS2

0.5 500.0 189.55 40.18 2.75

Moisture (%) 17.0
dry feed 0.415
0 500.0 10.37 -81.7 0.00 10 0 0 0 0 0.00
0.25 490.0 10.36 -218.0 19.79 10 198 198 9696 9894 11.42
0.5 480.0 10.41 -206.6 20.80 10 208 406 9984 10390 11.99
1 470.0 10.44 -183.2 21.00 10 210 616 9870 10485 12.10
2 460.0 10.44 -153.4 31.36 10 314 929 14426 15355 17.73
3 450.0 10.47 -129.8 53.26 10 533 1462 23967 25429 29.36
4 440.0 10.44 -111.9 74.24 10 742 2204 32666 34870 40.25
5 430.0 10.46 -107.3 91.04 10 910 3115 39147 42262 48.79
TOTAL 80 3115
(ppm) (mg) (%)
Solids (g) 0.0964 460200 44363 51.21
Solution (mls) 430.0 91.04 39147 45.19

Total 86625 100.00
Assay Head

TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g CoS2

0.5 500.0 67.91 40.18 2.75

Moisture (%) 17.0
dry feed 0.415
0 500.0 9.60 -34.1 1.76 10 18 18 880 897 0.00
0.25 490.0 9.56 -39.1 26.06 10 261 261 12769 13030 13.08
0.5 480.0 9.67 -37.8 49.34 10 493 754 23683 24437 24.54
1 470.0 9.64 -35.8 56.02 10 560 1314 26329 27644 27.76
2 460.0 9.64 -34.5 65.94 10 659 1974 30332 32306 32.44
3 450.0 9.67 -32.0 71.22 10 712 2686 32049 34735 34.88
4 440.0 9.64 -30.5 84.00 10 840 3526 36960 40486 40.66
5 430.0 9.66 -29.1 96.90 10 969 4495 41667 46162 46.36
TOTAL 80 4512
(ppm) (mg) (%)
Solids (g) 0.1177 453700 53400 53.63
Solution (mls) 430.0 96.90 41667 41.84

Total 99580 100.00
Assay Head
120 | P a g e

TEMPERATURE 60
WATER DI WATER
5M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g CoS2

0.5 500.0 137.39 40.18 2.75

Moisture (%) 17.0
dry f eed 0.415
0 500.0 9.75 -62.9 1.14 10 11 11 572 583 0.00
0.08 490.0 9.73 -98.2 100.54 10 1005 1005 49265 50270 39.88
0.25 480.0 9.72 -75.8 119.40 10 1194 1194 57312 58506 46.42
0.5 470.0 9.72 -74.1 139.52 10 1395 2589 65574 68164 54.08
1 460.0 9.73 -73.6 143.24 10 1432 4022 65890 69912 55.47
2 450.0 9.64 -69.4 152.92 10 1529 5551 68814 74365 59.00
3 440.0 9.64 -65.8 163.46 10 1635 7185 71922 79108 62.76
4 430.0 9.62 -62.2 175.78 10 1758 8943 75585 84529 67.06
5 420.0 9.64 -59.4 187.72 10 1877 10820 78842 89663 71.14
TOTAL 90 11837
(ppm) (mg) (%)
Solids (g) 0.0669 528600 35363 28.06
Solution (mls) 420.0 187.72 78842 62.55

Total 126043 100.00
Assay Head

TEMPERATURE 25
WATER DI WATER
5M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g CoS2

0.5 500.0 137.39 40.18 2.75

Moisture (%) 17.0
dry feed 0.415
0 500.0 10.79 -75.3 0.63 10 6 6 313 319 0.00
0.08 490.0 10.75 -279.1 82.20 10 822 822 40278 41100 45.65
0.25 480.0 10.76 -263.6 94.36 10 944 944 45293 46236 51.35
0.5 470.0 10.76 -242.5 100.84 10 1008 1952 47395 49347 54.81
1 460.0 10.74 -178.3 105.08 10 1051 3003 48337 51340 57.02
2 450.0 10.69 -94.5 111.54 10 1115 4118 50193 54311 60.32
3 440.0 10.70 -82.5 115.88 10 1159 5277 50987 56264 62.49
4 430.0 10.68 -79.3 123.70 10 1237 6514 53191 59705 66.31
5 420.0 10.68 -78.6 127.38 10 1274 7788 53500 61287 68.07
TOTAL 90 8616
(ppm) (mg) (%)
Solids (g) 0.0417 669600 27922 31.01
Solution (mls) 420.0 127.38 53500 59.42

Total 90038 100.00
Assay Head
121 | P a g e
TEST No LEACH TEST 7(b)

TEMPERATURE 60
WATER DI WATER
5M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5 M Na2SO3 + 0.5g CoS2

(Hours) Ore Solution Ammonia Carbonate S2O3 Na2SO3 pH ORP Co Vol Co Co Vessel Total Total
0.5 500.0 137.39 40.18 2.75 63.0

Moisture (%) 17.0
dry f eed 0.415
0 500.0 10.32 -260.3 1.99 10 20 20 993 1012 0.00
0.08 490.0 10.19 -554.0 111.02 10 1110 1110 54400 55510 49.53
0.25 480.0 10.13 -553.0 125.36 10 1254 1254 60173 61426 54.81
0.5 470.0 10.14 -541.0 131.48 10 1315 2568 61796 64364 57.44
1 460.0 10.20 -508.0 133.62 10 1336 3905 61465 65370 58.33
2 450.0 10.20 -455.0 153.04 10 1530 5435 68868 74303 66.30
3 440.0 10.17 -404.0 157.22 10 1572 7007 69177 76184 67.98
4 430.0 10.21 -370.0 179.66 10 1797 8804 77254 86058 76.79
5 420.0 10.10 -359.7 205.40 10 2054 10858 86268 97126 86.67
TOTAL 90 11988
(ppm) (mg) (%)
Solids (g) 0.2614 52820 13807 12.32
Solution (mls) 420.0 205.40 86268 76.98

Total 112063 100.00
Assay Head

TEMPERATURE 60
WATER DI WATER
DATE 10th February 2017
5M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.25 M Na2SO3 + 0.5g CoS2

(Hours) Ore Solution Ammonia Carbonate S2O3 Na2SO3 pH ORP Co Vol Co Co Vessel Total Total
0.5 500.0 137.39 40.18 2.75 31.5

Moisture (%) 17.0
dry feed 0.415
0 500.0 10.53 -298.6 0.00 10 0 0 0 0 0.00
0.08 490.0 10.38 -515.0 95.42 10 954 954 46756 47710 89.86
0.25 480.0 10.34 -490.0 97.92 10 979 979 47002 47981 90.37
0.5 470.0 10.33 -451.0 98.00 10 980 1959 46060 48019 90.45
1 460.0 10.28 -405.7 98.64 10 986 2946 45374 48320 91.01
2 450.0 10.32 -347.5 100.08 10 1001 3946 45036 48982 92.26
3 440.0 10.30 -340.5 101.58 10 1016 4962 44695 49657 93.53
4 430.0 10.32 -331.5 105.28 10 1053 6015 45270 51285 96.60
5 420.0 10.30 -329.1 107.26 10 1073 7088 45049 52137 98.20
TOTAL 90 8042
(ppm) (mg) (%)
Solids (g) 0 0.00
Solution (mls) 420.0 107.26 45049 84.85

Total 53091 100.00
Assay Head
122 | P a g e

SAMPLE COPPER SULFIDE (Cu2S)
TEMPERATURE 45
WATER DI WATER
5M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Cu2S
Additions Solution Data Removed In Sample Cu Cu Cu

(Hours) Ore Solution Ammonia Carbonate S2O3 pH ORP Cu Vol Cu Cu Vessel Total Total
0.5 500.0 137.39 40.18 2.75

Moisture (%) 0.0
dry f eed 0.5
0 500.0 10.22 -72.4 0.25 10 2 2 123 125 0.00
0.08 490.0 10.22 -261.4 170.68 10 1707 1707 83633 85340 32.95
0.25 480.0 10.17 -249.3 189.82 10 1898 1898 91114 93012 35.91
0.5 470.0 10.18 -224.5 214.50 10 2145 3852 100815 104667 40.41
1 460.0 10.22 -212.1 280.66 10 2807 6658 129104 135762 52.42
2 450.0 10.20 -170.0 345.44 10 3454 10113 155448 165561 63.92
3 440.0 10.23 -135.4 379.62 10 3796 13909 167033 180942 69.86
4 430.0 10.21 -129.8 410.10 10 4101 18010 176343 194353 75.04
5 420.0 10.25 -122.8 417.50 10 4175 22185 175350 197535 76.27
TOTAL 90 24086
COPPER EXTRACTION CALCULATIONS COMMENTS :
COPPER
(ppm) (mg) (%)
Solids (g) 0.1150 517900 59559 23.00
Solution (mls) 420.0 417.50 175350 67.70

Total 258994 100.00
Assay Head

TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Cu2S

0.5 500.0 67.91 40.18 2.75

Moisture (%) 0.0
dry feed 0.5
0 500.0 9.60 -36.6 0.10 10 1 1 50 51 0.00
0.08 490.0 9.62 -177.2 180.10 10 1801 1801 88249 90050 24.44
0.25 480.0 9.60 -148.3 240.88 10 2409 2409 115622 118031 32.04
0.5 470.0 9.63 -101.2 321.40 10 3214 5015 151058 156073 42.37
1 460.0 9.61 -82.7 380.92 10 3809 8824 175223 184047 49.96
2 450.0 9.60 -78.4 430.22 10 4302 13126 193599 206725 56.12
3 440.0 9.64 -76.3 498.80 10 4988 18114 219472 237586 64.49
4 430.0 9.65 -85.7 621.60 10 6216 24330 267288 291618 79.16
5 420.0 9.64 -67.2 677.20 10 6772 31102 284424 315526 85.65
TOTAL 90 33512
COPPER
(ppm) (mg) (%)
Solids (g) 0.0879 573900 50446 13.69
Solution (mls) 420.0 677.20 284424 77.21

Total 368382 100.00
Assay Head
123 | P a g e

TEMPERATURE 45
WATER DI WATER
7M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Cu2S

0.5 500.0 189.55 40.18 2.75

Moisture (%) 0.0
dry feed 0.5
0 500.0 10.50 -93.3 0.64 10 6 6 321 327 0.00
0.08 490.0 10.44 -288.4 175.98 10 1760 1760 86230 87990 24.44
0.25 480.0 10.44 -271.3 211.22 10 2112 2112 101386 103498 28.74
0.5 470.0 10.43 -250.5 254.12 10 2541 4301 119436 123737 34.36
1 460.0 10.44 -235.8 338.08 10 3381 7682 155517 163199 45.32
2 450.0 10.48 -190.3 410.42 10 4104 11786 184689 196475 54.56
3 440.0 10.49 -167.1 428.46 10 4285 16071 188522 204593 56.82
4 430.0 10.50 -161.9 436.02 10 4360 20431 187489 207919 57.74
5 420.0 10.49 -155.3 630.00 10 6300 26731 264600 291331 80.91
TOTAL 90 28849
COPPER
(ppm) (mg) (%)
Solids (g) 0.1323 503600 66626 18.50
Solution (mls) 420.0 630.00 264600 73.48

Total 360076 100.00
Assay Head

TEMPERATURE 45
WATER DI WATER
3M [NH3] + 0.5M [CO2] + 0.022M S2O3 + 0.5g Cu2S

0.5 500.0 79.83 19.64 2.75

Moisture (%) 0.0
dry f eed 0.5
0 500.0 10.24 -62.8 1.72 10 17 17 861 878 0.00
0.08 490.0 10.16 -215.5 173.76 10 1738 1738 85142 86880 27.74
0.25 480.0 10.16 -199.9 198.94 10 1989 1989 95491 97481 31.12
0.5 470.0 10.17 -182.2 249.36 10 2494 4231 117199 121430 38.77
1 460.0 10.11 -159.7 300.92 10 3009 7240 138423 145664 46.51
2 450.0 10.17 -113.7 339.42 10 3394 10635 152739 163374 52.16
3 440.0 10.16 -104.4 370.92 10 3709 14344 163205 177549 56.69
4 430.0 10.18 -102.6 395.46 10 3955 18298 170048 188346 60.13
5 420.0 10.19 -100.5 570.40 10 5704 24002 239568 263570 84.15
TOTAL 90 26009
COPPER
(ppm) (mg) (%)
Solids (g) 0.0891 534600 47633 15.21
Solution (mls) 420.0 570.40 239568 76.49

Total 313210 100.00
Assay Head
124 | P a g e

TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1.5M [CO2] + 0.022M S2O3 + 0.5g Cu2S

0.5 500.0 57.02 58.92 2.75

Moisture (%) 0.0
dry f eed 0.5
0 500.0 9.36 -31.8 0.12 10 1 1 60 61 0.00
0.08 490.0 9.35 -188.8 167.06 10 1671 1671 81859 83530 22.86
0.25 480.0 9.30 -184.7 187.68 10 1877 1877 90086 91963 25.17
0.5 470.0 9.31 -164.3 204.56 10 2046 3716 96143 99859 27.33
1 460.0 9.28 -151.9 244.64 10 2446 6163 112534 118697 32.48
2 450.0 9.32 -134.1 301.22 10 3012 9175 135549 144724 39.61
3 440.0 9.31 -57.6 410.16 10 4102 13276 180470 193747 53.02
4 430.0 9.38 -51.8 565.20 10 5652 18928 243036 261964 71.69
5 420.0 9.35 -50.9 686.80 10 6868 25796 288456 314252 86.00
TOTAL 90 27674
COPPER
(ppm) (mg) (%)
Solids (g) 0.1003 491200 49267 13.48
Solution (mls) 420.0 686.80 288456 78.94

Total 365398 100.00
Assay Head

TEMPERATURE 60
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Cu2S

0.5 500.0 67.91 40.18 2.75

Moisture (%) 0.0
dry feed 0.5
0 500.0 9.60 -36.6 0.10 10 1 1 50 51 0.00
0.08 490.0 9.62 -177.2 180.10 10 1801 1801 88249 90050 24.44
0.25 480.0 9.60 -148.3 240.88 10 2409 2409 115622 118031 32.04
0.5 470.0 9.63 -101.2 321.40 10 3214 5015 151058 156073 42.37
1 460.0 9.61 -82.7 380.92 10 3809 8824 175223 184047 49.96
2 450.0 9.60 -78.4 430.22 10 4302 13126 193599 206725 56.12
3 440.0 9.64 -76.3 498.80 10 4988 18114 219472 237586 64.49
4 430.0 9.65 -85.7 621.60 10 6216 24330 267288 291618 79.16
5 420.0 9.64 -67.2 677.20 10 6772 31102 284424 315526 85.65
TOTAL 90 33512
COPPER
(ppm) (mg) (%)
Solids (g) 0.0879 573900 50446 13.69
Solution (mls) 420.0 677.20 284424 77.21

Total 368382 100.00
Assay Head
125 | P a g e

TEMPERATURE 25
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Cu2S

0.5 500.0 67.91 40.18 2.75

Moisture (%) 0.0
dry feed 0.5
0 500.0 9.46 -48.5 1.03 10 10 10 513 523 0.00
0.08 490.0 9.47 -191.2 156.62 10 1566 1566 76744 78310 20.09
0.25 480.0 9.48 -171.5 176.06 10 1761 1761 84509 86269 22.13
0.5 470.0 9.49 -162.4 200.64 10 2006 3573 94301 97873 25.11
1 460.0 9.47 -146.0 248.34 10 2483 6056 114236 120292 30.86
2 450.0 9.47 -104.5 296.66 10 2967 9023 133497 142520 36.56
3 440.0 9.48 -94.4 297.74 10 2977 12000 131006 143006 36.69
4 430.0 9.48 -90.3 306.76 10 3068 15068 131907 146974 37.71
5 420.0 9.47 -86.6 408.02 10 4080 19148 171368 190516 48.88
TOTAL 90 20919
COPPER
(ppm) (mg) (%)
Solids (g) 0.1633 1209430 197500 50.67
Solution (mls) 420.0 408.02 171368 43.96

Total 389787 100.00
Assay Head

TEMPERATURE 45
WATER DI WATER
DATE 6th of March 2017
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Cu2S + 0.25M Na2SO3

(Hours) Ore Solution Ammonia Carbonate S2O3 Na2SO3 pH ORP Cu Vol Cu Cu Vessel Total Total
0.5 500.0 67.91 40.18 2.75 31.5

Moisture (%) 0.0
dry f eed 0.5
0 500.0 9.97 -132.5 0.33 10 3 3 167 170 0.00
0.08 490.0 9.94 -212.9 221.04 10 2210 2210 108310 110520 22.67
0.25 480.0 9.93 -196.7 280.40 10 2804 2804 134592 137396 28.18
0.5 470.0 9.92 -180.4 340.86 10 3409 5619 160204 165823 34.01
1 460.0 9.82 -157.1 753.60 10 7536 13155 346656 359811 73.81
2 450.0 9.88 -148.0 828.80 10 8288 21443 372960 394403 80.90
3 440.0 9.71 -134.1 888.40 10 8884 30327 390896 421223 86.40
4 430.0 9.77 -132.0 983.40 10 9834 40161 422862 463023 94.98
5 420.0 9.76 -127.1 1033.80 10 10338 50499 434196 484695 99.42
TOTAL 90 53306
COPPER
(ppm) (mg) (%)
Solids (g) 0 0.00
Solution (mls) 420.0 1033.80 434196 89.07

Total 487502 100.00
Assay Head
126 | P a g e

TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.5g Cu2S + 0.5M Na2SO3

0.5 500.0 67.91 40.18 2.75 63.0

Moisture (%) 0.0
dry feed 0.5
0 500.0 10.13 -166.8 0.29 10 3 3 147 149 0.00
0.08 490.0 10.11 -232.3 196.52 10 1965 1965 96295 98260 24.09
0.25 480.0 10.14 -230.6 263.42 10 2634 2634 126442 129076 31.65
0.5 470.0 10.08 -213.8 305.26 10 3053 5018 143472 148490 36.41
1 460.0 10.08 -199.5 399.96 10 4000 9017 183982 192999 47.32
2 450.0 10.11 -182.2 619.20 10 6192 15209 278640 293849 72.05
3 440.0 10.06 -168.8 758.60 10 7586 22795 333784 356579 87.43
4 430.0 10.12 -158.9 840.80 10 8408 31203 361544 392747 96.30
5 420.0 10.13 -152.0 869.80 10 8698 39901 365316 405217 99.35
TOTAL 90 42539
COPPER
(ppm) (mg) (%)
Solids (g) 0 0.00
Solution (mls) 420.0 869.80 365316 89.57

Total 407855 100.00
Assay Head
127 | P a g e
TEST No LEACH TEST 1A

SAMPLE COPPER FLOTATION CONCENTRATE
TEMPERATURE 45
WATER DI WATER
5M [NH3] + 1M [CO2] + 0.022M S2O3

10.0 500.0 137.39 40.18 2.75

Moisture (%) 0.0
dry feed 10
0 500.0 10.39 -75.3 0.34 10 3 3 168 171 0.00
0.08 490.0 10.36 -210.5 20.45 10 205 205 10021 10226 1.77
0.25 480.0 10.43 -210.8 35.10 10 351 351 16848 17199 2.98
0.5 470.0 10.41 -206.9 39.50 10 395 600 18565 19165 3.32
1 460.0 10.45 -203.5 49.08 10 491 1090 22577 23667 4.10
2 450.0 10.47 -197.7 73.02 10 730 1821 32859 34680 6.01
3 440.0 10.46 -195.4 89.34 10 893 2714 39310 42024 7.28
4 430.0 10.39 -193.1 110.36 10 1104 3818 47455 51272 8.88
5 420.0 10.44 -189.9 129.40 10 1294 5112 54348 59460 10.30
6 410.0 10.41 -186.5 155.84 10 1558 6670 63894 70564 12.22
24 400.0 10.28 -185.3 428.68 10 4287 10957 171472 182429 31.59
30 390.0 10.28 -185.3 624.80 10 6248 17205 243672 260877 45.18
TOTAL 120 17559
COPPER
(ppm) (mg) (%)
Solids (g) 1.7860 177037 316188 54.76
Solution (mls) 390.0 624.80 243672 42.20

Total 577419 100.00
Calculated Head 5.8
Assay Head
128 | P a g e
TEST No LEACH TEST 1B

SAMPLE COPPER FLOTATION CONCENTRATE
TEMPERATURE 45
WATER DI WATER
DATE
5M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.25M Na2SO3

10.0 500.0 137.39 40.18 2.75 31.5

Moisture (%) 0.0
dry feed 10
0 500.0 10.19 -352.6 0.17 10 2 2 84 86 0.00
0.08 490.0 10.15 -460.0 4.45 10 44 44 2180 2224 0.83
0.25 480.0 10.10 -481.0 5.39 10 54 54 2585 2639 0.98
0.5 470.0 10.11 -492.0 5.97 10 60 104 2806 2911 1.08
1 460.0 10.12 -477.0 6.79 10 68 172 3124 3296 1.22
2 450.0 10.12 -458.0 6.97 10 70 242 3138 3380 1.26
3 440.0 10.12 -459.0 7.41 10 74 316 3260 3576 1.33
4 430.0 10.12 -469.0 7.43 10 74 390 3195 3586 1.33
5 420.0 10.11 -459.0 7.59 10 76 466 3189 3656 1.36
6 410.0 10.12 -451.0 9.13 10 91 558 3744 4301 1.60
24 400.0 10.01 -442.0 10.19 10 102 659 4076 4735 1.76
30 390.0 10.00 -451.0 11.59 10 116 775 4520 5295 1.97
TOTAL 120 831
COPPER
(ppm) (mg) (%)
Solids (g) 1.0100 261302 263915 98.01
Solution (mls) 390.0 11.59 4520 1.68

Total 269266 100.00
Calculated Head 2.7
Assay Head
129 | P a g e
TEST No LEACH TEST 2A

SAMPLE NICKEL FLOTATION CONCENTRATE
TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3

10.0 500.0 67.91 40.18 2.75

Moisture (%) 0.0
dry feed 10
0 500.0 9.75 -39.2 0.79 10 8 8 397 404 0.00
0.08 490.0 9.81 -394.7 6.55 10 65 65 3207 3273 1.23
0.25 480.0 9.82 -396.4 7.63 10 76 76 3660 3737 1.40
0.5 470.0 9.84 -305.2 9.17 10 92 157 4308 4465 1.67
1 460.0 9.84 -201.5 11.63 10 116 273 5349 5623 2.11
2 450.0 9.86 -205.9 13.87 10 139 412 6242 6654 2.49
3 440.0 9.84 -205.7 17.21 10 172 584 7572 8156 3.06
4 430.0 9.79 -198.5 51.94 10 519 1104 22334 23438 8.78
5 420.0 9.85 -158.5 62.44 10 624 1728 26225 27953 10.47
6 410.0 9.85 -143.7 67.08 10 671 2399 27503 29902 11.20
24 400.0 9.80 -144.6 78.40 10 784 3183 31360 34543 12.94
30 390.0 9.75 -135.0 91.74 10 917 4100 35779 39879 14.94
TOTAL 120 4184
NICKEL
(ppm) (mg) (%)
Solids (g) 1.8740 121097 226936 85.03
Solution (mls) 390.0 91.74 35779 13.41

Total 266899 100.00
Calculated Head 2.7
Assay Head
130 | P a g e
TEST No LEACH TEST 2B

SAMPLE NICKEL FLOTATION CONCENTRATE
TEMPERATURE 45
WATER DI WATER
3M [NH3] + 1M [CO2] + 0.022M S2O3 + 0.25M Na2SO3

10.0 500.0 67.91 40.18 2.75 31.5

Moisture (%) 0.0
dry feed 10
0 500.0 10.70 -353.6 0.26 10 3 3 128 130 0.00
0.08 490.0 10.67 -406.6 0.33 10 3 3 159 163 0.14
0.25 480.0 10.64 -431.0 2.77 10 28 28 1329 1356 1.14
0.5 470.0 10.66 -440.0 5.82 10 58 61 2736 2798 2.35
1 460.0 10.65 -440.0 7.14 10 71 133 3283 3415 2.87
2 450.0 10.66 -432.0 7.48 10 75 208 3367 3575 3.00
3 440.0 10.66 -433.0 8.06 10 81 288 3546 3835 3.22
4 430.0 10.68 -438.0 8.30 10 83 371 3569 3941 3.31
5 420.0 10.66 -423.0 9.63 10 96 468 4046 4514 3.79
6 410.0 10.67 -419.0 17.92 10 179 647 7346 7992 6.71
24 400.0 10.48 -408.5 84.62 10 846 1493 33848 35341 29.68
30 390.0 10.49 -403.6 139.86 10 1399 2892 54545 57437 48.24
TOTAL 120 2922
NICKEL
(ppm) (mg) (%)
Solids (g) 9.0600 6798 61590 51.73
Solution (mls) 390.0 139.86 54545 45.81

Total 119057 100.00
Calculated Head 1.2
Assay Head
131 | P a g e
APPENDIX C. EFMS dissolution data
Dissolution 1
TIME (Hrs) Ni (mg/L)
(uM/cm2)
DISSOLUTION (µM/cm2)
0 0 0.00 0.75
0.08 6.13 0.69
0.25 6.75 0.76 0.5 y = 3.5719x
0.50 7.32 0.83
1 8.22 0.93 0.25
2 9.03 1.02
3 9.89 1.12
0
4 10.47 1.18 0 0.05 0.1 0.15 0.2 0.25
5 13.10 1.48 TIME (Hrs)
FIGURE 90. Dissolution of nickel sulfide.
TIME Co Dissolution 0.10

(Hrs) (mg/L) (uM/cm2)
0.08
0 0.000 0.000
0.08 0.658 0.074 0.06 y = 0.2177x
0.25 0.725 0.082
0.50 0.767 0.086 0.04
1 0.842 0.095
0.02
2 0.871 0.098
3 0.949 0.107 0.00
4 1.042 0.117 0 0.1 0.2 0.3 0.4 0.5
5 2.210 0.249 TIME (Hrs)
FIGURE 91. Dissolution of cobalt sulfide.
TIME Cu Dissolution 0.14

(Hrs) (mg/L) (uM/cm2) 0.12
0 0.000 0.000 0.10

0.08 0.720 0.081
0.08
0.25 1.053 0.118
0.06 y = 0.5222x
0.50 1.069 0.120
1 1.134 0.128 0.04
2 1.196 0.135 0.02
3 1.240 0.140
0.00
4 1.362 0.153 0 0.05 0.1 0.15 0.2 0.25
5 1.400 0.157 TIME (Hrs)
FIGURE 92. Dissolution of copper sulfide.
132 | P a g e
APPENDIX D. SMMS XRD data
FIGURE 93. XRD analysis of nickel sulfide.
FIGURE 94. XRD analysis of cobalt sulfide.
FIGURE 95. XRD analysis of copper sulfide.
133 | P a g e
APPENDIX E. SMMS kinetic model plots
0.9
3M R² = 0.95
0.8
5M R² = 0.96
0.7
7M R² = 0.88
0.6
1-(1-x)1/3
0.5
0.4
0.3
0.2
0.1
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 96. Plot of surface reaction model vs time for leaching nickel from nickel sulfide at
different ammonia concentrations.
1
3M R² = 0.94
0.9
5M R² = 0.97
0.8
7M R² = 0.90
0.7
1-3(1-x)2/3 + 2(1-x)
0.6
0.5
0.4
0.3
0.2
0.1
0
0 1 2 3 4 5
TIME (Hrs)
134 | P a g e
0.8
3M R² = 0.87
0.7
5M R² = 0.97
1-2(1-x)1/3 + (1-x)2/3 0.6 7M R² = 0.90
0.5
0.4
0.3
0.2
0.1
0
0 1 2 3 4 5
TIME (Hrs)
ammonia concentrations.
0.9
0.5M R² = 0.99
0.8
1M R² = 0.95
0.7
1.5M R² = 0.97
0.6
1-(1-x)1/3
0.5
0.4
0.3
0.2
0.1
0
0 1 2 TIME (Hrs) 3 4 5
FIGURE 99. Plot of surface reaction model vs time for leaching nickel from nickel sulfide at
different ammonium carbonate concentrations.
135 | P a g e
1
0.5M R² = 0.96
0.9
1M R² = 0.94
0.8
1.5M R² = 0.97
0.7
1-3(1-x)2/3 + 2(1-x)
0.6
0.5
0.4
0.3
0.2
0.1
0
0 1 2 TIME (Hrs) 3 4 5
0.8
0.5M R² = 0.94
0.7
1M R² = 0.87
1-2(1-x)1/3 + (1-x)2/3
0.6 1.5M R² = 0.96

0.5
0.4
0.3
0.2
0.1
0
0 1 2 3 4 5
TIME (Hrs)
ammonium carbonate concentrations.
136 | P a g e
0.4
0.35
0.3
0.25
1-(1-x)1/3
0.2
0.15
0.1 3M R² = 0.98
5M R² = 1.00
0.05
7M R² = 0.97
0
0 1 2 3 4 5
TIME (Hrs)
0.35
3M R² = 0.96
0.3 5M R² = 1.00
7M R² = 0.91
0.25
1-3(1-x)2/3 + 2(1-x)
0.2
0.15
0.1
0.05
0
0 1 2 TIME (Hrs) 3 4 5
137 | P a g e
0.14
3M R² = 0.96
0.12 5M R² = 1.00
1-2(1-x)1/3 + (1-x)2/3 7M R² = 0.90
0.1
0.08
0.06
0.04
0.02
0
0 1 2 TIME (Hrs) 3 4 5
0.4
0.35
0.3
0.25
1-(1-x)1/3
0.2
0.15
1M R² = 1.00
0.1
2M R² = 0.98
0.05
3M R² = 0.94
0
0 1 2 3 4 5
TIME (Hrs)
138 | P a g e
0.35
0.3
1-3(1-x)2/3 + 2(1-x) 0.25
0.2
0.15
0.1 1M R² = 1.00
2M R² = 0.99
0.05
3M R² = 0.92
0
0 1 2 3 4 5
TIME (Hrs)
0.14
0.12
0.1
1-2(1-x)1/3 + (1-x)2/3
0.08
0.06
0.04 1M R² = 1.00
2M R² = 0.99
0.02
3M R² = 0.91
0
0 1 2 TIME (Hrs) 3 4 5
139 | P a g e
0.6
3M R² = 0.97
0.5 5M R² = 0.93
7M R² = 0.82
0.4
1-(1-x)1/3
0.3
0.2
0.1
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 108. Plot of surface reaction model vs time for leaching copper from copper sulfide at
0.5
3M R² = 0.95
0.45
5M R² = 0.95
0.4
7M R² = 0.76
1-3(1-x)2/3 + 2(1-x)
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0 1 2 TIME (Hrs) 3 4 5
FIGURE 109. Plot of ash layer diffusion model vs time for leaching copper from copper sulfide at
140 | P a g e
0.25
3M R² = 0.92
5M R² = 0.97
0.2
1-2(1-x)1/3 + (1-x)2/3 7M R² = 0.72
0.15
0.1
0.05
0
0 1 2 3 4 5
TIME (Hrs)
0.6
0.5M R² = 0.80
0.5 1M R² = 0.97
1.5M R² = 0.93
0.4
1-(1-x)1/3
0.3
0.2
0.1
0
0 1 2 TIME (Hrs) 3 4 5
FIGURE 111 . Plot of surface reaction model vs time for leaching copper from copper sulfide at
141 | P a g e
0.5
0.5M R² = 0.74
0.45
1M R² = 0.95
0.4
1-3(1-x)2/3 + 2(1-x) 1.5M R² = 0.87
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0 1 2 3 4 5
TIME (Hrs)
FIGURE 112. Plot of ash layer diffusion vs time for leaching copper from copper sulfide at
0.25
0.5M R² = 0.70
1M R² = 0.92
0.2
1-2(1-x)1/3 + (1-x)2/3
1.5M R² = 0.83
0.15
0.1
0.05
0
0 1 2 3 4 5
TIME (Hrs)
142 | P a g e
APPENDIX F. Amount of reagents calculations
Source of CO2 is solid reagent NH4HCO3NH2COONH4. This could also be written as 3NH3 + 2CO2 + H2O
Sources of NH3 are the reagent NH4HCO3NH2COONH4 plus aqueous ammonia solution.
Contained
CO2 NH3 CO2 M.W.
Reagent mol mol g
NH4HCO3NH2COONH4 3 2 157.13
Contained NH3 S.G.

NH3 % g/mL
Solution 28 0.91
Target Required additions of per 1 liter of solution

concentration M.W. NH4HCO3NH2COONH4 Contained NH3 solution
g/L g mol/L g g mol g mL
CO2 45 44.00 1.02 80.35 45.00 1.02
NH3 90 17.03 5.28 26.13 1.53 228.12 250.68
FIGURE 114. Reagent amounts calculations.
143 | P a g e
APPENDIX G. RMS XRD data
FIGURE 115. XRD analysis of Nickel Sulfide flotation concentrate feed.
FIGURE 116. XRD analysis of Nickel Leach Residue A.
144 | P a g e
FIGURE 117. XRD analysis of Nickel Leach Residue B.
FIGURE 118. XRD analysis of Copper Sulfide flotation concentrate feed.
145 | P a g e
FIGURE 119. XRD analysis of Copper Leach Residue A.
FIGURE 120. XRD analysis of Copper Leach Residue B.
146 | P a g e
147 | P a g e
148 | P a g e

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The leaching of metal sulfides in

ammoniacal carbonate solutions

This thesis is presented for the Degree of Honours in Mineral Science,

School of Engineering and Information Technology

Supervisor : Dr. Aleks Nikoloski

I declare that this thesis is my own account of my research and

The leaching of metal sulfides in ammoniacal solutions is of industrial importance for

The Caron process involves an oxidative dissolution of pre-reduced iron-based nickel

- Total Concentration of Carbonate species

- Total Concentration of Ammonia species

- Concentration of Ammonia added as

First and foremost, I would like to thank my supervisor, Dr. Aleks

Nikoloski for providing me with endless guidance, support and advice.

I am forever grateful for all his time and dedication spent in

mentoring me throughout this challenging journey.

I would like to express my gratitude to Dr. Drew Parsons for always

being willing to help when I needed a question answered.

I wish to place my sincere thanks to Dr. David Hough for his

I would also like to take this opportunity to acknowledge the other

faculty in the School of Engineering and Information Technology at

Murdoch University. Their teachings have guided my academic

Finally, I would like to thank my friends and family for their

unconditional love, support, advice and encouragement. Without

them, none of this would indeed be possible.

I would like to dedicate this work to the memory of my father –

2.2 AMMONIACAL LEACHING PROCESS

1) There must be a diffusion of the reagents to the mineral surface, as well as

The electrochemical mechanism of leaching sulfides can be represented by the following

Cathodic Reaction: [Eq.1]

Anodic Reaction: [Eq.2]

An ammonia-ammonium carbonate system was first used to recover non-ferrous metals

2.2.1 The Caron Process

2.2.2 The Sherritt Gordon Process

COPPER BOIL SOLID / LIQUID

OXYDROLYSIS NICKEL REDUCTION

CRYSTALLISATION METAL STRIPPING

FIGURE 4. A flowsheet showing the Sherritt Gordon process.

2.4 IRON PASSIVATION LAYER FORMATION

2.5 ELECTROCHEMICAL PRINCIPLES

2.5.2 Corrosion Potential

The anodic metal dissolution can be represented as an exponential function of the

where and are parameters.

1) The characteristic equilibrium potentials of both redox systems will be shifted by

= current density as a result of imposed potential (A/cm2)

= exchange current density (A/cm2)

F = Faraday’s constant (C/mol)

n = number of electrons in the half-reaction

R = universal molar gas constant (kJ/mol)

2.5.4 Cyclic Voltammetry

FIGURE 10. A schematic representation of current-potential relationship as metal undergoes

Recently, there has been an increased interest in characterisation techniques specific to

In order to use synchrotron radiation in the characterisation of electrochemical systems

Reflection cells contain an X-ray transparent window, situated parallel or perpendicular

A significant innovation in studies of electrochemical interface systems in-situ has been

FIGURE 13.SEM micrographs showing nickel electrodeposition obtained at different potentials

As described by Brant et al. (2013), in-situ electrochemical cells cannot be converged to

3.1.1 Electrochemically formed Metal Sulfides (EFMS)

3.1.2 Synthetic Monometallic Metal Sulfides (SMMS)

3.1.3 Flotation Concentrate Samples (RMS)

3.1.4 Test Solutions

TABLE 1. Solution compositions used in the electrochemical portion of this project.

mol/L mol/L x 10-3

3.2 METHODS USED FOR ELECTROCHEMICAL STUDY