Glycine As A Lixiviant For The Leaching of Low Grade Copper Gold Ores Bennson Chemuta Tanda

Western Australian School of Mines
GLYCINE AS A LIXIVIANT FOR THE LEACHING OF LOW

GRADE COPPER-GOLD ORES
Bennson Chemuta Tanda
This thesis is presented for the Degree of
Doctor of Philosophy
of
Curtin University
February 2017
List of Publications
Tanda, B. C., Eksteen, J. J., & Oraby, E. A. (2017). An Investigation into the Leaching Behaviour
of Copper Oxide Minerals in Aqueous Alkaline Glycine Solutions. Hydrometallurgy, 167, 153-
162
Tanda, B. C., Oraby, E. A., & Eksteen, J. J. (2017). Recovery of Copper from Alkaline Glycine
Leach Solution Using Solvent Extraction. Separation and Purification Technology, 187, 389-
396
Eksteen, J. J., Oraby, E. A., & Tanda, B. C. (2017). A Conceptual Process for Copper Extraction
from Chalcopyrite in Alkaline Glycinate Solutions. Minerals Engineering, 108, 53-66
Oraby, E. A., Eksteen, J. J., & Tanda, B. C. (2017). Gold and Copper Leaching from Gold-Copper
Ores and Concentrates Using a Synergistic Lixiviant Mixture of Glycine and Cyanide.
Hydrometallurgy, 169, 339-345
Eksteen, J. J., Oraby, E. A., & Tanda, B. C. (2016). Developing Robust Hydrometallurgical
Processes to Recover Metals from Deposits with Large Geometallurgical Variation. Paper
presented at the The Third AusIMM International Geometallurgy Conference, Perth-
Australia, 15-20
Eksteen, J. J., Oraby, E. A., & Tanda, B. C. (2016). An Alkaline Glycine Based Process for Copper
Recovery and Iron Rejection from Chalcopyrite. Proceedings of the 46th Annual
Hydrometallurgy Meeting and the 4th International Symposium of Iron Control in
Hydrometallurgy. Eds. E.M.L. Peek, M. Buarzaiga, & J.E. Dutrizac. 11-15 September, Quebec
City, Quebec, pp. 349-358
ii
Abstract
In gold processing, resources that can be efficiently processed by the well-established
cyanide process are in decline. Most recently, research focus has shifted towards the
processing of low grade, complex ore bodies that contain impurities such as copper, arsenic,
antimony, nickel and zinc which are detrimental to the cyanide process. Copper-containing
gold ores are an important source of both copper and gold as they are obtainable in huge
deposits in many countries throughout the world. The conventional cyanidation of gold ores
is inefficient in the treatment of copper-gold ores since the presence of copper minerals
results in increased reagent consumption (cyanide, lime and oxygen) and decreased gold
dissolution rate. In addition to these technical challenges, the use of cyanide in the mining
industry has been banned or restricted in some parts of the world due to its toxicity and the
associated environmental concerns .
Glycine is an environmentally benign reagent which has been reported to form stable
complexes with copper and gold. In this research, glycine, was investigated as a potential
lixiviant for low grade copper-gold ores at alkaline pH. Although alkaline glycine solutions
have been reported to selectively leach copper over gold from a copper flotation
concentrate, the leaching behaviour of individual copper minerals in alkaline glycine
solutions has not been studied. Also, there are no publications on the leaching kinetics of
any copper minerals in the alkaline glycine system. Low grade copper–gold ores have not
been leached in the proposed lixiviant system in order to establish the influence of process
variables on copper and gold leaching and the deportment of impurity metals. Furthermore,
no data has been published on the recovery of copper from alkaline glycine leach system.
This research project is thus novel and will present a significant contribution to knowledge
as it endeavours to fill the gaps in knowledge mentioned above.
Copper minerals were bottle rolled in alkaline glycine solutions under ambient conditions
and the results revealed that, with the exception of chyrsocolla, copper oxide minerals leach
more rapidly than their sulfide counterparts. Copper extractions from azurite, malachite,
cuprite, chrysocolla, metallic copper, chalcocite and chalcopyrite were 97, 90, 94, 19, 92, 42,
6 %, respectively. However, during the leaching kinetic investigations for malachite,
chalcocite and chalcopyrite carried out in a glass reactor whereby process variables could be
controlled, higher copper extractions rates were obtained. Up to 99 % Cu was extracted from
malachite in just 30 minutes. Leaching of a finely ground chalcocite (P80 18 µm) resulted in
iii
78 % Cu extraction in 48 hours. The leaching of a P100 of 10 µm chalcopyrite resulted in 90 %
Cu extraction after 96 hours.
Copper speciation in the PLS identified Cu (II) ions as the stable Cu species that form the
stable Cu-glycinate complex. Sulfur speciation of chalcopyrite PLS showed that, over 90.0 %
of leached sulfur was in the form of sulfate (SO42-). It was determined that chalcopyrite
leaching was dominantly controlled by diffusion through the product layer. The leaching of
copper from malachite and chalcocite was also noted to be controlled by diffusion through
the product layer. It was also predicted that chalcocite leaches in two stages; the first stage
involves the rapid dissolution of surface chalcocite leaving behind a covellite residue which
leaches rather slowly in the second stage.
Copper-gold ores (oxides: Cu-Au ore A, sulfides: Cu-Au B and Cu-Au C) leaching in alkaline
glycine solution revealed that, Cu and Au simultaneously leach from both ore types.
However, Cu leaches faster than gold. Glycine concentration, temperature, initial leach
solution pH, dissolved oxygen had no significant influence on copper dissolution from the
gold-copper oxide ore as about 75.0 % was obtained for all variables after 96 hours of
leaching. Over the same time, Au dissolution was significantly improved by increased
temperature. At 60 °C , 32 % Au was leached while only 0.5 % was leached at 25 °C. Galvanic
interactions caused by the addition of 20 g/t pyrite to the Au-Cu oxide ore led to 60 % Au
dissolution which is a 36 % increase from that with no added pyrite. During the leaching of
the Au-Cu sulfide ore, gold dissolution occurred concurrently with copper dissolution at 25
°C. This observation was attributed to galvanic interactions since the sulfide ore naturally
contained pyrite. Increases in glycine concentration also improved the dissolution of both
copper and gold from the sulfide ore. Upto 66 and 25 % Cu and Au, respectively, was leached
from Cu-Au ore C (sulfide) after 96 hours in the glass reactor.
Copper recoverability from the glycine leached PLS was investigated by solvent extraction
and and sulfide precipitation. Solvent extraction experiments using Mextral 84H (oxime) and
Mextral 54-100 (diketone) at an Aqueous-to-Organic ratio (A:O) of 2:1, recovered 99 % and
96 % Cu, respectively make up solutions. Glycine was not extracted by either extractants and
can thus be recycled to the leaching circuit. Copper was completely stripped with make-up
spent electrolyte solution from Mextral 54-100, while only 80.0 % was stripped from Mextral
84H. Copper solvent extraction from ore leachates showed similar results. However, Zn , Co
and Ni were simultaneously extracted with Cu although to a much lesser extent. Au is not
extracted by either extractant.
iv
Copper precipitation using sodium hydrogen sulfide (NaHS) showed that 99.0 % of copper
was precipited at a Cu:S molar ratio of 1:1. The precipitate was identified by XRD analysis to
be 100 % covellite with a particle size distribution of P80 66 µm. As was the case with solvent
extraction, Zn, Ni and Co that are concomitantly leached with copper are also prepecipited
but to a much lesser extent than Cu. The gold content in solution was observed to be
reduced by up to 16.2 % during copper precipitation.
The results obtained in this research enabled the development of flowsheets according to
the type of ore being processed. Low grade ores are best processed by heap leaching, solvent
extraction and electrowinning of copper. Any gold present in ore is simultaneously leached
with the copper, and then recovered by activated carbon after solvent extraction of copper.
For Cu-Au flotation concentrates, the feed is subjected to ultrafine grinding and then leached
at elevated temperatures (60 °C) in tanks.
v
Acknowledgements
The achievement of this thesis is thanks to the significant contribution of many people. Most
particularly, I would like to express my deepest and sincere thanks to my supervisors
Professor Jacques Eksteen and Dr Elsayed Oraby for their guidance, tolerance, support,
endurance and encouragement during this process. I immensely appreciate their enthusiasm
and motivation which inspired me to conduct and complete this research.
My sincere gratitude goes to the all the members of the Gold Technology Group for all their
encouragement and assistance throughout this project.
I acknowledge with thanks the financial support from Curtin University and the Gold
Technology Group, without which the work presented in this thesis would not have been
possible.
Last but not the least, I would like to express my wholehearted gratitude to my wife, Melvice
Tanda, my daughter Lumafanwi Tanda, my entire family and friends whose support and love
has been invaluable throughout this journey.
vi
Table of Contents
Author’s Declaration ....................................................................................................... i
List of Publications ......................................................................................................... ii
Abstract…………. ..............................................................................................................iii
Acknowledgements........................................................................................................vi
Table of Contents .......................................................................................................... vii
List of Figures… ............................................................................................................. xv
List of Tables… ............................................................................................................ xxiii
List of Abbreviations ................................................................................................. xxvii
Chapter 1 Introduction ............................................................................................ 1
1.1 Background to this study ........................................................................ 1
1.2 Objectives and significance of this study ................................................ 5
1.3 Scope of this study .................................................................................. 6
1.4 Thesis Overview ...................................................................................... 7
Chapter 2 Review of Literature ............................................................................... 9
2.1 Chapter Objective ................................................................................... 9
2.2 Copper-Gold Resources .......................................................................... 9
2.2.1 Mineralogical variation in porphyry copper-gold deposits .................. 11
2.3 Processing of Copper-Gold Ores ........................................................... 15
2.3.1 Copper-Gold Cyanidation Challenges ................................................... 15
2.3.2 Coping with Copper-Gold Cyanidation Challenges ............................... 19
2.4 Attributes of Good Lixiviants ................................................................ 21
2.4.1 Attributes of Copper and/or Gold Ore Lixiviants .................................. 23
2.5 Alkaline Ammoniacal Hydrometallurgy of Copper and Gold ................ 25
vii
2.5.1 Aqueous Chemistry of Copper and Ammonia ...................................... 29
2.5.2 Metal Recovery from Ammoniacal PLS................................................. 36
2.5.3 Challenges of Ammonia Leaching ......................................................... 37
2.6 Glycine as Copper and Gold Lixiviant.................................................... 38
2.6.1 Structure, Physical and Chemical Properties ........................................ 38
2.6.2 Industrial Applications of Glycine ......................................................... 39
2.6.3 Glycine Production................................................................................ 39
2.6.4 Aqueous Chemistry of Glycine .............................................................. 40
2.6.5 Glycine Analysis .................................................................................... 45
2.7 Leaching Methods Applicable to Low Grade Ores................................ 46
2.7.1 Dump Leaching ..................................................................................... 48
2.7.2 Heap Leaching ....................................................................................... 49
2.7.3 Vat Leaching .......................................................................................... 50
2.7.4 Bioleaching............................................................................................ 51
2.8 Summary ............................................................................................... 52
Chapter 3 Materials and Methods......................................................................... 53
3.1 Chapter Objectives................................................................................ 53
3.2 Materials and Reagents ........................................................................ 53
3.3 Procedures ............................................................................................ 55
3.3.1 Mineral and Ore Specimens Preparation ............................................. 55
3.3.2 Leaching Behaviour of Copper Minerals ............................................... 56
3.3.3 Copper Speciation ................................................................................. 57
3.3.4 Leaching Kinetics Experiments ............................................................. 57
3.3.5 Leaching of Copper-Gold Ores .............................................................. 59
3.3.6 Column Leaching................................................................................... 59
3.3.7 Solvent Extraction ................................................................................. 61
3.3.8 Precipitation.......................................................................................... 63
viii
3.4 Instrumental Analysis ........................................................................... 63
3.4.1 X-Ray Diffraction (XRD) ......................................................................... 64
3.4.2 X-Ray Fluorescence (XRF)...................................................................... 65
3.4.3 TESCAN Integrated Mineral Analyser (TIMA) ....................................... 65
3.4.4 UV-Visible (UV-Vis) Spectrophotometry ............................................... 65
3.4.5 Particle Size Analysis (PSA) ................................................................... 66
3.4.6 Atomic Absorption Spectrometry (AAS) ............................................... 66
3.4.7 Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES)

and Inductively Couple Plasma Mass Spectrometry (ICP-MS).............. 67
3.4.8 High Performance Liquid Chromatography (HPLC) .............................. 68
3.4.9 Scanning Electron Microscopy (SEM) ................................................... 68
3.4.10 X-Ray Photoelectron Spectroscopy ...................................................... 69
3.4.11 Miscellaneous Analysis ......................................................................... 70
3.4.12 Auxiliary Equipment .............................................................................. 70
Chapter 4 Differential Leaching Behaviour of Copper Minerals: Towards a

Geometallurgical Indicator ................................................................... 71
4.1 Chapter Objectives and Background .................................................... 71
4.2 Azurite ................................................................................................... 72
4.2.1 Mineralogy and Elemental Composition .............................................. 72
4.2.2 Effect of Initial Glycine Concentration .................................................. 73
4.2.3 Effect of Initial Solution pH ................................................................... 73
4.3 Malachite A ........................................................................................... 75
4.4 Cuprite .................................................................................................. 78
ix
4.5 Chrysocolla ............................................................................................ 81
4.5.3 Effect of Initial solution pH ................................................................... 82
4.6 Metallic Copper..................................................................................... 84
4.6.3 Effect of Hydrogen Peroxide ................................................................. 86
4.7 Chalcocite A .......................................................................................... 87
4.7.5 Effect of Additives ................................................................................. 91
4.8 Chalcopyrite A ....................................................................................... 93
4.9 Dissolution of Impurities....................................................................... 97
4.10 Summary ............................................................................................... 99
Chapter 5 Mechanisms and Kinetics of Leaching Malachite, Chalcocite, and

Chalcopyrite in Glycine Solutions ....................................................... 102
5.1 Chapter Objectives and Background .................................................. 102
5.2 Copper Speciation in Alkaline Glycine Solutions ................................ 107
x
5.3 Sulfur Speciation from Copper Sulfides Leaching ............................... 110
5.4 Leach Residue Analysis ....................................................................... 111
5.4.1 Chalcocite............................................................................................ 111
5.4.2 Chalcopyrite ........................................................................................ 113
5.5 Proposed Leaching Equations ............................................................. 116
5.6 Leaching Kinetics of Malachite, Chalcocite and Chalcopyrite ............ 116
5.6.1 Malachite B ......................................................................................... 116
5.6.2 Chalcocite B ........................................................................................ 124
5.6.3 Chalcopyrite B ..................................................................................... 132
5.7 Summary ............................................................................................. 143
Chapter 6 Leaching of Copper-Gold Ores ............................................................ 145
6.1 Chapter Objectives.............................................................................. 145
6.2 Copper- Gold Ore A............................................................................. 145
6.2.1 Mineralogical and Elemental Composition ......................................... 145
6.2.2 Effect of Glycine .................................................................................. 146
6.2.3 Effect of Initial Solution pH ................................................................. 148
6.2.4 Effect of Hydrogen Peroxide ............................................................... 149
6.3 Copper - Gold Ore B ............................................................................ 151
6.3.1 Mineralogy and Elemental Composition ............................................ 151
6.3.4 Effect of Temperature......................................................................... 154
6.3.5 Effect of Oxygen .................................................................................. 155
6.3.6 Effect of Galvanic Interactions ............................................................ 157
6.4 Copper-Gold Ore C .............................................................................. 158
6.4.1 Mineralogical and Elemental Composition ......................................... 158
xi
6.4.5 Effect of Oxygen .................................................................................. 163
6.4.6 Effect of Galvanic Interaction ............................................................. 164
6.5 Heap Leach Simulation ....................................................................... 166
6.5.1 Copper-Gold ore C .............................................................................. 166
6.5.2 Copper-Gold ore D .............................................................................. 168
6.5.3 Improving heap leaching rates ........................................................... 170
6.6 Summary ............................................................................................. 171
Chapter 7 Recovery of Metals from Alkaline Glycine Pregnant Leach Solutions 172
7.1 Chapter Overview and Background .................................................... 172
7.2 Solvent Extraction of Copper from Synthetic Copper Glycinate

Solution ............................................................................................... 174
7.2.1 Effect of Aqueous pH .......................................................................... 174
7.2.3 Effect of Contact Time ........................................................................ 175
7.2.4 Effect of Glycine Concentration .......................................................... 176
7.2.5 Effect of Extractant Concentration ..................................................... 176
7.2.6 Loading Capacity of Mextral 84H and Mextral 54- 100 ...................... 177
7.2.7 Extraction Distribution Isotherm ........................................................ 178
7.2.8 The Fate of Glycine during Solvent Extraction.................................... 178
7.2.9 Sulfuric Acid Stripping of Copper Loaded Organics ............................ 179
7.2.10 Stripping Isotherm and Counter Current Stripping Simulation .......... 180
7.3 Solvent extraction from Malachite leachate and stripping of Cu from

Extractant............................................................................................ 180
7.4 Solvent Extraction of Copper from Chalcopyrite B Leachate and Cu

Stripping from Extractant ................................................................... 182
xii
7.5 Solvent Extraction of Copper from a Copper-Gold leachate .............. 185
7.6 Qualitative Comparison of Cost Drivers of the Alkaline Glycine Leach-SX

and Conventional Sulfuric Acid Leach-SX Processes for Copper Ores. 186
7.7 Copper Precipitation from a Synthetic Copper Glycinate Solution .... 188
7.7.1 Effect of Copper to Sulfide Ratio (Cu:S) .............................................. 188
7.7.2 Effect of pH ......................................................................................... 188
7.7.3 Precipitate Analysis ............................................................................. 189
7.8 Copper Precipitation from a Malachite Ore Leachate ........................ 190
7.9 Copper Precipitation from Chalcopyrite B Leachate .......................... 190
7.10 Copper Precipitation from a Copper-Gold Ore leachate .................... 191
7.11 Summary ............................................................................................. 192
Chapter 8 Conclusions ......................................................................................... 194
8.1 Retrospective and Discussions............................................................ 194
8.2 Enumerated Conclusions .................................................................... 195
8.2.1 Leaching of Copper Minerals .............................................................. 195
8.2.2 Mechanisms and Kinetics of Leaching Malachite, Chalcocite and

Chalcopyrite ........................................................................................ 196
8.2.3 Leaching of Copper- Gold Ores ........................................................... 197
8.2.4 Recovery of Metals from Leach Solutions .......................................... 198
8.3 Proposed Process Flowsheets for Different Copper or Copper and Gold
Ores ..................................................................................................... 199
8.3.1 Large Deposit of Low Grade Gold-Copper Ore ................................... 199
8.3.2 Lean Deposit of High Grade Copper Oxide Ore .................................. 201
8.3.3 Copper Sulfide Flotation Concentrate with Gold Mineralization ....... 202
8.4 Recommendations for Further Research............................................ 203
xiii
Bibliography 205
Appendices 239
Appendix A: XRD Patterns ....................................................................................... 239
Appendix B: Instrumental Detection Limits ............................................................ 241
Appendix C: Particle size Distribution ..................................................................... 242
Appendix D: XPS Spectra ......................................................................................... 243
Appendix E: Properties of Reagents ........................................................................ 244
Appendix F Examples of Metal leaching Calculations ............................................. 249
Appendix G SEM Images of Un-leached and Leached Mineral Specimens ............. 250
Appendix H Experimental Leaching Data ................................................................ 251
xiv
List of Figures
Figure 2.1 Mineralogical World distribution of porphyry copper deposits (Johnson et
al., 2015) .................................................................................................... 10
Figure 2.2 Alterations in a porphyry Cu-Au deposit model (Sillitoe, 1995). ................ 12
Figure 2.3 Potential-pH diagram of Cu-NH3-H2O system: 25 °C, Cu activity of 0.5 and
[NH3] of 7 kmol/L (Konishi, 2007) ............................................................. 30
Figure 2.4 Eh-pH diagram for Au- NH3-H2O system: 25 °C, 101.3 kPa, activity of ions 10-
4, [NH3] of 1.0 M (Meng & Han, 1996) ...................................................... 35
Figure 2.5 General structure of amino acid ................................................................. 38
Figure 2.6 Structure of glycine ..................................................................................... 38
Figure 2.7 Titration curve of a 0.1 M glycine solution with NaOH. Frames indicate pH
plateaus (Hegyi et al., 2013) ...................................................................... 41
Figure 2.8 Eh-pH diagram for copper-water-glycine system at a total dissolved copper
activity of 10-5 and total glycine activity of 10-2 at 25℃ and 1 atm (Aksu et
al., 2003). ................................................................................................... 43
Figure 2.9 Falling industrial copper ores head grade trends (Brook Hunt) ................. 47
Figure 2.10 Energy consumption in mineral processing (Stadler, 2015) ..................... 47
Figure 2.11 Total energy consumption as a function of head grade for various process
routes (Marsden, 2008) ............................................................................. 48
Figure 2.12 Dump leaching (Näveke, 1986) ................................................................. 49
Figure 2.13 Heap leaching (Biomine, 2014) ................................................................. 50
Figure 2.14 Vat leaching of copper at Mantos Blancos, Chile, 1995 (Source: INNOVAT
Limited)...................................................................................................... 51
Figure 3.1 Diagram of leaching kinetics apparatus setup ............................................ 58
Figure 3.2 Laboratory leaching apparatus setup ......................................................... 58
Figure 4.1 Effect of initial glycine concentration on the dissolution of copper from
azurite: pH 11, P100 75 µm and % solids 0.95 % w/v.................................. 73
xv
Figure 4.2 Effect of initial leach solution pH on copper dissolution from azurite: Gly:Cu
4:1, P100 75 µm and % solids 1.95 % w/v .................................................. 74
Figure 4.3 Correlation between the change in copper concentration and pH change
during leaching of azurite: Cu:Gly 1:4, P100 75 µm and % solids is 0.95 % w/v
................................................................................................................... 75
Figure 4.4 Effect of initial glycine concentration on the dissolution of copper from
malachite A: pH 11, P100 75 µm and % solids is 1.62 % w/v ...................... 76
Figure 4.5 Effect of initial solution pH on the dissolution of copper from malachite A:
Gly:Cu 4:1, P100 75 µm and % solids 0.96 % w/v ........................................ 77
Figure 4.6 Correlation between the change in copper concentration and pH change
during the leaching of malachite ............................................................... 78
Figure 4.7 Effect of initial glycine concentration on copper dissolution from cuprite
mineral specimen: pH 11, P100 75 µm and % solids 1.99 % w/v ................ 79
Figure 4.8 Effect of initial pH on copper dissolution from cuprite: Gly:Cu 4:1, P100 75 µm
and % solids 1.95 % w/v ............................................................................ 80
Figure 4.9 Correlation between copper concentration and leach solution pH during the
leaching of cuprite ..................................................................................... 80
Figure 4.10 Effect initial glycine concentration on chrysocolla leaching; pH 11, P100 75
µm and % solids is 1.62 % w/v................................................................... 82
Figure 4.11Effect of initial leach solution pH on chrysocolla leaching: Gly:Cu 4:1, P100 75
µm and % solids 1.62 % w/v ................................................................... 83
Figure 4.12 Correlation between [Cu] in solution and change in solution pH during
glycine leaching of chrysocolla .................................................................. 83
Figure 4.13 SEM photographs of unleached (a) and partially leached (b) chrysocolla 84
Figure 4.14 Effect of initial glycine concentration on metallic copper dissolution: pH 11,
0.5 % H2O2, P100 75 µm and % solids 0.40 % w/v........................................ 85
Figure 4.15 Effect of initial solution pH on metallic Cu dissolution; Gly:Cu 4:1, 0.5 %
H2O2, , P100 75 µm and % solids 0.40 % w/v ............................................... 86
Figure 4.16 Effect of peroxide on metallic Cu dissolution: Gly:Cu 4:1, pH 11, , P100 75 µm
and % solids 0.40 % w/v ............................................................................ 87
xvi
Figure 4.17 Effect of initial glycine concentration on the dissolution of chalcocite A: pH
11, 0.5 % H2O2, P100 75 µm and % solids 0.51 % w/v .................................. 89
Figure 4.18 Effect of initial solution pH on the dissolution of chalcocite A: Gly:Cu 4:1, 0
% H2O2, P100 75 µm and % solids 0.51 % w/v.............................................. 90
glycine leaching of chalcocite .................................................................... 90
Figure 4.20 Effect of peroxide on chalcocite A dissolution: Gly:Cu 4:1, pH 11, , P100 75
µm and % solids 0.51 % w/v ...................................................................... 91
Figure 4.21 Effect of additives on copper dissolution from chalcocite A: Gly:Cu 4:1, pH
11, 0 % H2O2, P100 75 µm and % solids 0.40 % w/v................................... 92
Figure 4.22 Effect of glycine concentration on copper dissolution from chalcopyrite A:

peroxide 0.5 %, pH 11, P100 75 µm and % solids 0.51 % w/v ..................... 94
Figure 4.23 Effect of initial peroxide concentration on chalcopyrite A leaching: Gly:Cu

4:1, pH 11, P100 75 µm and % solids 2.7 % w/v .......................................... 95
Figure 4.24 Effect of initial leach solution pH on chalcopyrite A leaching: Gly:Cu 4:1,
peroxide 0.5 %, P100 75 µm and % solids 0.27 % w/v ................................ 96
Figure 4.25 Change in solution pH during the leaching of chalcopyrite A: (a) different
glycine concentrations, (b) different initial solution pH............................ 96
glycine leaching of chalcopyrite A ............................................................. 97
Figure 4.27 Comparative degree of extraction of Cu and impurity elements in final

leach solutions of chalcopyrite A............................................................... 99
Figure 4.28 Comparative dissolution behaviour of copper minerals in the alkaline

glycine solutions: Cu:Gly 1:4, pH 11, room temperature. ....................... 100
Figure 5.1 Representation of concentrations of reactants and products for a particle of

unchanging size (Levenspiel, 1999). ........................................................ 104
Figure 5.2 UV-Vis spectrum of Cu (II) sulfate and Cu (I) chloride dissolution in alkaline
glycine at pH 11, Gly:Cu 3:1. .................................................................... 108
xvii
Figure 5.3 UV-Vis spectrum of Cu (II) sulfate (with alkaline glycine), azurite, chrysocolla,
cuprite, chalcopyrite, and chalcocite in aqueous alkaline glycine of pH
11 ............................................................................................................. 109
Figure 5.4 Correlation between Cu (II) concentration with UV-Vis and total copper by
AAS........................................................................................................... 110
Figure 5.5 The survey spectrum of un-leached and leached chalcocite samples...... 112
Figure 5.6 The high-resolution spectra for copper from un-leached and leached
chalcocite samples................................................................................... 112
Figure 5.7 SEM-EDS spectra for unleached and leached chalcocite .......................... 113
Figure 5.8 High-resolution spectra of oxygen from un-leached and glycine leached
chalcopyrite specimen............................................................................. 114
Figure 5.9 The high resolution spectra of un-leached and leached chalcopyrite
specimen ................................................................................................. 115
Figure 5.10 SEM-EDS spectra for un-leached and glycine leached chalcopyrite ....... 115
Figure 5.11 Effect of glycine concentration on copper dissolution from malachite B: 25

°C, +53-75 µm, 350 rpm and 0.36 %w/v solids........................................ 118
Figure 5.12 Effect of temperature on copper dissolution from malachite B: [Gly] 0.4 M,
+53-75 µm, 350 rpm, and 0.36 %w/v solids. ........................................... 119
Figure 5.13 Effect of stirring speed on copper dissolution from malachite B: [Gly] 0.4
M, 25 °C, +53-75µm and 0.36 %w/v solids. ............................................. 120
Figure 5.14 Effect of particle size on copper dissolution from malachite B: [Gly] 0.4 M,
25 °C, 350 rpm and 0.36 %w/v solids ...................................................... 121
Figure 5.15 Arrhenius plot for product layer diffusion controlled malachite
leaching ................................................................................................... 123
Figure 5.16 Effect of glycine concentration on chalcocite B leaching kinetics: 25°C, 400
rpm, DO 8 ppm, PS 38-53 µm, 0.25 %w/v solids. .................................... 125
Figure 5.17 Effect of stirring speed on chalcocite B leaching kinetics: 0.5 M Gly, 25°C,
DO 8 ppm, PS 38-53 µm, 0.25 %w/v solids. ............................................ 126
Figure 5.18 Effect of particle size on chalcocite B leaching kinetics: 0.5 M Gly, 25 °C,
400 rpm, DO 8 ppm, 0.25 %w/v solids. ................................................... 127
xviii
Figure 5.19 Effect of dissolved oxygen on chalcocite B leaching kinetics: 0.5 M Gly, 25
°C, 400 rpm, and +38-53 µm, 0.25 %w/v solids....................................... 128
Figure 5.20 Effect of temperature on the leaching kinetics of chalcocite B: 0.5 M Gly,
400 rpm, DO 8 ppm, 38-53 µm, 0.25 %w/v solids. .................................. 129
Figure 5.21 Arrhenius plot for product layer diffusion controlled chalcocite
leaching ................................................................................................... 132
Figure 5.22 Effect of glycine concentration on the leaching kinetics of chalcopyrite B:

pH 11.5, [O2] 15 ppm, PS 20-38 µm, 50 °C, SS 400 rpm, and 0.76 %w/v solids
................................................................................................................. 134
Figure 5.23 Effect of stirring speed on the leaching kinetics of chalcopyrite B: [Gly] 0.5
M, pH 11.5, [O2] 15 ppm, PS 20-38 µm, 50 °C and 0.76 %w/v solids ...... 135
Figure 5.24 Effect of particle size on the leaching kinetics of chalcopyrite B: [Gly] 0.5
M, 50 °C, pH 11.5, [O2] 15 ppm, SS 400 rpm, and 0.76 %w/v solids. ...... 136
Figure 5.25 Effect of dissolved oxygen on the leaching kinetics of chalcopyrite B: [Gly]
0.5 M, pH 11.5, 40 °C, PS 20-38 µm, SS 400 rpm, and 0.76 %w/v solids. 137
Figure 5.26 Effect of temperature on the leaching kinetics of 20-38 µm chalcopyrite B:

[Gly] 0.5 M, DO 15 ppm, pH 11.5, PS 20-38 µm, SS 400 rpm and 0.76 %w/v
solids ........................................................................................................ 138
Figure 5.27 Effect of temperature on the leaching kinetics of < 10 µm chalcopyrite B

size fraction: [Gly] 0.5 M, DO 10 ppm, pH 11.5, PS < 10µm, SS 500 rpm 139
Figure 5.28 Arrhenius plot for product layer diffusion controlled leaching of
chalcopyrite B .......................................................................................... 142
Figure 5.29 Arrhenius plot for product layer diffusion controlled leaching of <10 µm
chalcopyrite B fraction ............................................................................ 142
Figure 6.1 Effect of glycine concentration on Cu leaching from ore A: pH 11, 0 % H2O2,
P100 75 µm, 25°C, and 20 %w/v solids. .................................................... 147
Figure 6.2 Effect of glycine concentration on Au leaching from Cu-Au ore A: pH 11, 25
°C, 0 % H2O2, 168 h, P100 75 µm and 20 %w/v solids................................ 148
Figure 6.3 Effect of initial solution pH on Cu leaching from Cu-Au ore A: Gly:Cu 4:1, 0 %
H2O2, P100 75 µm and 20 %w/v solids. ..................................................... 149
xix
Figure 6.4 Effect of initial solution pH on Au leaching from Cu-Au ore A: Gly:Cu 4:1, 25
°C, ............................................................................................................ 149
Figure 6.5 Effect of peroxide on Cu leaching from Cu-Au ore A: Gly:Cu 4:1, pH 11, 25
°C, P100 75 µm and 20 %w/v solids. ........................................................ 150
Figure 6.6 Effect of peroxide on Au leaching from ore A: pH 11, Cu:Gly 1:4, P100 75 µm,
25 °C, 20 %w/v solids, 168 hours............................................................ 150
Figure 6.7 Effect of glycine on Cu leaching from Cu-Au ore B: pH 11.5, 25 °C, P100 75 µm
and 20 %w/v solids. ................................................................................. 152
Figure 6.8 Effect of glycine on Au leaching from Cu-Au ore B: pH 11.5, 25 °C, P100 75 µm
and 50 %w/v solids. ................................................................................. 153
Figure 6.9 Effect of initial pH on Cu leaching from Cu-Au ore C: [Gly] 0.5 M, 25 °C, P100
75 µm and 20 %w/v solids. ...................................................................... 153
Figure 6.10 Effect of initial pH on Au leaching from Cu-Au ore B: [Gly] 0.5 M, P100 75 µm
and 20 %w/v solids. ................................................................................. 154
Figure 6.11 Effect of temperature on Cu leaching from Cu-Au ore B: [Gly] 0.5 M, pH
11.5, O2 0.2 L/min, P100 75 µm and 20 %w/v solids. ................................ 155
Figure 6.12 Effect of temperature on Au leaching from Cu-Au ore B: [Gly] 0.5 M, pH
11.5, O2 0.2L/min, P100 75 µm and 20 %w/v solids. ................................. 155
Figure 6.13 Effect of oxygen on Cu leaching from Cu-Au ore B: [Gly] 0.5 M, pH 11.5, 60
°C, P100 75 µm and 20 %w/v solids........................................................... 156
Figure 6.14 Effect of oxygen on Au leaching from Cu-Au ore B: [Gly] 0.5 M, pH 11.5, 60
Figure 6.15 Effect of galvanic interactions on Cu leaching from Cu-Au ore B: [Gly] 0.5
M. pH 11.5, 60 °C, O2 0.05 L/min, P100 75 µm and 20 %w/v solids. ......... 158
Figure 6.16 Effect of galvanic interactions on Au leaching from Cu-Au ore B: [Gly] . 158
Figure 6.17 Effect of glycine on Cu leaching from Cu-Au ore C: pH 11.5, 25 °C, P100 75
µm and 50 %w/v solids............................................................................ 160
Figure 6.18 Effect of glycine concentration on Au leaching from Cu-Au ore C: pH 11.5,
25 °C, P100 75 µm and 50 %w/v solids...................................................... 160
xx
Figure 6.19 Effect of initial solution pH on Cu leaching from Cu-Au ore C: [Gly] 0.5 M,
Figure 6.20 Effect of initial solution pH on Au leaching from Cu-Au ore C: [Gly] 0.5 M,
Figure 6.21 Effect of temperature on Cu leaching from Cu-Au ore C: [Gly] 0.5 M, pH
Figure 6.22 Effect of temperature on Au leaching from Cu-Au ore C: [Gly] 0.5 M, pH
Figure 6.23 Effect of oxygen on Cu leaching from Cu-Au ore C: [Gly] 0.5 M. pH 11.5,60
Figure 6.24 Effect of oxygen on Au leaching from Cu-Au ore C: [Gly] 0.5 M. pH 11.5, 60
°C ............................................................................................................. 164
Figure 6.25 Effect of galvanic interactions on Cu leaching from Cu-Au ore B: [Gly] 0.5
M, pH 11.5, 60 °C, O2 0.05 L/min, P100 75 µm and 50 %w/v solids. ......... 165
Figure 6.26 Effect of galvanic interactions on Au leaching from Cu-Au C: [Gly] 0.5 M,
pH 11.5, 60 °C, O2 0.05 L/min, P100 75 µm and 50 %w/v solids. .............. 165
Figure 6.27 Column Cu leaching from Cu-Au ore C, pH 11, 25 °C, 33 L/m2/h............ 168
Figure 6.28 Column Cu leaching from Cu- Au ore D: pH 11, 25 °C, 135 L/m2/h ........ 169
Figure 7.1 The effect of extractant concentration on copper extraction: Gly:Cu 3:1 A:O
1:1, 20 °C, 10 minutes.............................................................................. 177
Figure 7.2 Extraction isotherm of copper with 5% Mextral 84H and 10% Mextral 54-
100. Conditions operating A:O 2:1, 20 °C, for 10 minutes. ..................... 178
Figure 7.3 Stripping isotherm of copper loaded organic. Conditions: 30 g/L Cu and 180
g/L H2SO4, A:O= 10:1, at 40°C ................................................................. 180
Figure 7.4 XRD pattern of precipitate produced from NaSH precipitation of copper
glycinate solution .................................................................................... 189
Figure 7.5 Particle size distribution of copper precipitate (CuS) from a copper glycinate
solution .................................................................................................... 190
xxi
Figure 8.1 Process flow diagram for glycine based leaching of a low Au-Cu ore in an
alkaline environment (copper is recovered by solvent extraction and
electrowinning while gold recovery is by carbon-in-column) ................. 201
Figure 8.2 Process flow diagram for glycine based leaching of a high grade lean copper
oxide deposit in an alkaline environment (copper is recovered by sulfide
precipitation) ........................................................................................... 202
Figure 8.3 A process flow diagram for the glycine based leaching of copper sulfide ore
and concentrates (with a gold content) in an alkaline environment (with
concentrate ultrafine grinding, copper recovery by SX-EW and gold
recovery by carbon-in-column included). ............................................... 203
xxii
List of Tables
Table 2.1 Principal alteration types with mineralogy, impact on a grind float circuit
modified from (Yildirim et al., 2014) ......................................................... 14
Table 2.2 Solubility of copper minerals in 0.099% NaCN solution (Hedley & Tabachnick,
1968).......................................................................................................... 17
Table 2.3 Technological solutions to nuisance copper in gold ore cyanidation .......... 20
Table 2.4 Common leaching agents and their applications ......................................... 22
Table 2.5 Outline for selecting appropriate lixiviants for gold (Gos & Rubo) .............. 23
Table 2.6 The acid consumption and estimated time to complete the dissolution of
major materials in 10 g/L sulfuric acid solutions (International Atomic
Energy Agency, 2001) ................................................................................. 27
Table 2.7 Copper glycine complexes and their stability constants (Aksu & Doyle,
2001).......................................................................................................... 44
Table 3.1 List of different copper minerals and gold-copper ores used in this study . 54
Table 3.2 List of different analytical grade reagents and gases used in this study...... 54
Table 3.3 Solid percentage used for the dissolution behaviour of copper mineral
specimens .................................................................................................. 56
Table 3.4 Leaching vessel, ore type, solution volume and ore mass for leaching Cu-Au
ores ............................................................................................................ 59
Table 3.5 Solution and aeration rates for leaching columns ....................................... 60
Table 3.6 Column leaching experimental setup .......................................................... 61
Table 3.7 Phase separation after solvent extraction ................................................... 63
Table 4.1 Mineralogical and chemical composition of azurite .................................... 72
Table 4.2 Mineralogy and chemical composition of Malachite A................................ 76
Table 4.3 Mineralogy and chemical composition of cuprite........................................ 79
Table 4.4 Mineralogical and chemical composition of chrysocolla specimen ............. 81
Table 4.5 Mineralogy and elemental composition of chalcocite A.............................. 88
Table 4.6 Mineralogical and elemental composition of chalcopyrite A ...................... 93
xxiii
Table 4.7 Concentration of copper and impurities in the final leach solutions and the
calculated degree of extraction from leaching copper oxides: Gly:Cu 4:1, pH
11, P100 75 µm ............................................................................................ 98
Table 5.1 Sulfur speciation for a copper sulfide (chalcopyrite) leached solution...... 110
Table 5.2 Binding energies of chalcocite and covellite from NIST database and from un-
leached and leached chalcocite............................................................... 112
Table 5.3 Elemental surface concentrations of un-leached and glycine leached

chalcopyrite sample calculated from their relative XPS survey spectra. 114
Table 5.4 Correlation coefficient values of shrinking core kinetic models for malachite
B ............................................................................................................... 122
Table 5.5 Data showing the rate-controlling model of malachite B at different

temperatures using the least square technique of constrained multi-linear
analysis .................................................................................................... 123
Table 5.6 Copper content in each particle size fraction of chalcocite B .................... 124
Table 5.7 Correlation coefficient values of shrinking core kinetic models for chalcocite
B ............................................................................................................... 130
Table 5.8 Rate-controlling model of chalcocite leaching determined for 0-6, 6-48 hours
and the overall leaching data at different temperatures using the least
square technique of constrained multi-linear analysis ........................... 131
Table 5.9 Mineralogical composition of chalcopyrite B............................................. 133
Table 5.10 Elemental composition of different size fractions of chalcopyrite B ....... 133
Table 5.11 Correlation coefficient values of shrinking core kinetic models for
chalcopyrite B .......................................................................................... 140
Table 5.12 Data showing rate-controlling model for 20-38 µm size fraction chalcopyrite
B at different temperatures using the least square technique of constrained
multi-linear analysis................................................................................. 141
Table 5.13 Data showing rate-controlling model for < 10 µm size fraction chalcopyrite
B at different temperatures using the least square technique of constrained
multi-linear analysis................................................................................. 141
Table 6.1 Mineralogy and elemental composition of Cu-Au ore A............................ 146
xxiv
Table 6.2 Mineralogical and elemental composition of Cu-Au ore B ........................ 151
Table 6.3 Mineralogical and Major Elemental composition of Cu-Au ore C.............. 159
Table 6.4 Particle size distribution for column leaching of Cu-Au ore C.................... 166
Table 6.5 Elemental composition of Cu-Au ore C used for heap simulation ............. 167
Table 6.6 Column Au leaching from Cu-Au ore C, pH 11, 25 °C, 33 L/m2/h ............... 168
Table 6.7 Mineralogy and elemental composition of Cu-Au ore D ........................... 169
Table 6.8 Column Au leaching from Cu-Au ore D: pH 11, 25 °C, 135 L/m2/h ............ 170
Table 7.1 Effect of pH on copper extraction. Experimental conditions: Gly:Cu 3:1, A:O
1:1, 20°C .................................................................................................. 175
Table 7.2 Effect of temperature on copper extraction. Gly:Cu 3:1, A:O 1:1, 20°C. ... 175
Table 7.3 Effect of mixing time on copper extraction. Gly:Cu 3:1, pH 11, A:O 1:1,
20°C. ........................................................................................................ 175
Table 7.4 Effect of glycine concentration on copper extraction: pH 11, A:O 1:1,
20°C ......................................................................................................... 176
Table 7.5 Stripping of copper loaded 5% Mextral 84H and 10% Mextral 54-100 with
various H2SO4 concentrations. Conditions: A:O ratio 1, 20°C................. 179
Table 7.6 Mineralogical and elemental composition of copper oxide (malachite)

specimen ................................................................................................. 181
Table 7.7 Percentage copper extractions from malachite by 10 % Mextral 54-100 and
Mextral 84H at different O:A ratios......................................................... 181
Table 7.8 Elemental analysis of malachite leachate and raffinate before and after
solvent extraction respectively with 10 % Mextral 54-100 and Mextral 84H
at an O:A ratio of 1:1 ............................................................................... 182
Table 7.9 Stripping of copper from loaded Mextral 54-100 and Mextral 84 H ( Cu loaded
from malachite leachate) using a proxy spent electrolyte solution (30 g/L
Cu, 180 g/L H2SO4) at various organic to aqueous ratios: 40 °C, 10
mins. ........................................................................................................ 182
Table 7.10 Mineralogical and elemental composition chalcopyrite B specimen ...... 183
Table 7.11 Percentage copper extractions from chalcopyrite B leachate by 10 %

Mextral 54-100 and Mextral 84H at different O/A ratios ....................... 183
xxv
Table 7.12 Elemental analysis of chalcopyrite B leachate and raffinate before and after
solvent extraction respectively with 10 % Mextral 54-100 and Mextral 84H
at an O:A ratio of 1:1 ............................................................................... 184
Table 7.13 Stripping of copper from loaded Mextral 54-100 and Mextral 84H ( Cu
loaded from chalcopyrite leachate) using a proxy spent electrolyte solution
(30g/L Cu, 180g/L H2SO4) at various organic to aqueous ratios: 40 ° C, 10
mins. ........................................................................................................ 184
Table 7.14 Copper extraction from Cu-Au ore C leachate using Mextral 54-100 and
Mextral 84H: A:O 2:1, pH 10.32, 25 °C .................................................... 186
Table 7.15 Effect of Cu:S ratio on copper precipitation from alkaline glycine
solution .................................................................................................... 188
Table 7.16 Effect of pH on copper precipitation from alkaline glycine solution: Cu:S 1:1.
................................................................................................................. 189
Table 7.17 Precipitation of copper and accompanying metals from a complex multi-
element chalcopyrite specimen .............................................................. 191
Table 7.18 Copper precipitation from a Cu-Au ore leachate using NaSH: 25 °C, 10 mins,
50 rpm. .................................................................................................... 191
xxvi
List of Abbreviations
XRD X-Ray Diffraction

XRF X-Ray Fluorescence
TIMA TESCAN Integrated Mineral Analyser
SEM Scanning Electron Microscopy
XPS X-Ray Photoelectron Spectroscopy
PLS Pregnant Leach Solution
UV-Vis Ultra Violet -Visible
AAS Atomic Absorption Spectrometry
ICP-OES Inductively Coupled Plasma- Optical Emission Spectroscopy
ICP-MS Inductively Coupled Plasma- Mass Spectroscopy
HPLC High Pressure Liquid Chromatography
Gly Glycine
PS Particle Size
SS Stirring Speed
DO Dissolved Oxygen
OD Outside Diameter
WAD Weak Acid Dissociable
EA Energy of Activation
xxvii
Chapter 1 Introduction
1.1 Background to this study
High grade reserves with readily recoverable gold deposits are gradually being depleted
(Zammit et al., 2012), leading to escalated interest in the mining and processing of low grade,
complex and refractory resources. Copper can often be a valuable by-product of these ores.
Cyanidation has been the most extensively applied method for the recovery of gold from ores
and concentrates for over a century. This is because cyanide forms very stable complexes
with gold and is relatively selective leading to high gold recoveries. In addition, the process
is robust and relatively low cost (Hilson & Monhemius, 2006b). Despite the popularity of the
cyanidation process, it has been recorded to be suboptimal in treating refractory and
polymetallic gold ores.
Refractory ores might have gold embedded in a mineral matrix or have components of the
ore that adsorb/precipitate the dissolved metal as preg-robbing materials or complex species
that consume the leaching agents (La Brooy et al., 1994). As a consequence of the continuous
depletion of non-refractory and high grade gold ores, there has been a significant focus on
processing complex low grade gold ores especially those containing easily soluble copper
minerals. Copper-containing gold ores are an important source of both copper and gold as
they are obtainable from many countries throughout the world including Australia, Chile,
Philippines, Saudi Arabia, Canada, Argentina, USA, Indonesia, Peru, Mexico, Indonesia and
China (Carlile & Mitchell, 1994; Green & Mueller, 1999; Sutulov, 1975; Wang et al., 2013). In
Australia, such deposits are found in Boddington-WA; Telfer-WA; Browns Creek, NSW;
Gabanintha-WA; and Red Dome-Qld, Olympic Dam-SA and Cadia Valley-NSW(Hsu et al.,
1997).
Cyanide is a “one way” reagent that shows poor ability to recovery and re-use; indicating that
it can be consumed in large amounts during the leaching of ores containing easily soluble
copper minerals. Cu-Au ores typically have high Cu:Au ratios of 500:1 to 5000:1 implying high
reagent use, particularly considering that CN:Cu ratios of greater than 4:1 are required to
provide free CN for Au dissolution and suppression of Cu co-adsorption onto activated
carbon. Due to the Weak Acid Dissociable (WAD) cyanide constraints on tailings, free and
WAD cyanide must be detoxified, destroyed at a significant expense (Dai et al., 2012).
1
In addition to the challenges of cyanidation to treat copper-gold ores, cyanide toxicity is a
health and environmental concern. The death of birds, animal and fish resulting from the use
of cyanide by gold mines has been extensively reported (Jeffrey et al., 2002; Korte &
Coulston, 1998). In the cyanide process, leachable copper has not only resulted in high
cyanide consumption causing low recoveries but also forms weak acid dissociable (WAD)
cyanide which is not easily amendable to natural degradation (Adams et al., 2008). Copper-
cyanide complexes from the Romanian tailings dam disaster were traced for some 2000 km
to the mouth of the Danube River(Korte et al., 2000). It is a result of these reported
environmental and health issues that, governments and non-governmental organisations
have encouraged the mining industry to develop alternatives to the cyanidation process. In
Australia, more stringent policies have been put in place to hinder the construction of cyanide
leaching plants (Jeffrey et al., 2002). The European Union has also adopted more stringent
directives on the use of cyanide while some states in the United States have imposed a
complete ban on cyanide usage in the mining industry. Both the technical difficulties of
cyanidation of copper-gold ores and the toxicity of cyanide continue to motivate research
into cyanide alternatives.
The development of an alternative process to cyanide leaching must therefore address both
the health and environmental issues associated with cyanide, and also the difficulties of
cyanidation to treat refractory and complex low grade copper-gold ores. Significant research
undertaken to develop plausible substitutes to cyanide have cited lixiviants such as thiourea,
halides, ammoniacal thiosulfate, nitriles, bisulfite, aqua-regia, and bacteria as potential
alternatives (Aylmore, 2005; Hilson & Monhemius, 2006b; Molleman & Dreisinger, 2002;
Senanayake, 2004; Sparrow & Woodcock, 1995; Syed, 2012). The applicability of most of the
alternatives has been limited due to gaps in knowledge, cost of reagents, toxicity and the
corrosive nature of some of the reagents.
The thiosulfate-copper-ammonia system, although considered a viable alternative

technology because of its lower toxicity and having gold leaching rate comparable to that of
cyanide, has been observed to have a very complex chemistry. Maintaining its stability under
variable pH/Eh conditions is a critical draw back to its extensive application in the gold
industry (Breuer & Jeffrey, 2000).
Less attention has been given to the use of organic acids as lixiviants in the mining industry
and, in particular, gold extraction (Hilson & Monhemius, 2006b). The role of organic acids on
the dissolution and transportation of gold in the soil, leading to the formation of gold
2
deposits has been reported by geochemists (Fetzer, 1934). Humic acid has been reported to
act as a solvent for copper and gold by forming complexes with the metals (Baker, 1973,
1978; Fetzer, 1946).
It has also been noted (Groudev et al., 1995) that, during the biological leaching of gold from
ores, the dissolution of gold occurred via gold-oxidising (peroxides) and gold complexing
(amino acids) agents secreted by the bacteria. Some of the identified micro-bacterial
synthesised amino acids are asparagine, glycine, aspartic, histamine, serine and phenylamine
and alanine (Korobushkina et al., 1974). A study of the dissolution mechanism of gold and
silver in glycine with peroxide as oxidising agent revealed that the reaction between glycine
and gold produces a complex anion and the bonding was postulated to be between the
carboxylic anions and the amino group nitrogen as a donor-acceptor (Mineev & Syrtlanova,
1984). It was established by Bogdanovskaya et al. (1986) that there is a chemical interaction
between a gold electrode and glycine through the adsorption of glycine on the gold electrode
in an alkaline environment. In the same way, amino acids have been reported to
electrochemically dissolve silver through the formation of a silver amino acid complex
(Safronov et al., 1983).
In the case of metallic copper, its interaction with amino acids (especially glycine) has been
extensively reported in the electronics industry and biological systems, but such interactions
are yet to be considered in the mining industry (where the copper is mineralised as oxides
and sulfides). The chemical-mechanical planarization of copper in the presence of glycine and
peroxide has drawn a lot of research in the production of copper interconnect
semiconductors for integrated circuit boards (Aksu & Doyle, 2001, 2002; Chen et al., 2013;
Seal et al., 2003; Zhang & Shankar, 2001). It has been shown that glycine acts as a chelating
agent; rapidly forming irreversible complexes with copper ions oxidised by the peroxide. In
a similar manner, the interaction between copper ions and proteins in biological systems has
been established to be through the formation of coordinate bonds between copper and the
functional groups on amino acids (Nunn et al., 1989; O'Brien & Nunn, 1982; Rubino & Franz,
2012; Thimann, 1932).
From the understanding that a prospective lixiviant for gold should be cheap or recyclable,
selective, non-toxic and compatible to downstream recovery processes (Avraamides, 1982),
glycine presents itself as a potential candidate to partially replace cyanide in the gold
industry. Glycine is the smallest amino acid with the formula NH2CH2COOH. It is an odourless,
sweet tasting crystalline solid with a solubility of 25g/100ml at 25℃. Toxicology information
3
on glycine via MSDS reports show that it is not toxic to humans or to the environment and
there are no special requirements for its transportation as is the case with cyanide. It is used
in food, pharmaceuticals and animal feed. Glycine can be synthesised industrially from
chloro-acetic acid and ammonia.
In an aqueous medium, glycine generally exists as a zwitterion (Tortonda et al., 1996) making
it stable in both acidic and basic environments. Feng and Van Deventer (2011) investigated
the effects of amino acids L-valine, glycine, DL-α- alanine, L-histidine on the stability of the
ammonical-thiosulfate system and observed that gold extraction from a pyrite concentrate
was (using thiosulfate as the lixiviant) improved in the presence of these amino acids as they
tend to form stronger complexes with copper than ammonia.
Scoping experiments done by Oraby and Eksteen (2013) to establish a frame work for glycine-
gold leaching showed that the glycine-peroxide system can effectively leach pure gold and
silver sheets. Observation, after 48 hours of gold leaching in solutions containing 0.5 M
glycine and 1 % peroxide at pH 11, showed a leaching rate of 0.322 µmol/m2.s. This rate is
comparable to the 0.22-0.25 µmol/m2.s gold leaching in thiosulfate-EDTA or thiosulfate-
oxalate systems after six days of leaching. It was also proven that activated carbon could be
used to recover gold and silver from the leach liquor. The gold–glycinate complex was found
to be effectively loaded on activated carbon up to 13.2 gAu/kgcarbon in 4 h (Oraby & Eksteen,
2015). The alkaline glycine system has been shown to selectively leach copper (ambient
temperature and pressure) from a copper-gold concentrate (Oraby & Eksteen, 2014).
Recently, it has been established that the alkaline glycine solutions can effectively leach
copper from its ores while rejecting impurities such as iron, calcium and magnesium which
can be detrimental to the leaching process (metal precipitation on heaps) and downstream
processes such as solvent extraction (Tanda et al., 2017).
Glycine, with all its advantages mentioned, firmly positions itself as a promising alternative
lixiviant for the economical processing of low grade copper-gold ores.
Although alkaline glycine solutions have been reported to leach copper from a float
concentrate, no studies have been done on the leaching behaviour of individual copper
minerals. The novel contribution of this research will be the studying and reporting of the
leaching behaviour of individual copper minerals in alkaline glycine solutions. The response
of gold-copper oxide and gold-copper sulfide ores towards varying process variables in the
alkaline glycine solution has not previously been investigated. Additionally, the thesis
4
investigated the recovery of copper from the leach liquor solutions and also determined the
deportment of glycine during metal recovery. This research project therefore endeavoured
to understand the effect of process conditions and variables on the leaching of copper and
gold from their resources using alkaline glycine solutions and also investigated possible
methods for recovering gold and copper from their pregnant leach solutions.
1.2 Objectives and significance of this study

The main aim of this research project is to achieve the following objectives:
• To investigate and establish the leaching behaviour of copper minerals in the alkaline
glycine solutions. The effects of process variables on the dissolution kinetics of
copper from its oxide and sulfide minerals will be studied;
• To study the effects of process variables, additives and impurities on the dissolution
of copper and gold from copper-gold ores;
• To evaluate different methods for metal, mainly copper recovery and the possibility
to recycle the barren solution;
• To propose a technically feasible high level flow sheet to treat Cu-Au ores using
glycine.
The attainment of the above objectives could have a meaningful influence in the copper and
gold industry. The main significant outcomes would be:
• To introduce an environmentally benign process for treating various types of copper

and gold ores;
• To enable the economic processing of gold ores having more than 0.5 % copper
oxides, or 1.0 % copper sulfides;
• To enable treatment of ores which fall below cut-off grades for conventional
processes;
• To provide a suitable reagent for the in-situ leaching of lean or placer gold deposits
which are difficult to access but also allow the lixiviant to be recycled and reused and
thereby significantly lowering costs.
5
1.3 Scope of this study
The scope of this research includes a range of topics related to the discipline of
hydrometallurgy. The mineralogical and elemental assessment of the variety of mineral
specimens and ores used was a critical aspect of the research.
As mentioned in Section 1.1, alkaline glycine solutions have been shown to selectively leach
copper from its different minerals from a copper-gold concentrate. It was thus paramount to
understand the leaching behaviour of different classes of copper minerals (oxides, secondary
and primary sulfides) in alkaline glycine solutions under various glycine concentrations and
solution pHs. Concomitantly, the metal dissolution-rates associated with leaching behaviour
of the various copper minerals is inextricably tied to this leaching behaviour. Therefore, part
of this study focuses on the leaching mechanisms and kinetics of a major copper oxide
(malachite) as well as secondary (chalcocite) and primary sulfide (chalcopyrite) minerals in
alkaline glycine solutions. The successful development and application of the glycine leaching
system will depend on a detailed knowledge of the leaching mechanism. Characterization of
the copper and sulfur species in solution and leach residues will provide the basis for
explaining the reaction steps that contribute to the observed leaching behaviour of the
copper minerals.
As the research topic indicates, glycine is being proposed as a lixiviant for copper-gold ores
as their traditional processing method (direct cyanidation or acid leaching followed by
cyanidation) poses economic and operability challenges. A portion of the research focuses
on the effect of process variables such as reagent concentration, solution pH, and
temperature on the dissolution of copper and/or gold from oxide and sulfide based copper-
gold ores. Literature (European Innovation Partnership on Raw Materials, 2014; Norgate &
Jahanshahi, 2010; VTT, 2016) has, however, indicated that, due to the continuous decline of
high grade ores deposits, low grade complex ores have drawn a lot of research interests. One
of the most economical method for processing such low grade ores is through heap leaching.
Therefore, heap leaching simulation through column leaching experiments was conducted to
deduce if the alkaline glycine solution could be used on heaps. The scope of the column
experiments was restricted to preliminary investigations and not extended to the optimum
conditions for dissolving copper and/or gold through heap leaching.
In order to consider the feasibility of alkaline glycine systems for leaching of copper and gold
from its resources, it is imperative to study both the leachability of copper from its ores and
6
the recovery of vital metals from the PLS. Solvent extraction and metal sulfide precipitation
were investigated as main methods for recovering copper from the pregnant leach solutions.
1.4 Thesis Overview

The thesis is divided into 8 chapters. An outline of the aspects covered by each chapter is
given below:
Chapter 2 is dedicated to a detailed review of literature on the major aspects of the thesis.
The importance of copper-gold ores and the influence of their mineralogy on
processing have been discussed. Challenges of traditional processing techniques
and limitations of current technologies to conquer these challenges will be
reviewed. Attributes of good lixiviants and the advantages presented by glycine
have also been presented. Lastly, leaching techniques applicable to low grade
copper-gold ores have also been appraised.
Chapter 3 introduces the materials and reagents used throughout the project. The Chapter
discusses experimental setup and methods to achieve the thesis objectives and
finally covers the analytical methods used to reach the required results.
Chapter 4 presents the leaching behaviour of major copper minerals in the alkaline glycine
solutions. The dissolution behaviour of impurity metals associated with the
copper minerals will also be studied and reported.
Chapter 5 investigates the mechanisms and kinetics of copper leaching in the glycine system.
It starts by giving a background on the importance of understanding the leaching
mechanisms and the rate controlling stages. The effect of process variables on the
leaching kinetics of malachite (oxides), chalcocite (secondary sulfide) and
chalcopyrite (primary sulfide) are also presented.
Chapter 6 involves the study of the effects of process variables on the leaching of copper and
gold from gold-copper oxide and gold-copper sulfide ores. Column leaching will
be carried out to simulate the heap leaching technique for the low grade ores.
Chapter 7 explores the possibility of recovering copper from the pregnant leach solutions.
The two techniques studied were solvent extraction and metal sulfide
7
precipitation. The fate of gold and other impurity elements concurrently leached
with copper was tracked and reported.
Chapter 8 summarizes the major results obtained during this study and also outlines
recommendations for further work.
8
Chapter 2 Review of Literature
2.1 Chapter Objective
This chapter reviews the available literature on the different aspects relating to the entire
project. As the project endeavours to propose and develop a new leach process by utilizing
a new lixiviant for low grade copper-gold ores, it is essential to first review the potential of
copper-gold ores as a major source of future copper, gold and other valuable metals. The
variation in copper-gold deposits and the influence of these variations on ore processing will
also be reviewed.
There has been an extensive research on the challenges facing the processing of copper-gold
ores and with numerous technological advances being proposed. Both the challenges and
the process developments will be critically appraised.
Selecting a lixiviant for leaching a particular ore entails the consideration of ore structure and
mineralogy, leaching techniques, the development of flowsheets, and environmental
management. The attributes of a good lixiviant and the aspects to be considered for selecting
a good leaching agent for a particular ore will be further elaborated in this chapter.
While proposing glycine as an alternative lixiviant for low grade copper-gold ores, it will be
vital to indicate the physical and chemical properties of glycine establishing it as a candidate
for the leaching of copper and gold from their ores.
Lastly, it is important to critically review the challenges of conventional leaching techniques

that are being employed for low grade copper-gold ores.
2.2 Copper-Gold Resources

In an examination of various primary gold deposits, by Schartz (1994) found that native gold
was intergrown with chalcopyrite in over 20% of the ores surveyed. Tetrahedrite, tennantite,
bornite as well as chalcocite were also found to have significant associations within certain
gold ores (Muir et al., 1989). Porphyry copper deposits are among the largest reservoirs of
gold in the upper crust and are important potential sources for gold (Kesler et al., 2002;
Sutulov, 1975) as they can contain up to 100t of gold (Kerrich et al., 2000). Sillitoe, (2010a)
reported that as of 2010, three quarters of the world’s Cu, one-fifth of Au and other valuable
9
metals come from porphyry copper systems. The close association of gold and copper is
believed to have occurred due to the introduction of the two metals together during the early
stages of alteration and mineralization. Secondary ion mass spectrometry (SIMS) was used
at the Advanced Mineral Technology Laboratory in London, Ontario to determine the gold
content of sulfide and oxide minerals in porphyry copper-gold deposits. The results indicated
that gold is found in porphyry copper deposits as solid solution in both Cu-Fe and Cu sulfides
and as small grains of native gold, commonly at bornite boundaries (Kesler et al., 2002).
Porphyry copper deposits are obtainable in many regions of the world as shown in Figure 2.1
Figure 2.1 Mineralogical World distribution of porphyry copper deposits (Johnson et al., 2015)
According to an assessment of copper resources, the United States Geological Survey (2014),
by 2100 million metric tons (Mt) of copper have been discovered with porphyry deposits
making up 60% of the identified resources. South America, South central Asia and Indochina,
and North America account for approximately 50 % the total global copper resources.
However, the world’s largest porphyry deposits are mined in South America. Other porphyry
deposits are found in Central America and the Caribbean, North-central Asia, Northeast Asia,
Eastern Europe, Southwestern Asia and Australia.
In Australia, such deposits are found in Boddington-WA; Telfer-WA; Browns Creek-NSW;

Gabanintha-WA; and Red Dome, Qld, Olympic Dam-SA, Northparkes-NSW, Cadia Valley-
NSW, Osborne-Qld, Ernest Henry-Qld, Ridgeway (Hsu et al., 1997; Geoscience Australia,
2007). Several large deposits containing significant resources of gold and copper
mineralization in Porphyry copper-gold, skarn, and high sulfidation enargite-gold deposits
10
have also been found in Indonesia, e.g., Grasberg-Ertsberg, Frieda River district, and Wafi-
Golpu (Carlile and Mitchell, 1994; Sillitoe, 2010b).
The quantity of undiscovered copper resources is postulated to be about twice the

discovered with the mean total of undiscovered resources for porphyry deposits being 3500
million tons (United States Geological Survey, 2014). With porphyry deposits accounting for
about 60% of the world’s copper, they become a valuable potential for copper-gold
extraction. Although porphyry deposits are generally large and contain millions of tonnes of
ore, metal grades vary considerably but often average less than 1% for Cu and less than 1 g/t
for Au.
2.2.1 Mineralogical variation in porphyry copper-

gold deposits
The determination of mineral processing methods and techniques depends most importantly
on the features and mineralogy of the ore. These characteristics result from a disparity in
metal grain size distribution, mineralogical mode of gold occurrence, host and gangue
mineral types, and mineral alterations (Marsden & House, 1992). In order to understand the
mineralogical variations in porphyry deposits, many researchers have tried to establish a
comprehensive definition for porphyry ores bodies that would incorporate geological,
economics and engineering views (Sutulov, 1975). The geological definition of porphyry
copper as being a disseminated copper mineralization in an acid igneous porphyric rock has
been refuted by many as being incomplete for not incorporating economical and engineering
aspects of the ore body. According to a number of publications(Bateman, 1952; Lowell, 1989;
Parson, 1957; Titley, 1982), porphyry copper deposits bear common features such as low
grade, large tonnage, disseminated replacements in porphyry, similar primary mineralogy,
supergene enrichment and overlaid by leached oxide cappings.
The formation of porphyry copper deposits has been attributed to hydrothermal systems
that developed in and around felsic intrusions and emplaced at relatively high levels in the
crust. As magma rises through the earth’s crust, it encounters pressure changes that cause
the magma to crystalize releasing mineral rich water which flows into surrounding rocks
through cracks and fractures leading to a vein-like mineralization (Briggs, 2014). Different
porphyry copper deposits vary in terms of morphology and architecture (irregular, oval,
cylindrical and inverted cup shapes), associated structures and mineralization styles (veins,
vein sets, stockworks, fractures, crackled zones and breccia pipes), mineralogy, and
11
alterations (Bateman, 1952; Sinclair, 2007). The mineralogy of porphyry deposits is highly
varied leading to the classing of deposits according to their principal component ores and
associated minerals. Different porphyry subtypes are: Cu, Cu-Mo, Cu-Mo-Au, Cu-Au, Au, Mo,
W-Mo, Sn, Sn-Ag, and Ag deposits. Alteration zones in many porphyry deposits are
composed of inner potassic zone, an outer zone of propylitic alteration, phyllic (sericitic) and
an argillic alteration zone (Sillitoe, 2000).
The alterations in a porphyry copper-gold deposit model are shown in Figure 2.2. Major zones
are accordingly described.
Figure 2.2 Alterations in a porphyry Cu-Au deposit model (Sillitoe, 1995).
• The argillic zone may have undergone weathering or leaching, supergene enrichment
depending on the depth and location of the water table. This zone is generally clay-rich
composing of quartz, illite, pyrite, kaolinite, smectite, montmorillite and calcite.
• Sericitic zone mostly composed of quartz, sericite and chlorite. Pyrite is associated with
the main orebody and the veins are filled with quartz and other silicates.
• Potassic zone, characteriszed by K-feldspar, is composed of secondary biotite-muscovite-
sericite-orthoclase feldspar-magnetite, associated with most of the ore in the stockwork
as well as along veins and fractures.
• Propylitic zone contains a bigger range of alteration minerals as a result of its typical
shallow depth and resultant higher degree of weathering. It is commonly composed of
12
quartz, sericite, pyrite, epidote-calcite and other clays (Holliday & Cooke, 2007).
These variations in the ore bodies significantly influence the applied mining and metal
extraction processes (Sutulov, 1975). The four major zones obtained in porphyry copper
deposits portray different mineralogy and textures and therefore require different
processing approaches. Deciding on whether to mine a particular ore body by open-pit or
underground mining technique depends on the nature and location of the deposit, the size,
depth and grade of the deposit (Norgate & Haque, 2010). The influence of textual variation
and gangue mineralogy of a porphyry ore on the recovery of copper was reviewed by Cropp
et al. (2013). They stated that seven key mineralogical factors:
• The fine-grained copper minerals;

• Locked minerals in composite particles;
• Surface coatings on valuable minerals;
• Gangue composites;
• Entrained gangue;
• Activated gangue, and
• Deleterious element distribution control the flotation recovery of copper from porphyry
ores.
Table 2.1, modified from Yildirim et al. (2014), shows the principal alteration and
mineralization in a typical porphyry copper deposit and some of their influences on grind and
float processes.
13
Table 2.1 Principal alteration types with mineralogy, impact on a grind float circuit modified from
(Yildirim et al., 2014)
Alteration type Position in Key minerals Principal Expected Expected

system sulfide effect on effect on
(abundance) assemblages mill flotation
(minor) throughput
Potassic Copper zones Biotite, K- Pyrite, High Low
of porphyry feldspar chalcopyrite,
(K-silicate)
copper deposits bornite,
digenite and
chalcocite
Chlorite- Upper parts of Chlorite, Pyrite, Moderate Moderate
sericite(sericite- porphyry Cu sericite/illite, chalcopyrite
clay-chlorite) core zone hematite
Sericite (phyllic) Upper parts of Quartz, Pyrite, Moderate Moderate
porphyry Cu sericite chalcopyrite,
core zone enargite,
tennantite,
bornite,
sphalerite
Advanced Above Quartz, Pyrite, Low High
argillic porphyry Cu alunite, enargite,
deposits, pyrophyllite, chalcocite,
constitutes dickite, covellite
lithocaps kaolinite
Propylitic Marginal parts Chlorite, Pyrite, N/A N/A
of systems epidote, albite, sphalerite,
below lithocaps carbonate galena
Sodic-calcic Deep, including Albite/ Typically N/A N/A
below porphyry absent
oligioclase,
Cu deposits
actinolite,
(un-common)
magnetite
The geological and mineralogical variation of an ore body at different horizons as noted with
porphyry copper deposits can radically influence leaching characteristics (Iasillo et al., 2013).
The supergene zone at the top of most porphyry deposits consist of an upper oxidized layer
referred to as the cap and an underlying sheet-like zone called the blanket zone. The cap is
composed of Cu oxides, Cu carbonates, Cu sulfates, Cu chlorides, Cu silicates and native Cu
while the blanket are mostly secondary copper and iron sulfides such as chalcocite, covellite,
bornite, and remnants of chalcopyrite (Petruk, 2000). The difference in alterations is
significant enough to warrant separate flowsheets for each ore type. The type of leaching
agent and method depend on the type of ore. Copper oxide ores are easily leachable by
sulfuric acid but when they contain huge amounts of carbonates, sulfuric acid leaching
becomes uneconomical due its high reagent demand (Habashi, 1970). Such ores can be
14
processed by leaching with alkaline lixiviants such as ammonia and its derivatives or generally
not exploited at all. Copper sulfide minerals are rather more difficult to leach requiring more
aggressive conditions such as strong oxidizing agents and high temperatures. It is well known
that chalcopyrite, although being the most abundant copper mineral, is also the most difficult
to leach thereby attracting a high volume of research,(Nazari et al., 2011; Turkmen & Kaya,
2009).
2.3 Processing of Copper-Gold Ores

Copper-gold association in ore bodies can either be one that contains predominantly copper
minerals with significant levels of gold mineralization or where the presence of copper is at
nuisance levels to the gold deposit. Where the copper level dominates and copper can be
recovered for its economic value (through grinding, flotation and smelting), gold is generally
recovered as a by-product (slime) from the copper smelting and refining process. Gold can
also be recovered from the flotation tailings by hydrometallurgical routes. The most
economical approach for sulfide ores has been to produce a gold-copper flotation
concentrate for metal recovery by smelting (Dunne, 1991).
On the other hand, where copper has no economic value, it poses serious problems to the
conventional cyanide leaching of gold by consuming reagents and adversely affecting the
downstream processes (Sceresini, 2005). It has been extensively researched and published
by many researchers (Abbruzzese et al., 1995; Adams et al., 2008; Bas et al., 2012; Dai et al.,
2012; Deschênes & Prud'homme, 1997; Jiang et al., 2013; La Brooy et al., 1991a; Muir, 2011;
Muir et al., 1989; Sparrow & Woodcock, 1995) that the presence of copper minerals in gold
ores poses significant problems during cyanidation of gold. These problems arise during
leaching, recovery and purification stages. Typically, ores containing 0.3%-0.5% Cu in the
form of oxide or >1 % Cu in the form of sulfide are not amenable to conventional cyanidation
(Deng, 1995).
2.3.1 Copper-Gold Cyanidation Challenges
2.3.1.1 Leaching
During leaching, the presence of cyanide soluble copper can result in high cyanide
consumption as well as low dissolution of gold. Most copper minerals are soluble in cyanide
(Shantz & Reich, 1978) to various degrees. They form a series of complexes: CuCN, [Cu(CN)2]-
15
, [Cu(CN)3]2-, [Cu(CN)4]3- whose equilibria in free cyanide and un-dissociated hydrocyanic acid
is described by Equations 2.1 to 2.5.
Cu+ + CN− = CuCN(s) logK= -20 (2.1)
CuCN + CN− = [Cu(CN)2]− logK= +24 (2.2)
[Cu(CN)2]− + CN− = [Cu(CN)3]2− logK= +5.3 (2.3)
[Cu(CN)3]2− + CN− = [Cu(CN)4]3− logK= +1.5 (2.4)
H+ + CN− = HCN(aq) logK= -9.21 (2.5)
Lu et al. (2002) reviewed the aqueous chemistry of copper cyanide and reported that
according to published data, the dissociation constants of the various complexes at 25 ° C,
as shown in their respective equilibrium equations (2.1 to 2.5), are the most agreeable.
The predominant Cu-CN species in solution depend on the cyanide-copper ratio,

temperature and pH. The Eh-pH diagram for Cu-CN-H2O indicates that, under normal
leaching conditions, [Cu(CN)3]2- is the most common species in solution. As Cu (I) forms a very
strong cyanide complex, it is generally recognized that CN:Cu molar ratio must be higher than
3:1 for gold leaching to start. Natural cyanide degradation at the tailing dam depletes free
and weakly bound cyanide so that [Cu(CN)2]- in recycle water will react with more free
cyanide in leach liquor to form [Cu(CN)3]2- and [Cu(CN)4]3- (Sceresini, 2005). Thus, copper has
to be removed from the leach circuit to maintain high amounts of free cyanide in solution.
When the copper concentration in the recycling solution is high, the solution is considered
to be fouled and its leaching efficiency decreases. This is particularly a problem when the
minerals being processed have readily-soluble copper minerals such as azurite, malachite,
cuprite, chalcocite and bornite (Alonso-González et al., 2009). It has been statistically shown
by Jiang et al. (2001) that gold recovery and cyanide consumption are both linearly related
to the soluble copper content (metallic copper, copper oxides and secondary copper
sulfides). The solubility of different copper minerals in 0.099% NaCN at 23 and 45 °C is given
in Table 2.2 (Hedley & Tabachnick, 1968).
16
Table 2.2 Solubility of copper minerals in 0.099 % NaCN solution (Hedley & Tabachnick, 1968)
Mineral Formula % Cu leached

At 23 °C At 45 °C
Azurite 2Cu(CO)3.Cu(OH)2 94.5 100
Malachite 2CuCO3(OH)2 90.2 100
Chalcocite Cu2S 90.2 100
Metallic copper Cu 90 100
Cuprite Cu2O 85.5 100
Bornite FeS.2Cu2S.CuS 70 100
Enargite Cu3AsS4 65.8 75.1
Tetrahedrite (Cu, Fe,Ag,Zn)12Sb4S13 21.9 43.7
Chrysocolla CuSiO3.nH2O 11.8 15.7
Chalcopyrite CuFeS2 5.6 8.2
Muir (2011) stated that copper bearing ores can consume up to 30 kg/ton NaCN for every 1%
of reactive copper present. When copper sulfides such as covellite are present, cyanide
consumption can reach 51 kg/ton due to the formation of thiocyanate and cyanate (Lower &
Booth, 1965).
2.3.1.2 Recovery
Copper is precipitated along with gold and silver in the Merrill-Crowe process and
consequently resulting in higher consumption of zinc dust (Parga et al., 2015). The removal
of copper from the precipitate by digesting with sulfuric acid prior smelting is costly, time
consuming and produces copper in an acidic medium which must be neutralized before
disposal.
During the recovery of gold by CIL or CIP, copper competes with gold to adsorb on carbon
and, under certain conditions, copper readily adsorbs onto activated carbon and displaces
gold. At low pH values and low free cyanide concentrations, with Cu (CN) 2- predominant in
solution, the kinetics of copper loading on activated carbon is enhanced.
In operations where water is hypersaline, it is impracticable to obtain pH values above 10

due to the magnesium precipitation which starts at pH 9.3 resulting in high alkali
consumption to maintain high pH. Copper contamination in such situations presents serious
problems due to the evident low pH that would favour copper adsorption (Sceresini, 2005).
17
Recovery of gold from copper–gold cyanide liquors by electrolysis is problematic due to the
contamination of the final gold product by copper impurities.
In gold electrowinning, gold can be selectively electrowon over copper provided the molar
ration of CN: Cu exceeds 3:1 (Muir et al., 1989). But if the activated carbon recovered from
leach circuits has very high copper/gold ratio resulting from high concentrations of copper
cyanide liquors, the clarified carbon eluates will also be rich in copper. The high concentration
of copper-cyanide in the electrowinning cell results in the co-deposition of gold and copper
which decreases the capacity of the electrowinning cell to plate gold and also affects
adherence of deposited metal and flow of electrolyte through the cell by overloading the
cathodes (Avraamides et al., 1992).
2.3.1.3 Effluent Treatment

Another problem that arises from the cyanidation of copper bearing gold ores is the level of
tailings management. The biggest concern when processing copper containing ores is the
discharge of copper cyanide complexes to the tailings dam because most metal complexes,
including those of copper, are highly toxic to most forms of life. Copper cyanide complexes
are significantly problematic as they are more stable than free cyanide ions (Strizhko et al.,
2013) and thus not easily degradable by nature. The death of birds, animal and fish resulting
from the use of cyanide by gold mines has been extensively reported (Jeffrey et al., 2002;
Korte & Coulston, 1998). A good example of such a report is the collapse of the tailings dams
at Omai in Guayana and Baia Mare in Romania leading to a cyanide spill. Copper-cyanide
complexes from the Romanian disaster were traced for some 2000 km to the mouth of the
Danube River (Korte et al., 2000). Although technological approaches are currently being
used in the mineral processing industry for the detoxification of cyanide tailings (Dai et al.,
2012), these elevate the overall processing cost and decrease profit margins.
2.3.1.4 Socio Economic – Adherence to the “Cyanide

Code”
Apart from the challenges encountered during the cyanidation process, the use of cyanide
also poses socio-economic challenges. The international cyanide management code for the
gold industry (International Cyanide Management Institue, 2009) has outlined guidelines that
must be adhered to during production, transportation, handling, operations,
decommissioning, worker safety, emergency, training and dialogue.
18
Although a mining company may not be directly involved in the production, distribution and
transportation of cyanide, it is the operator’s responsibility to ensure that its contractors
follow the cyanide code. Interruptions on operator’s primary purchasing arrangements for
cyanide can occur as a result of production or transportation problems beyond its control. It
might then be necessary to purchase cyanide from alternate sources for a limited time to
ensure continued gold production.
The cyanide code also requires operators to routinely initiate dialogue with stakeholders to
discuss their cyanide management procedures and also provide an opportunity for the
stakeholders to communicate issues of concern in direct and responsive manner (Logsdon et
al., 1999). Mining companies involved in the use of cyanide are required to implement the
cyanide code to maintain their licenses. Implementation of the code continues to add to the
operational costs of companies.
2.3.2 Coping with Copper-Gold Cyanidation

Challenges
Several approaches have been proposed to cope with the noted challenges occurring during
the cyanidation of copper-gold ores. These approaches could be classified as those that seek
to improve the cyanidation process and those that employ non cyanide based lixiviants to
efficiently process copper in the copper-gold ores.
Table 2.3 presents technological solutions to cope with the presence of nuisance copper in
copper-gold materials.
19
Table 2.3 Technological solutions to nuisance copper in gold ore cyanidation
Approach Technology Drawback References

Cyanide Pre- Roasting Added cost Xu et al., 2014
based treatment
Oxidation Added cost 1 Dalton et al., 1991
approach
(1chemical, 2bio-
2 Chiacchiarini et al.,
oxidation)
2003
Selective leaching Muir, 2011

of Cu
Selective Ammoniacal- Lower recoveries as Hayes & Corrans, 1992;
gold cyanide leaching compared to cyanide only Vukcevic, 1997; Hunt,
leaching 1901
Selective Ion flotation of Au Galvin et al., 1992;
recovery Malcolm et al., 1991
Solvent extraction Xie & Dreisinger, 2009
of Cu
Zinc cementation Tran & Hsu, 1996
of (Cu)
Acid precipitation Sorensen, 1988a, 1988b
(Au)
Tailings AVR Added costs Sceresini, 2005
treatment
SART Ford et al., 2008
Cutech Fleming, 2005
Inco Scott, 1981
Augment Xie et al., 2013
Hannah SGS Minerals Services,
2013
Vitrokele Tran et al., 2000
Membrane Lombardi, 2008
filtration
electrowinning Dai et al., 2012
(Cu)
Non- Thiosulfate leaching Complex chemistry and Breuer & Jeffrey, 2000;
Cyanide reagent degradation, Jiang et al., 2013;
based problematic gold Langhans Jr et al., 1992
recovery, high reagent
consumption
Thiourea leaching High reagent use and cost Hilson & Monhemius,
2006a; Lacoste-Bouchet
et al., 1998
Halides Bromine-bromide Un-economical as Muir et al., 1989
reagents are expensive.
Chlorine-chloride Sparrow & Woodcock,
May be considered for
concentrates 1995
Iodine-iodide Davis et al., 1993
20
2.4 Attributes of Good Lixiviants
Leaching is one of the most important unit operations in hydrometallurgical processing of
minerals as its efficiency significantly influences the technical and economic success of a
business (Crundwell, 2013). The leaching process involves the dissolution of minerals or
metals in an aqueous solution. Generally, metals bound in minerals are transformed into
metal ions that are released into an aqueous solution, i.e. immobilized metals become
mobilized. The major objective of leaching is to maximize the valuable metal distribution to
either the leach solution or the residue (solid phase) with desired characteristics (Gupta &
Mukherjee, 1990). The choice of lixivant depends first and most importantly on the
mineralogical composition of the ore material to be leached. According to Olubambi et al.
(2006), the selection of optimum technical and economic routes for minerals requires a
complete knowledge of the ore, especially its chemical and mineralogical compositions,
relative amounts of minerals, and particle size distribution.
Water alone can solubilize many sulfates, chlorides and nitrates. Acids, however, are the
most common leaching agents for oxides and sulfates. Sulfuric acid is the most commonly
used acid because of its low cost, availability and low volatility as well as high chemical
stability in aqueous solutions. The use of other acids, such as nitric and hydrochloric acids, is
limited to specific systems owing to undesirable properties such as high costs, volatility,
corrosiveness and indiscriminate gangue dissolution (Burkin, 2001). Alkaline lixivants are also
used for leaching and the most common alkaline lixiviant is sodium hydroxide (used in the
Bayer process). Alkaline ammonia and its derivatives are used on the basis of their target
minerals selective dissolution. Certain salts such as sodium cyanide have been used for more
than a century for the leaching of gold and silver (Burkin, 2001). Table 2.4 shows the
commonly used leaching agents and their applications.
21
Table 2.4 Common leaching agents and their applications
Leaching agent Leaching agent Application

type
Acids diluted H2SO4 Copper oxides, zinc oxides
diluted H2SO4 + Copper sulfides, zinc and nickel sulfides, uranium
oxidant oxide
concentrated H2SO4 Sulfidic copper concentrates, nickel laterites
HNO3 Copper sulfides, nickel and molybdenum sulfides,
Mo strap, uranium concentrates, zirconium oxides
HCl ilmenite, nickel matte, cassiterite
Bases NaOH Bauxite
Na2CO3 Uranium oxides, scheelite
NH4OH + ammonia Copper sulfides, nickel sulfides, reduced laterites
salts + oxygen (Ni)
Salts Fe2(SO4)3 , FeCl3 Sulfidic concentrates of base metals
CuCl2 Sulfidic concentrates of base metals
KCN (NaCN) + oxygen Au and Ag, Cu effluents
FeSO4 + oxygen effluents FeSO4 + oxygen nickel sulfide
Chlorine (in water Aqueous chlorine, Sulfidic concentrates of Ni, Cu, Zn, Pb, Hg, Mo,
solution) Chlorates(I) reduced laterites (Ni)
Water water Water soluble sulfates, chlorides, molybdates,
vanadates, tungstates, perrhenates.
The selection of a suitable leaching reagent should consider the following factors
(Avraamides, 1982):
• It should be selective and have high activity to dissolve components of interest rapidly
enough to make commercial extractions possible;
• It should be inexpensive with the possibility to be produced in bulk industrial quantities;
• Compatible with downstream recovery process and also recyclable; and
• Environmentally friendly.
Gos and Rubo, (2001) outlined basic criteria which should be considered for selecting
appropriate lixiviants for gold based on technical aspects, toxicity and economics. This is
outlined in Table 2.5.
22
Table 2.5 Outline for selecting appropriate lixiviants for gold (Gos & Rubo)
Economics Toxicity Process Applicability

• Capital investment • Emissions • Limitations (e.g. ore type,
• Extraction economics • Handling selectivity, control,
• Availability • Environmental separation, etc.)
• Costs considering toxicity • Recyclability
detox/recycling • Detoxifiability
• Large scale application
(proven technology)
As presented in Table 2.5, a perfect lixiviant should therefore be economical, be applicable

to most ore types, can be safely transported, handled and easy to detoxify or recycle.
According to most researchers, of all the alternative lixiviants that have been proposed for
leaching gold for example, there is none that fulfils all the criteria of an ideal lixiviant (Barbetti
& Avraamides, 2003; DeVries & Hiskey, 1992; Gos & Rubo, 2001; Hilson & Monhemius,
2006b; Senanayake, 2004; Sparrow & Woodcock, 1995).
2.4.1 Attributes of Copper and/or Gold Ore

Lixiviants
2.4.1.1 Acids
Sulfuric acid is the most widely used leaching agent for copper ores due to its affordability,
its fast attack on oxidized ores, and the fact that it might be regenerated during the leaching
of sulfate and sulfide minerals (Biswas & Davenport, 1976). Acids have rather been observed
to be deficient in the leaching of ores containing calcium-magnesium carbonate as gangue
material since these carbonates are very soluble in acids. The high dissolution of carbonates
leads to the consumption of huge amounts of acid during the leaching of such ores; making
the process uneconomical (Habashi, 1970, 1980; You-Cai et al., 2013). For acid leaching of
carbonates (dolomite, calcite, ankerite), 1 ton of ore requires about 1 ton of H2SO4
(International Atomic Energy Agency, 2001). This makes the use of sulfuric for such ores
uneconomical.
2.4.1.2 Ammonia
Ammonia and its derivatives, such as ammonium hydroxide, form stable complexes with
some metal cations (cobalt, nickel and copper) through the nitrogen group and this has been
observed to significantly enhance both the solubility and stability of the metals in solution
23
(Greenberg, 1951). It has also been reported that ammoniacal leaching selectively leaches
metals of interest over gangue metals. Despite ammoniacal leaching having the advantage
of selectivity leaching of target metals over impurities or gold, its use presents technical and
environmental challenges which include its unpleasant odour detected even at low
concentrations, its toxicity to aquatic organisms, and its adverse health effects such as
corrosiveness to the respiratory track, and burning of the skin. According to the National
Institute for Occupational Safety and Health (NIOSH), the threshold limit value for ammonia
is 25 ppm for a normal 8-hour shift. Additionally, the volatility of ammonia leads to reagent
loss. Ammonia can also be oxidised. These challenges have limited the application of the
ammoniacal systems to enclosed agitated tank processes and precludes low grade leach
options such as in-situ leaching or heap leaching.
2.4.1.3 Cyanide
Cyanidation has been the most extensively applied method for the recovery of gold from ores
and concentrates for over a century. This is because cyanide forms very stable complexes
with gold. Unlike WAD cyanide, the gold-cyanide complex is a strong acid dissociable (SAD)
that requires strong acidic conditions (pH<2) to dissociate and release HCN(g). Also, gold
cyanidation is relatively selective and this leads to high gold recoveries. The process is robust
and relatively low cost (Hilson & Monhemius, 2006b). Despite the popularity of the
cyanidation process, cyanide is a toxic reagent. If cyanide is not properly handled, i.e.,
solution pH not maintained above 9, HCN gas is produced which can result in human fatality
if exposed. The death of birds, animals and fish in surrounding ecosystems to gold mine sites
extensively reported (Jeffrey et al., 2002; Korte & Coulston, 1998). Also, the cyanidation
process becomes uneconomical for many polymetallic ores.
Technically, the cyanidation process is ineffective in treating refractory and complex gold
ores due to preg-robbing and high content of cyanide consuming minerals such as copper
oxides (La Brooy et al., 1991b; La Brooy et al., 1994), unless preceeded with some form of
ore or concentrate pretreatment.
2.4.1.4 Thiosulfate
The thiosulfate system has been considered the most viable alternative technology to
cyanidation because of its low toxicity and also for having comparable gold leaching rate to
that of cyanide, but has been noted to have a very complex chemistry. Maintaining its
24
stability under variable pH/Eh conditions is a critical drawback to its extensive application in
the gold industry (Breuer & Jeffrey, 2000). Although thiosulfate is relatively available at
reasonable price, the reported high reagent consumption of up 48.6 kg/t indicate that the
extraction cost could be significantly higher than that of cyanidation. Also, high oxygen
demand of four moles to a mole of thiosulfate increase the operating cost (Gos & Rubo,
2001). However, thiosulfate has its first commercial application at Barrick’s Goldstrike
operation in Nevada, USA for the processing of preg robbing gold ore (Vaikuntam et al.,
2016).
2.4.1.5 Halides
The potential of chlorides, bromides and iodides to leach gold has been well established and
pre-dates cyanidation (La Brooy et al., 1994). Gold extraction by halides is generally faster
than in cyanide but extraction with halide-based systems comes at a higher cost (Free,
2013). Chloride and bromide systems need special construction equipment for their
operation (Hilson & Monhemius, 2006b). The oxidants used in these halide systems are,
however, the halogens of the halides themselves that all have lethal and occupational health
standards higher than that of hydrogen cyanide. This high toxicity and consumption levels
have hindered a significant consideration of halides as favourable alternatives to cyanide
(Gos & Rubo, 2001).
2.5 Alkaline Ammoniacal Hydrometallurgy of

Copper and Gold
It is well known that large, high grade ores which are normally processed by conventional
pyrometallurgical processes are in continuous decline (Ata et al., 2001). Most research in
hydrometallurgy is being tilted towards the processing of low-grade polymetallic ores which
are normally not exploited due to the non-availability of cost effective technologies. The
development of leaching-solvent extraction-electrowinning (L-SX-EW) processing route in
the 1970’s led to the commercial exploitation of such low grade ores (Prasad & Pandey,
1998). Currently, about 22 % of the world’s copper is obtained via the L-SX-EW route
(International Copper Study Group, 2013). In hydrometallurgy, acids especially sulfuric acid
has been widely accepted as the most effective lixiviant for the extraction of base metals
from their ores. However, acid interacts with various altered and layered silicates to solubilise
a range of metallic cations (K+, Na+, Mg2+, Al3+, Ca2+, Fe3+, Mn2+) as well as anions such as
25
sulfates (SO42-) and halides (Cl-, F-) which are corrosive, and may leave behind silica gels. These
silica gels, together with the accumulation of ions due to often prevalent water balance
constraints, can cause severe operating challenges in solvent extraction circuits due to crud
formation, necessitating expensive crud removal and purification systems. The high ion
loading may also lead to significant water treatment and neutralisation costs. Many copper
minerals are inherently alkaline (oxides, carbonates, hydroxyl-halides and basic sulfates), due
to the surrounding host rock of gangue minerals.
Sulfuric acid, which is widely employed as the main lixiviant for leaching copper oxide
minerals, has been observed to be infeasible for the leaching of ores containing high calcium-
magnesium carbonate as gangue materials since these carbonates are very soluble in acids
(Habashi, 1970; Pokrovsky et al., 2005; Vignes, 2013). Table 2.6 shows the acid consumption
and estimated time to complete the dissolution of major carbonaceous materials in 10 g/L
sulfuric acid solutions. It can be seen that for acid leaching, each 1 ton of carbonate minerals
(dolomite, calcite, ankerite) requires about 1 ton of sulfuric acid.
26
Table 2.6 The acid consumption and estimated time to complete the dissolution of major materials
in 10 g/L sulfuric acid solutions (International Atomic Energy Agency, 2001)
Minerals Formula Specific acid Time for

consumption, kg/t complete
dissolution
1 day 250 days
Albite 𝑁𝑁𝑁𝑁[𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴3 𝑂𝑂8 ] 0.3 1.6 100-150 years
Microcline 𝐾𝐾[𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴3 𝑂𝑂8 ] 0.6 0.2 100-150 years
Muscovite 𝐾𝐾𝐾𝐾𝐾𝐾2 (𝑂𝑂𝑂𝑂)2 · [𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴3 𝑂𝑂10 ] 1.6 7.0 ~ 100 years
Biotite 𝐾𝐾(𝑀𝑀𝑀𝑀, 𝐹𝐹𝐹𝐹)2 · [𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴3 𝑂𝑂10 ] · (𝑂𝑂𝑂𝑂, 𝐹𝐹)2 20.1 140.2 2-8 years
Vermiculite (𝑀𝑀𝑀𝑀, 𝐴𝐴𝐴𝐴, 𝐹𝐹𝐹𝐹)3 · (𝑂𝑂𝑂𝑂)2

39.3 247.2 2-8 years
(hydromica) [(𝑆𝑆𝑆𝑆, 𝐴𝐴𝐴𝐴)4 𝑂𝑂10 ] · 4𝐻𝐻2 𝑂𝑂
Kaolinite 𝐴𝐴𝐴𝐴,4 (𝑂𝑂𝑂𝑂)8 [𝑆𝑆𝑆𝑆4 𝑂𝑂10 ] 2.6 23.7 30-50 years
Montmorilloni (𝐶𝐶𝐶𝐶, 𝑁𝑁𝑁𝑁)(𝑀𝑀𝑀𝑀𝑀𝑀, 𝐴𝐴𝐴𝐴, 𝐹𝐹𝐹𝐹)2
te 15.7 64.2 10-20 years
. (𝑂𝑂𝑂𝑂)2 [(𝑆𝑆𝑆𝑆, 𝐴𝐴𝐴𝐴)4 𝑂𝑂10 ] · 𝑛𝑛𝐻𝐻2 𝑂𝑂
Chlorite (𝑀𝑀𝑀𝑀, 𝐹𝐹𝐹𝐹)3−𝑛𝑛 (𝐴𝐴𝐴𝐴, 𝐹𝐹𝐹𝐹 3+ )𝑛𝑛
18.9 138.9 1 day to 8 years
/𝑂𝑂𝑂𝑂/4 𝐴𝐴𝐴𝐴𝑛𝑛 𝑆𝑆𝑆𝑆2−𝑛𝑛 𝑂𝑂5 (𝑛𝑛 = 0.3 − 1)
Carbonized
33.6 60.5 Over 10 years
organics
Pyrite 𝐹𝐹𝐹𝐹𝑆𝑆2 2.5 2.8
Calcite 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶3 930 998 1-10 days
Dolomite 𝐶𝐶𝐶𝐶(𝑀𝑀𝑀𝑀)[𝐶𝐶𝐶𝐶3 ]2 980 1065 up to 10 days
Ankerite 𝐶𝐶𝐶𝐶(𝑀𝑀𝑀𝑀, 𝐹𝐹𝐹𝐹)[𝐶𝐶𝐶𝐶3 ]2 940 1026 3-8 days

Siderite 𝐹𝐹𝐹𝐹𝐶𝐶𝐶𝐶3 262 920 8-10 days
Magnesite 𝑀𝑀𝑀𝑀𝐶𝐶𝐶𝐶3 114 1149 3-4 months
Limonite 𝐹𝐹𝐹𝐹2 𝑂𝑂3 · 𝑛𝑛𝑛𝑛2 𝑂𝑂(𝑛𝑛 = 1 − 4) 1-7 months
The presence of carbonates during acid heap leaching processes also results in the
precipitation of gypsum (CaSO4·2H2O) which reduces heap permeability and solution
percolation as was observed at the Twin Buttes mine in Arizona (Bartlett, 1998). In addition,
the large quantities of gypsum may coat and passivate precious metals. Acid also reacts with
sulfide minerals present in the transition zone to form elemental sulfur which is problematic
when precious metals are present due to surface passivation (particularly of silver and
electrum) and significant cyanide consumption due to the elemental sulfur reacting with
27
cyanide to form the leaching inactive thiocyanate species. Moreover, the formation of
jarosites, which can lock up silver in highly insoluble form, may lead to significant precious
metal losses, as well as toxic heavy metal inclusions that may be remobilised during
weathering of leach residues. In the recovery of valuable metals from deposits containing
high acid consumable materials, an alkaline leaching medium presents lots of advantages
over an acidic medium as being more selective, less corrosive, and with lower reagent
consumption.
Considering the current trend of declining metals grades in ore deposits, the advantages of
alkaline leaching cannot be over-emphasised. The most widely used and industrially applied
alkaline leaching reagent for base metals and especially copper is ammonia and its
derivatives. Ammonia leaching also serves as an important reference case and basis for
comparison to the alkaline glycine leach approach. The ability of ammonia to dissolve
metallic copper has been known for more than a century (Meng & Han, 1996; Reilly & Scott,
1977). By 1946, considerable research had been conducted to investigate the direct leaching
of copper by aqueous ammonia solutions (Lane & McDonal, 1946). The Sheritt Gordon
ammonia pressure leaching process has been extensively used for the leaching of nickel-
copper concentrates (Biswas & Davenport, 1994) during which sulfide sulfur is converted to
sulfate and copper recovery from PLS is by high pressure hydrogen reduction (Paynter, 1973).
A modification of the Sheritt Gordon process, the Arbiter process, was the only
commercialised ammoniacal leaching process for treating copper sulfide concentrates
(Peters, 1992). It eliminated high pressures by employing the use of oxygen and vigorous
agitation in order to achieve good oxygen dissolution. Copper was recovered by solvent
extraction and not by precipitation as was the case with the Sheritt process (Paynter, 1973).
Recently, MetaLeach Limited, has been testing and evaluating a proprietary ammonia based
process, “Ammleach” for the selective extraction of base metals from their concentrates and
amenable ore deposits (MetaLeach Limited, 2017). The major difference between the
Ammleach process and previous ammoniacal processes is the introduction of the pre-
treatment step which will be tailored for a specific ore deposit. It is claimed that the
Ammleach process could be modified to cope with changing mineralogy that is often
obtained in porphyry copper deposits.
Alkaline ammonia/oxygen processes are ideal when the host rock is acid consuming such
(e.g., calcareous or dolomitic minerals) beacause they minimise reagent consumption.
Additionally, alkaline leach systems alleviate corrosion problems observed in acidic systems
28
by limiting dissolution of impurity elements such as Fe and Mn that, if present in significant
amounts in the leach liquor, will require adequate purification and controlled methodological
recovery of the metals of interest (Bell et al., 1995; Paynter, 1973; Prasad & Pandey, 1998).
These additional purification steps would increase operating costs.
In ammoniacal systems, dissolved metal ions have been observed to be stabilised in solution
through the formation of soluble ammine complexes via the reactive nitrogen-containing
group (Greenberg, 1951). Similarly, glycine, which is being proposed as the main lixiviant in
this research is also known to dissolve metals from their ores via the formation of metal-
glycinate complexes through its amino group (Aksu & Doyle, 2002; Bukharov et al., 2014).
Both alkaline glycine and ammonia solutions (Park et al., 2007) act as buffer solutions further
making the two systems very similar.
The similarities between the alkaline ammoniacal and alkaline glycine systems thus make it
imperative for this thesis to review and understand the reaction chemistry and kinetics of
copper and gold in alkaline ammoniacal systems. The review will elucidate the understanding
of the leaching behaviour, mechanisms and kinetics of copper minerals and gold in the
alkaline glycine solutions.
2.5.1 Aqueous Chemistry of Copper and

Ammonia
Potential-pH diagrams which are used to present the thermodynamic behaviour of leaching
systems (Radmehr et al., 2013) show the stability regions of chemical species present in the
leaching solution. However, Eh-pH diagrams only illustrate thermodynamic relationships and
do not give any information on reaction kinetics (Meng & Han, 1996).
For ammoniacal copper leaching systems, depending on the Eh and pH of the solution, either
Cu(I) and Cu(II) amine species can exist in solution as shown in Figure 2.3 (Konishi, 2007; Xi
et al., 2011). According to the Eh-pH diagram for Cu–H2O-NH3, Figure 2.3, the Cu (I) species,
Cu(NH3)2+, is stable between pH 5 – 12 and Eh between -0.2 to 0.2 V. The Cu(II) species,
Cu(NH3)42+ is stable between pH 8.5 -11.5 and Eh between -0.15 and 1.3 V. However, on
comparing the stability constants of Cu(NH3)2+ being 3.8*1010 and that of Cu(NH3)42+ being
4.8 *1012 (Chmielewski et al., 2009), the cupric ion is thermodynamically more stable in
solution.
29
Figure 2.3 Potential-pH diagram of Cu-NH3-H2O system: 25 °C, Cu activity of 0.5 and [NH3] of 7
kmol/L (Konishi, 2007)
2.5.1.1 Kinetics of Metallic Copper Dissolution in

Ammoniacal Solutions
Copper reacts readily with aqueous ammonia in the presence of oxygen, as shown in
Equation 2.6:
Cu + ½ 02 + 4NH3 + H2O → Cu(NH3)42+ + 2OH- (2.6)
Halpern (1953) studied the dissolution kinetics of metallic copper in ammonia –ammonium
solutions over a wide range of NH3 and NH4+ concentrations, oxygen pressures, temperatures
and stirring speeds. He noted that, at low oxygen pressure, copper dissolution rate was
limited by the transport of oxygen to the surface while, at increased oxygen pressure, surface
chemical reaction limited copper dissolution rate.
The dissolution rate of metallic copper plate in aqueous cupric ammine solutions was studied
by Uchida et al. (1996) at 0.05-1.0 mol CuSO4 concentration, 0-3000 rpm rotation speed and
temperatures between 10-90°C. They found that copper dissolution increases with an
increase in temperature and rotation speed, while a maximum rate was observed with
increasing Cu(II) concentration. They concluded that, at temperatures below 30 °C copper
dissolution rate was mainly controlled by chemical reaction while, at temperatures higher
than 40 °C, diffusion of cupric complex was the rate controlling step.
30
2.5.1.2 Kinetics of Malachite Leaching in Ammoniacal
Solutions
Malachite, being the most common copper oxide mineral and easily amenable to alkaline
leaching, has attracted a substantial amount of research on its leaching kinetics by
ammonia/ammonium salt solutions such as (NH4)2CO3, (NH4)2SO4 or NH4Cl (Wang et al., 2009).
Bingöl et al. (2005) examined the leaching of malachite with aqueous ammonia/ammonium
carbonate solution at 25 °C, solid to liquid ratio of 1:10, stirring speed of 300 rpm, particle
size less than 450 µm, and observed that up to 98 % of copper was extracted in 120 minutes
with very limited dissolution of impurity gangue minerals. Other researchers (D'Aloya &
Nikoloski, 2012; Liu et al., 2012a; Oudenne & Olson, 1983a; Wang etal., 2009; Yartaşi &
Çopur, 1996) have also established that ammonia solutions are suitable for leaching
carbonaceous copper ores due to their ability to selectively leach copper over the
carbonaceous gangue. The leaching kinetics of malachite was examined in water saturated
ammonia gas by Arzutug et al. (2004) and it was found that the leaching rate fitted a pseudo-
second order kinetic model with an Ea of 85.16 kJ/mol. On investigating the dissolution
kinetics of malachite in ammonium chloride solutions, Yartaşi and Çopur (1996) noted that
the reaction was controlled by diffusion through the product film with a required Ea of 81.3
kJ/mol.
Oudenne and Olson (1983b) conducted experiments to investigate the leaching kinetics of
malachite in ammonium carbonate solutions. They found that the leaching process occurred
in two reaction stages with rapid dissolution of malachite occurring in the first 10 % of the
first stage which then decreased due to the formation of needle-structured Cu(OH)2
intermediate. Stage two reactions involved the dissolution of the intermediate product which
occurs only after all pure malachite has been dissolved. Ea’s for the first and second stages
were 64 kJ/mol and 75 kJ/mol, respectively. Künkül et al. (1994) observed that the kinetics
of malachite leaching in ammonia solutions is controlled by the diffusion through the product
layer with the Ea determined to be 22.338 kJ/mol. On evaluating the leaching kinetics of a
low-grade copper ore containing Ca-Mg carbonate in ammonia-ammonium sulfate with
persulfate, Liu et al. (2012b) used the shrinking core model and showed that the leaching
rate is influenced by both interfacial transfer and diffusion across the product layer requiring
an Ea of 22.91 kJ/mol. The contribution of process variables on the dissolution kinetics of
malachite ore in ammonium chloride solution was studied by Ekmekyapar et al. (2003). The
results indicated an increase in the dissolution kinetics when reaction temperature,
31
ammonium chloride concentration, and stirring speeds were increased. The Ea for the
process was stated as 71 kJ/mol and the dissolution model was established to be mixed
kinetics.
Recently, copper dissolution from a malachite ore in ammonium nitrate solutions was
reported by Ekmekyapar et al. (2012) to be a mixed kinetic model, including both surface
chemical control (30 to 50 °C) and diffusion through a porous ash product layer (50 to 70 °C).
It was noted that the sequential stages had Ea’s of 95.10 kJ/mol and 29.50 kJ/mol,
respectively. A kinetic study performed by Künkül et al. (2013) on the dissolution of
malachite in ammonium acetate reported the leaching process to follow a mixed kinetic
control model with a calculated Ea of 59.6 kJ/mol.
The overall reaction of malachite and ammonia is as illustrated by Equation 2.7:
CuCO3 ·Cu(OH)2 + 8NH3 → 2[Cu(NH3)4]2+ + CO32- + 2OH- (2.7)
2.5.1.3 Kinetics of Chalcocite Leaching in Ammoniacal

solutions
According to Salvador (1978), chalcocite leaching in a low-pressure, oxygen ammonia system
occurs in two stages. In the first stage, chalcocite is rapidly converted to soluble cupric ions
and a blue-remaining covellite. The residual covellite material then leaches at a much slower
rate in the second stage producing more cupric ions and sulfate. In the first stage and below
35 °C, copper dissolution is initially controlled by surface chemical reaction (Ea of 66.94
kJ/mol) and then by diffusion through the product layer with an Ea of 55.65 kJ/mol. Above 35
°C, and during the first stage, copper dissolution is controlled by a diffusion process with a
calculated Ea of 25.94 kJ/mol. In the second stage, copper dissolution is controlled by an
electrochemical model in which the rate is proportional to the concentration of oxygen and
hydroxide ion concentration and independent of initial surface area. The estimated apparent
Ea for the second stage is 46.86 kJ/mol.
Filmer et al. (1979) modelled the kinetics of chalcocite (Cu2S) to covellite (CuS) in buffered
aqueous ammonia solution at pH 10.5 using the shrinking core of the Cu2S within a thickening
shell of CuxS(X≥1). Their main objective was to determine the nature and role of any diffusion-
controlling solid state films which are formed on chalcocite and covellite on the dissolution
rate. They noted that diffusion of cupric ions through the CuxS controls the reaction rate. The
oxidation of covellite to cupric ions, sulfur and sulfate is controlled by mixed chemical and
32
diffusion models. It was noted that the presence of sulfur, if any, does not influence rate or
oxidation mechanism.
Chalcocite generally reacts with ammonia according to equation 2.8:
Cu2S + 4NH3 + ½O2 + H2O = CuS + Cu(NH3)42+ + 2OH- (2.8)
2.5.1.4 Kinetics of Chalcopyrite Leaching in

Chalcopyrite is the most abundant copper containing mineral (Dutrizac, 1978; Watling, 2013)
accounting for about 70 % of world copper reserves (Córdoba et al., 2008). Ironically,
chalcopyrite is also the most recalcitrant or refractory of the copper minerals to
hydrometallurgical processes due to its inertness in aqueous systems (Haver & Wong, 1971).
Because of its abundance and difficulties encountered during its processing, chalcopyrite is
one of the most investigated copper minerals (Li et al., 2013b).
XPS analysis by Brion (1980) found that when ground chalcopyrite is exposed to air for a few
minutes, iron hydroxide/oxyhydroxide is formed. This is followed by the formation of a basic
iron sulfate which increases with time. Prolonged exposure results in a reduction of the
concentration of surface copper.
Gardner and Woods (1979) noticed that, during the oxidation of chalcopyrite in basic and
neutral mediums, ferric hydroxide is the main component of the surface layer. It was also
affirmed by Zachwieja et al. (1989) that a hydrated iron hydroxide layer is formed in air-
saturated alkaline solutions. Yin et al. (1995), investigated the electrochemical oxidation of
chalcopyrite with different electrolytes and concluded from XPS data that, the type of
passivation layers formed depended on the solution pH and applied potential. The
composition of the surface layer in alkaline solution (pH 9.2) was CuS2 and Fe2O3 at potentials
lower than 540 mV SHE while S0, CuO and Fe2O3 were formed at potentials greater than 740
mV SHE. It was, however, noticed that the passivation effect was less noticeable in weakly
acidic of pH 6.8 or strongly alkaline solutions of pH 13 (Yin et al., 1995).
Reiley and Scott (1977) investigated the rate of chalcopyrite dissolution in ammoniacal
solution under the following conditions 50-95 °C, oxygen pressure of 689 kPa and [NH3] of
2.5 – 7.0 mol/L. They used an electrochemical surface reaction model to dtermine that
oxygen reduction on the solid surface is the rate determining step requiring an Ea of 74.1
kJ/mol.
33
During a study of the dissolution of chalcopyrite in different ammonium salt solutions, Moyo
and Petersen (2016) observed that different surface products arise from different solutions.
Ammonium sulfate and ammonium perchlorate solutions resulted in the formation of Fe-
oxyhydroxide layer with moderate sulfur, ammonium-ammonium carbonate resulted in no
surface layer formation although a marginal amount of iron was found on the mineral
surface. The reaction kinetics were influenced by the formation of surface products indicating
that reaction kinetics and passivation must be studied concomitantly.
Beckstead and Miller (1977) investigated chalcopyrite leaching using mono-size particles in
stirred reactor at dilute solid phase concentration so that oxygen transport at the gas/liquid
interface would not limit the rate. They reported that the reaction kinetics is controlled by a
catalytic electrochemical surface reaction with a calculated Ea of 41.84 kJ/mol.
The leaching kinetics of chalcopyrite in ammonium iodide solutions with iodine studied by
Guan and Han (1997) using the rotating disk method revealed that the leaching rate was
limited by an electrochemical reaction. At temperatures between 16 and 35 °C, the Ea of was
50 kJ/mol while between 35 and 60 °C, it was estimated to be 30.3 kJ/mol .
According to Das and Anand (1995), the ability of ammonia-ammonium sulfate solution to
leach copper while rejecting iron is believed to occur through the initial leaching of Fe(II)
which subsequently oxidises and then precipitates as Fe(III) oxides in sodium hydroxide
environments. Reduction of oxygen on the surface was assumed to be rapid with the
slow step being the diffusion of dissolved oxygen from the bulk solution phase to the solid
surface.
Chalcopyrite leaching in oxygenated ammonia solutions can be presented by Equation 2.9
CuFeS2 + 4NH3 + 17/4O2 +2OH- → Cu(NH3)42+ +1/2Fe2O3 +2SO42- +H2O (2.9)
2.5.1.5 Aqueous Chemistry of Gold- Ammonia System

and Kinetics of Gold Dissolution in
The Eh-pH diagram of Au-NH3-H2O in Figure 2.4 shows that Au+ and Au3+ can react with
ammonia to form Au(NH3)2+ and Au(NH3)43+ complexes, respectively. The wide pH stability
range of the ionic gold species indicate that gold can be dissolved in ammoniacal solutions
even at room temperature (Dasgupta et al., 1997). However, only Au(NH3)2+ is predominant
34
within the stablity region of water (Meng & Han, 1996).
Figure 2.4 Eh-pH diagram for Au- NH3-H2O system: 25 °C, 101.3 kPa, activity of ions 10-4, [NH3] of
1.0 M (Meng & Han, 1996)
A review on gold dissolution in ammoniacal solutions by Meng and Han (1996) indicated that
gold dissolution is only significant at temperatures higher than 80 °C. Oxygen was found to
be an effective oxidant even though it has a low solubility in aqueous solutions. The order of
the oxidation ability for investigated ionic oxidants was Cu2+ > Co2+ > OCl-. Gold dissolution in
the ammonia solution was predicted to be limited by the electrochemical transfer of
electrons. Depending on experimental conditions, calculated apparent Ea is in the range of
47.1-86.2 kJ/mol. Han and Fuerstenau (2000) studied the influence of factors on gold
dissolution rate in ammoniacal solutions and confirmed that gold dissolution practically does
not occur unless the temperature is raised to at least 80 °C and more practically above 120
°C. They also noted that, although cupric ammine is an effective oxidant for gold dissolution,
iodine was the most effective because it acts as both an oxidant and a complexing agent.
Additionally, iodine could be regenerated in the presence of oxygen. At temperatures
between 160-200 °C, up to 95 % gold could be extracted in ammonia/ammonium solutions
within 1-2 hours of leaching.
The general reaction equation between gold and ammonia is presented in Equation 2.10
2Au + 4NH3 + 1/2O2 + H2O → 2Au(NH3)2+ + 2OH- (2.10)
35
2.5.2 Metal Recovery from Ammoniacal PLS
2.5.2.1 Copper
Copper recovery from alkaline ammoniacal solutions adaptoed the solvent extraction
approach. Solvent extraction was first introduced into the mining industry in the late 1940s
for the processing of uranium solutions. The success of these operations initiated the transfer
of the technology to the treatment of copper pregnant leach solutions (PLS) in 1969. Solvent
extraction involves the mixing the PLS (containing the desired metal, usually in low
concentrations and accompanied with other impurity metals) with an immiscible organic
solution containing an extractant. The reaction between the extractant and the desired metal
forms a chemical compound which is soluble in the organic solvent. The immiscible solutions
are then separated and the loaded organic solvent is mixed with another aqueous phase to
produce a more concentrated and pure aqueous solution of the metal of interest (stripping)
while the organic solvent (raffinate) is recovered and recycled back into the extraction
process (Gálvez et al., 2004; Gupta & Mukherjee, 1990).
In the solvent extraction of copper from ammoniacal solutions, a variety of extractants have
been tested and applied industrially to recover copper (Meng & Han, 1996). In Anaconda's
Arbiter Plant and BHP's Coloso plant in Chile, after leaching, the slurry was filtered and copper
was solvent extracted by LIX-64N. The loaded organic was then stripped by sulfuric acid and
electrowon to give metallic copper. Ammonia was recovered by lime addition to the raffinate
with gypsum precipitation (Radmehr et al., 2013; Wang et al., 2009).
LIX64N was noted to have low copper extraction capacity and also significantly transfers
ammonia onto the organic phase and this hampered its further application (Jergensen, 1999).
LIX84 which has been very successful in extracting copper from acidic solutions has been
reported to exhibit high copper extraction from ammonia solutions (more than 50 g/L) but,
unfortunately, also picks up ammonia. In such cases, ammonia needs to be scrubbed in order
to prevent the accumulation of and precipitation of ammonium sulfate during the electrolytic
process (Parija & Sarma, 2000). In 1995, LIX54, a beta diketone which had shown high copper
loading ability from its ammoniacal leach solutions with low ammonia transfer, was used at
a pilot plant in Escondia-Chile. It was, however, realised that the keto group of the LIX54
extratant deteriorated over time due to its reaction with ammonia to produce a ketamine.
Copper stripping from the organic phase became very challenging and the pilot plant was
eventually closed down (Hu et al., 2010).
36
Using sterically hindered beta-diketone, Hu et al. (2010) were able to show that, at 25 °C
upwards of 95.09 % of copper could be extracted from ammoniacal solutions while only 14.5
mg/L of ammonia was detected in the organic phase.
2.5.2.2 Gold
Investigations on the recovery of gold from ammoniacal solutions have mostly focused on
adsorption by activated carbon and ion exchangers. However, ion exchange resins containing
selective functional groups have been widely tested for noble metal-ions separation from
various solutions (Pilśniak & Trochimczuk, 2007; Pilśniak et al., 2009). Woźniak et al. (2008)
observed that the diamine Au(I) cationic complex from ammonia solution could be adsorbed
onto alpha zirconium(IV) bismonohydrogen phosphate intercalated with butylamine. On
testing a series of synthesised resins for gold adsorption from ammoniacal solutions, Pilśniak
and Trochimczuk (2007) found that 1-methylimidazole resin shows the highest affinity
towards gold with as high as 15.5 mgAu/gresin sorption from a 100 g/dm3 NH4OH, 50 g/dm3
(NH4)2SO4 solution in the presence of copper.
2.5.3 Challenges of Ammonia Leaching

Despite ammoniacal leaching medium having the advantage of selectivity leaching of copper,
it has many technical, operational and environmental challenges. Some of these challenges
include its volatility, its noxious odour detected even at low concentrations, its toxicity to
aquatic organisms, and its adverse health effects such as corrosiveness to the respiratory
track and burning of the skin. The conventional suite of alkaline lixiviants, such as ammonia
and its derivatives, is very limited particularly when reagent consumption is significant as
obtained with oxidised base metal ores. Ammonia also has problems, volatility, high lixiviant
to base metal stoichiometric requirements, recovery and recycle, and ease of oxidation.
These challenges have limited the application of the ammoniacal system, especially in the
heap leaching of low grade ores and other open systems (vat leach and in-situ leach).
Ammonia is not well received by nearby communities and the use thereof may face
significant legislative hurdles. These reagents are particularly unsuitable for base metal
extraction through heap leaching, which is often seen as the only viable alternative to treat
low grade oxide and transition ore deposits.
To improve copper recovery from ammoniacal solutions, there is a continuous search for
37
extractants that can efficiently load high concentrations of copper from solutions while
rejecting ammonia.
As a result of the aforementioned limitations of ammonia leaching, and with the acceptance
that alkaline leaching is the way forward for processing low grade ores (which are rather
becoming a norm in the mineral industry), the motivation of this research which proposes
glycine as an alkaline lixiviant for leaching low-grade copper gold ores is further justified. The
following section discusses the properties and the aqueous copper/gold- glycine chemistry.
2.6 Glycine as Copper and Gold Lixiviant
2.6.1 Structure, Physical and Chemical Properties

Glycine or aminoacetic acid is the simplest amino acid. As indicated by their name, amino
acids are organic compounds containing both a carboxyl group (-COOH) and an amino group
(-NH2) bonded to the same carbon atom in α position. The distinguishing factor for different
amino acids is the side chain denoted as R, which in turn governs the properties of the amino
acid. The general structure of an amino acid is given by Figure 2.5.
H
O
H2N C C
OH
R
Figure 2.5 General structure of amino acid
Glycine (2- aminoacetic acid) is the simplest amino acid having a hydrogen atom as a side
chain, H2N-CH2-COOH(de Farias et al., 1999).
H
O
H2N C C
OH
H
Figure 2.6 Structure of glycine
Glycine is characterised as follows (Wade, 2013):
• Colourless, odourless, sweet crystalline solid in pure form;

• Soluble in water (25 g/100mL at 25 °C), acids, alkalis but not soluble in organic solvents
38
(0.038 g/100mL) (Fleck & Petrosyan, 2014);
• High melting point of 262 °C and decomposition point 292 °C (Huang et al., 2013); and
• Optically inactive because of the two hydrogen atoms at the alpha carbon (Chan et al.,
2006; Nelson & Cox, 2013).
2.6.2 Industrial Applications of Glycine

The applications of glycine can be found in pharmaceuticals, medicine, agronomy, nutrition
and some metal processing applications (Drauz et al., 2000; United States International Trade
Commission, 2008). The following points summarize the uses and applications of glycine in
different industrial fields:
• Taste enhancer and sweetener in food production industries;

• Buffering agent in cosmetics, most deodorants and antiperspirants;
• Dietary supplement as restorative iron supplements for humans are produced from an
Fe-glycine complex;
• Chelating agent in crop production for cationic micronutrients and also as a fertilizer
source of nitrogen;
• Pharmaceuticals and medicine in intravenous injections, for treatment of schizophrenia
(Tsai et al., 1998), stroke, benign prostatic hyperplasia. Glycine in combination with other
amino acids used to heal wounds and treat ulcers.
• Main ingredient in the production of Glyphosate (N-phosphonomethyl-glycine which is
the most widely used herbicide worldwide (Nicolia et al., 2014), and is manufactured by
Monsanto sold as “Roundup”; and
• Levelling agent in acidic electroplating of Cu(Aksu & Doyle, 2001) and Zn-Fe (Karahan,
2013) to produce smoother deposits by modifying the structure and topography .
2.6.3 Glycine Production

Glycine can be produced through chemical synthesis or from the hydrolysis of natural
compounds that have high levels of protein (Couriol et al., 1999). Chemical synthesis is the
main method of producing glycine industrially as it is more economical. Common chemical
synthesis methods for glycine are: Bucher method, the Strecker method and the
ammonolysis of monochloroacetic acid (MCA). The most widely used pathways for producing
glycine industrially are the Strecker and MCA-ammonia methods.
39
The Strecker method involves the reaction of formaldehyde with ammonia and hydrogen
cyanide to form aminoacetonitrile (Equation 2.11) which is then hydrolysed to produce
glycine (Fujiwara et al., 1993; Koch et al., 2008). This is one of the simplest and most
economical methods of producing glycine both in the laboratory and on an industrial scale
(Cai & Xie, 2014).
RCHO + NH3 + HCN → NH2RHCCN + H2O → NH2RCOOH (2.11)
Ammonolysis of monochloroacetic (MCA) acid proceeds with the neutralization of MCA by

ammonia to produce an ammonium salt of MCA. This salt is then reacted with
hexamethylenetetramine to produce a quaternary ammonium salt and ammonium chloride
as co-product. The quaternary ammonium salt is further ammonolysed leading to the
production of glycine and hexamethylenetetramine. These reactions are illustrated by
Equations 2.12, 2.13 and 2.14:
ClCH2COOH + NH3 → ClCH2COO- + NH4+ (2.12)
C6H12N4 + ClCH2COO- + NH4+ → [C6H11N4+ – CH2-COO-] + NH4Cl (2.13)
[C6H11N4+ – CH2COO-] + NH3 → C6H12N4 + H3N+CH2COO- (2.14)
The ammonolysis of MCA produces a higher quality product and does not require hazardous
reagents like the Strecker method.
2.6.4 Aqueous Chemistry of Glycine

Glycine occurs as an amphoteric agent in aqueous solution acting as an acid (proton donor)
and a base (proton acceptor) depending on the solution pH. Below the pH of 2.35; the
glycinium cation +H3NCH2COOH (H2L) is predominant. The zwitterion +H3NCH2COO-(HL) is
stable between the pH of 2.35 to 9.78. When the pH is above 9.78 the glycinate anion
H2NCH2COO-(L) is predominant. Energetically, the zwitterion is more stable both in solid state
and in solution (Rega et al., 1998; Smith & Martell, 1989; Tortonda et al., 1996; United States
International Trade Commission, 2008). The association of these monomeric species results
from the formation of hydrogen-bonds between them in concentrated solutions while their
stability in dilute solutions is ensured by the formation of hydrogen bonds with water
molecules. Apart from the monomeric proton complexes, polymeric associated forms like
40
[HL2]-, H2L2 and [H3L2]+ might exist in highly concentrated solution (Kiss et al., 1991). During
the titration of glycine, two equilibrium reactions occur with each having its own dissociation
constant (pKa) value (Equations 2.15 and. 2.16).
+H NCH COOH
(aq) H3NCH2COO (aq) + H+(aq) pKa1= 2.34 (2.14)
+ −
3 2
+H NCH COO−  H2NCH2COO-(aq) + H+(aq) pKa2 = 9.6 (2.15)

3 2 (aq)
The titration curve for glycine with NaOH shown in Figure 2.7, is unique to glycine and can be
used to identify the presence of glycine in solution as each amino acid has its own distinctive
titration curve
Figure 2.7 Titration curve of a 0.1 M glycine solution with NaOH. Frames indicate pH plateaus
(Hegyi et al., 2013)
In the presence of strong oxidizing agents, the amino group is attacked and converted into
an iminocarboxylic acid. This iminocarboxylic is unstable and can be further hydrolysed to an
oxocarboxylic acid which then undergoes decarboxlylation to produce ammonia and
aldehyde (Drauz et al., 2000).
The oxidation of glycine by both one-electron oxidants (e.g., Mn3+, Fe(CN)63-, two-electron
oxidants (e.g., K2S2O8) and multi-electron oxidants (e.g., KBrO3, Mn(H2O)32+, KMnO4) have
been reported to generally produce formaldehyde, carbon dioxide and ammonia although
minor products are formed from different oxidizing agents (Insausti et al., 1992; Sarathi et
al., 2005). Ozone and hydroxyl radicals (•OH) were reported by Berger et al. (1999) to oxidize
41
glycine where the hydroxyal radical is unchanged, derived from the breakdown of hydrogen
proxide, and should not be confused with the hyroxyl anion). The products formed from
molecular ozonation of glycine were ammonia, nitrites and nitrates while ammonium ions,
oxalic acid and formic acid were produced from hydroxyl radical decomposition of glycine.
It is important to point out that no research to date has shown oxidative degradation of
glycine with dissolved oxygen. However, the studies above clearly indicate that, in the
presence of sufficiently strong oxidants, glycine can be degraded and destroyed.
In the presence of bacteria such as cell suspensions of Proteus and Pseudomonas aeruginosa,
glycine can be aerobically oxidised to ammonia, carbon dioxide, cyanide and water
(Campbell, 1955; Wissing, 1974). However, this oxidation process could be inhibited by
pyrrolnitrin (Wissing, 1974).
Glycine has also been observed to undergo oxidation on platinum and gold electrodes in
acidic, neutral and basic solutions (Chia et al., 2013; Marangoni et al., 1989). Cyclic
voltammetry analysis of glycine adsorption on Au electrode in 0.1 M phosphate buffer at
room temperature indicated irreversible oxidation of glycine at E > 0.6 V. The main products
of the electrolytic oxidation of glycine include: ammonia, formaldehyde, formic acid, carbon
dioxide, cyanide, carbon monoxide, and methyl, dimethyl, and trimethyl amines. According
to Marangoni et al., (1988), the main product of electro-oxidation of glycine under both acidic
and basic conditions is formaldehyde. In basic glycine solutions, they calculated the
thermodynamic potential for which glycine oxidation occurs to be 1.33 V, ESCE. They noted
that the potential corresponds to that at oxygen evolution. Thus, the electrochemical
oxidation of glycine in alkaline medium occurs when the solution potential is higher than that
for H2O/O2 decomposition.
If free amino acids are heated above 200℃, especially in the presence of soda lime or metal
ions, they readily decarboxylate to form amines (Drauz et al., 2007).
Glycine has the ability to form complexes (acting as chelating ligand) with metals through the
oxygen atom of the carboxylic group and the nitrogen atom of the amine group. These groups
can simultaneously form two bonds with metals by donating a pair of electrons. Glycine has
been observed to form complexes with copper, gold, silver, arsenic, cobalt, vanadium (Kajala
& Gupta, 2009; Khorrami et al., 1996; Remko & Rode, 2006; Uvdal et al., 1990).
42
2.6.4.1 Aqueous Chemistry of Copper and Glycine
In the semiconducting industry, copper is increasingly being used as an interconnect metal in
integrated circuit boards due to its high electrical conductivity. Chemical-mechanical
planarization (CMP) is a method which proceeds by the mechanical removal of surface layers
and the dissolution of the abraded particles in CMP solution. The chemical composition of
the CMP fluid is important as it needs to facilitate oxidation and removal of excess copper
(Deshpande et al., 2004). The new model of using peroxide and glycine as CMP solution has
led many researchers to investigate the fundamental interaction between the different
chemical constituents in the solution (Aksu & Doyle, 2001, 2002; Chen et al., 2013; Green &
Jeffrey J. Mueller, 1999; Du et al., 2004; Seal et al., 2003; Tianbao et al., 2004; Tripathi et al.,
2010; Zhang & Shankar, 2001). The proposed mechanism is that the peroxide oxidizes the
copper and the oxidized copper ions form a stable, water soluble Cu-glycinate complex
(Tianbao et al., 2004). It was observed that, in either acidic or basic medium, the dissolution
of copper increased as the glycine concentration was increased while an increase in
hydrogen peroxide concentration beyond 0.25 wt % H2O2 led to a decrease in copper
dissolution (Aksu & Doyle, 2003). As it can be seen in Figure 2.8, the copper glycinate complex
is stable over a wide pH range (2.6 – 12). The major copper(II) glycinate complexes are:
Cu(H3NCH2COO)2+ (CuHL2+), Cu(H2NCH2COO)+ (CuL+) and Cu(H2NCH2COO)2 (CuL2), while the
predominant copper(I) complex is Cu(H2NCH2COO)2- (CuL2-).
Figure 2.8 Eh-pH diagram for copper-water-glycine system at a total dissolved copper activity of
10-5 and total glycine activity of 10-2 at 25℃ and 1 atm (Aksu et al., 2003).
43
Table 2.7 indicates the stability constants of Cu (I) and Cu(II) glycinate complexes.
Table 2.7 Copper glycine complexes and their stability constants (Aksu & Doyle, 2001)
Copper ion Copper-glycine complex logK

2+
Cu Cu(H2NCH2COO)2 15.6
Cu+ Cu(H2NCH2COO)2- 10.1
Cu2+ Cu(H2NCH2COO)+ 8.6
The copper glycinate complex has been identified in biological systems, especially in enzymes
where it occurs in active sites. This has led to a huge research to understand the mechanisms
of interaction between the cupric ions and amino acids which act as the medium for
transporting copper in living organisms (Bukharov et al., 2014). In an earlier investigation,
Bukharov et al. (2012) determined the mechanisms and effectiveness of chemical reactions
and studied the rotational dynamics of copper(II) amino complexes by electron
paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) relaxation methods
and observed that the trans isomer of Cu(Gly)2 is the dominant species in solution.
The solubility of copper glycinate in alkaline solutions, however, depends on temperature,

concentration of components and pH (Gyliné, 2001). Experiments conducted by Gyliné,
(2001) showed that both cis-Cu(Gly)2 and trans-Cu(Gly)2 form precipitates after several hours
or days when NaOH or KOH is used as pH modifier.
2.6.4.2 Aqueous Chemistry of Gold and Glycine

Liedberg et al. (1985) performed investigations to understand and explain the interaction
between biological molecules and metals occuring in many biological processes. They studied
the adsorption of glycine on hydrophilic gold and noted that glycine forms thin films on the
surface of gold with the nitrogen end directed towards the gold surface. To further elucidate
the interactions between gold/silver and glycine, Pakiari and Jamshidi (2007) used the
density functional theory (DFT) to postulate that the interaction between gold and silver
clusters with glycine is governed by two principal bonding factors: the anchoring N-Au and
O-Au bonds and the nonconventional N-H----Au hydrogen bonds. This observation has been
confirmed by Xie et al. (2012) who used the same DFT to report that complexes having the
Au-NH2 anchoring bond are more energetically stable with sole pair of electrons being
transferred to the antibonding orbitals of gold.
It has been reported that bacteria secrete complexing chemicals like amino acids which in
44
the presence of oxidizing agents such as oxygen and potassium permanganate or peroxide
can solubilize gold from ores (Groudev et al., 1995). Glycine, amongst a range of amino acids,
secreted by bacteria, reacts with gold in the presence of permanganate to form a gold(I)
glycine complex through the formation carboxyl ions and the amino acid group nitrogen
(donor-acceptor) bonds (Mineev & Syrtlanova, 1984). The solubility of gold in different amino
acids has originally been studied by (Brown et al., 1982; Jingrong et al., 1996) e.g. in studies
looking at the interaction of jewellery with body fluids. The interaction between gold and
glycine was also reported in the adsorption of glycine on a gold electrode in alkaline solutions
(Bogdanovskaya et al., 1986). Gold extractions in thiosulfate solutions have been reported to
be improved by the addition of amino acids (L-valine, glycine, DL-a-alanine and L-
histidine)(Feng & Van Deventer, 2011).
Recently, extensive research in the use of amino acids as leaching agent for copper and/or
precious metals by Eksteen and Oraby (2015b) of the Gold Technology Group-Curtin
University has led to the development of a patent for the recovery of these metals from their
resources. They reported that, although amino acids can act in synergy to dissolve gold,
glycine shows the highest gold dissolution as a single amino acid (Eksteen & Oraby, 2015a).
The leaching rate of gold in solutions containing 0.5 M glycine, 1 % peroxide at pH 11 and 60
°C for 48 hours was found to be 0.322 µm/m2. This is comparable to the gold leaching rate
of 0.22-0.25 µm/m2 in thiosulfate-oxalate systems in the presence of thiourea for six days
(Oraby & Eksteen, 2014a). The general reaction between gold and glycine is illustrated by
Equation 2.16
4Au + 8NH2CH2COOH + 4NaOH + O2  4Na[Au(NH2CH2COO)2] + 6H2O (2.16)
2.6.5 Glycine Analysis

A lot of research has been undertaken to develop on-the-spot sensitive methods for the
determination of both the presence and concentration of free glycine.
As amino acids, including glycine, do not have wavelengths in regions of interests,

colorimetric indicators with different UV spectra in acidic and basic medium have been
developed to study the dissociation of amino acids (Ryan et al., 1997; Xiang & Johnston,
1994). Moore & Stein (1954) introduced the ninhydrin method for the photometric
quantitative determination of amino acids in the 1940s and this has undergone several
modifications to make it safer and reliable (Sun et al., 2006). The method is based on the
45
reaction of amino acids with reduced ninhydrin (triketihydrindenhydrate) at a pH of 5.
Stannous chloride is employed as the reducing agent (Rosen, 1957). This reaction yields a
“Ruhemann’s purple” colour as an end product and the resulting mixture is assayed
colorimetrically to determine the content of amino acid (Yokoyama & Hiramatsu, 2003). The
ninhydrin method has been used in the determination of the concentration of glycine in
antiperspirant (Chin & Achari, 1982).
The most acceptable and widely applied method for quantitative analyses of amino acids is
the reverse-phase-high performance liquid chromatography (RP-HPLC) which is preceeded
by the precolumn derivation of the amino acids. The precolumn derivation presents
covalently bound chromophores vital for interactions with apolar stationary phase for high
resolution and also for photometric detection (Kochhar et al., 2002). The HPLC method has
also been reportedly used for glycine analysis in antiperspirant.
2.7 Leaching Methods Applicable to Low

Grade Ores
The leaching technique employed for any extraction project depends most importantly on
the mineralogical composition of the ore, head grade, and the expected value of metal in
solution. Any leaching technique should produce as much wanted metals in solution as
possible, in the shortest possible time, using as little as possible energy and reagents. It is
also well known that there is the continuous growth in the inventory of low grade copper
resources falling below the cut-off grade for conventional concentrate production method.
As can be seen in Figure 2.9, head grades for most copper deposits will fall below 1% by 2022.
46
Figure 2.9 Falling industrial copper ores head grade trends (Brook Hunt)
For most conventional processing methods, decreasing ore grades results in an exponential
increase in the operating cost with mining and milling incurring the highest proportion as
shown in Figure 2.10 (Tiang et al., 2012).
Chart Title
1% 2%
Drilling and Blasting

10%
22% Excavation and Hauling
Crushing
18%
Ore Conveying
7% Grinding
4% Flotation/Concentration
Leach/Absorption
35% Tailing Disposal
Figure 2.10 Energy consumption in mineral processing (Stadler, 2015)
Copper ore grades of <0.8 % and <0.5 % as obtained in Greenfield and Brownfield
applications respectively are uneconomical by conventional processing paradigms (AMIRA
International, 2014). With grinding taking up to 35% of the energy consumption of most mine
sites, declining ore grades is an indication that most mining operations should be moving
from conventional methods to energy efficient strategies for low grade ores (Stadler, 2015).
Investigations on the total energy consumption for mineral processing routes by Marsden
47
(2008) demonstrated that hydrometallurgy consumed less energy as compared to alternative
grinding, floating and refining routes. It was also shown that lower grade ores demand more
energy for their processing as obtained in Figure 2.11
Figure 2.11 Total energy consumption as a function of head grade for various process
routes (Marsden, 2008)
Hydrometallurgical methods are therefore mostly optimum for the recovery of low grade
ores because of the low capital and operational costs, short construction time, simplicity of
operation, proven technologies and environmental advantages. The main techniques that
are preferable for the processing of low grade ores are dump, heap and vat leaching (Watling,
2013).
2.7.1 Dump Leaching

Historically, the application of this method dates back to the sixteenth century in the Harz
Mountains in Germany (Habashi, 1980). Dump leaching is generally applied to run-of-mine
(without any significant crushing) which contains very small amounts of valuable metal that
is uneconomical (i.e., below cutoff grade) to treat by any traditional leaching method. The
dumps, which can be as high as 200m, 250m wide, containing 50,000 to 300,000 tons, are
placed on impervious ground close to the mine site using the natural terrain which can be
steep-sided valleys or hillside to enhance drainage. Processing is done by sprinkling the
leaching solution on top and, as the solvent trickles down, the metal passes into solution and
the pregnant leach solution (PLS) is collected at the bottom for recovery (Habashi, 1989).
48
Figure 2.12 shows a dump leaching technique on a slope to facilitate drainage.
Figure 2.12 Dump leaching (Näveke, 1986)
2.7.2 Heap Leaching

Heap leaching is applied for valuable metals recovery from low-grade ore (i.e., at ir above
cutoff grade) that has been deposited on a prepared lined pad (impermeable) constructed
using synthetic material, asphalt or compacted clay. In heap leaching, the ore is frequently
beneficiated by some type of size reduction (usually crushing and sometimes agglomeration)
prior to placement on the pad. The lixiviant solution sprayed on top of the heap permeates
and transverses the heap by gravity implying that the process is slow and might last for
several days and up to 600 days for some sulfide ores (Mellado et al., 2009; Zanbak, 2012).
Just as in dump leaching; most leach sites are selected to take advantage of existing natural
slope of ridges and valleys for the collection of PLS. Heap leaching has found world
applications in the processing of low grade gold, silver, uranium, and copper ores. There are
several parameters that have been identified to influence this process, e.g. pH of the
lixiviants, height of the heap, ore particle size distribution, spraying flow rate, irrigation
technique, permeability, porosity, aeration, impurities, valuable metals, accompanying
metals, temperature of the PLS, solid-to-liquid ratio, etc. (Lwambiyi et al., 2009). Heap
leaching can be performed using both oxygenated acidic solutions or solutions containing
bacteria as is the case in Talvivara–Finland. A schematic presentation of heap leaching is
shown in Figure 2.13. Heap leaching finds application in the recovery of low grade ores
49
because of its low cost, short construction time, operational simplicity, and environmental
advantages (Watling, 2006).
Figure 2.13 Heap leaching (Biomine, 2014)
2.7.3 Vat Leaching

In vat leaching, the leaching agent is added onto the ore that has been placed in a tank fitted
with a false bottom covered with a filtering medium. These tanks are usually placed in series
and arranged in counter current system in which the ores remains in the tank and is
successively leached with leaching reagent of increasing strength. The particle size and
porosity of the material are of absolute importance, making impossible the application of this
method to slimy materials which will block the efficient flow of the leaching reagents. The
major advantages of this method are the low consumption of leaching reagents, production
of high concentration PLS, and the elimination of the use of expensive thickeners and filters.
Figure 2.14 shows vat leaching of copper at Mantos Blancos, Chile, 1995.
50
Figure 2.14 Vat leaching of copper at Mantos Blancos, Chile, 1995 (Source: INNOVAT Limited)
2.7.4 Bioleaching
Bioleaching refers to the leaching of sulfide ores involving a variety of microorganisms
including not only bacteria, but also archaea (group of single-celled microorganisms) at
various temperatures and pH ranges (Suzuki, 2001). The involvement of bacteria in the
leaching of metals in natural environments has been practised for many years although the
bacteria (Thiobacillus Ferrooxidans) that plays a major role in dump leaching was only
identified in the 1940s (Trivedi & Tsuchiya, 1975). Sand et al. (2001) indicated that bacterial
solubilisation of minerals containing iron is achieved both by direct (contact) leaching by
bacteria and by indirect leaching with ferric irons. For indirect leaching, the microorganisms
derive their energy by oxidising ferrous ion to ferric ion and, by so doing, generate solutions
with relatively high redox potential that leach the sulfide minerals. In direct leaching, the
bacteria attaches to the mineral sulfide and oxidises the mineral to sulfate and metal cations
by an enzyme-oxygen system.
Bioleaching is mostly suitable for dump and heap or possibly vat (large tanks) operations. A
full scale example is the BacTech and Mintech process in Monterrey, Mexico and Talvivara,
Finland (Habashi, 2009).
51
2.8 Summary
A literature review has revealed that there is a huge reserve of discovered and undiscovered
copper-gold resources in the form of porphyry copper deposits that are distributed all over
the world. Out of the 2100 million metric tonnes of identified copper deposits porphyry
copper deposits account for 60 %. It is postulated that twice the amount of identified copper
reserves is yet to be identified. The literature has also established that the current
technologies for the processing of copper-gold ores are inefficient or not environmentally
benign and the need for further research on ways to effectively extract the metals of interest
from these resources in a benign manner is necessitated. Attributes of good lixiviants have
also been investigated. Glycine, which is the simplest amino acid, is physically and chemically
stable over a wide pH-Eh range, forms stable complexes with metals, has shown great
capabilities for the selective leaching of copper, gold and other metals. With ore grades on a
continuous decline, different processing techniques such as dump, heap and vat leaching
applicable to such ores have been explored and may see increasing use in the future.
52
Chapter 3 Materials and Methods
3.1 Chapter Objectives
A variety of materials and research methods have been used to meet the goals of this thesis
as outlined in Chapter 1. The main objective of this chapter is therefore to give a detailed
description of the materials, procedures and analytical techniques that were employed in
this research.
With the primary aim of investigating the leachability of low grade copper-gold ores and
copper minerals in a new leach process, ores and minerals samples used for all
experimentation are described, along with the methods for sample characterization and
preparation for experiments. These minerals and ores underwent a variety of batch leach
tests including leaching, solvent extraction and sulfide precipitation. The equipment and
conditions used for these experiments are detailed in this chapter. Glycine as the main
lixiviant in this study and other reagents used for the various experiments are listed in this
chapter as well.
Lastly, this chapter explains the fundamentals of different techniques that were used to
collect the data needed in the subsequent chapters. The experimental conditions,
parameters and different procedures for samples preparation, copper minerals leaching,
copper speciation, leaching kinetics, copper-gold ores leaching, column leaching, solvent
extraction and metals precipitation are described in the following sections.
3.2 Materials and Reagents

All reagents were of analytical grade. De-ionized water was used for preparing all solutions.
A list of different copper minerals and gold-copper ore samples used for different
experiments are given in Table 3.1. Table 3.2 also shows a list of the analytical grade reagents
and gases used in different experiments described in the thesis.
53
Table 3.1 List of different copper minerals and gold-copper ores used in this study
Mineral/ore sample Experiment

Azurite Leaching behaviour
Malachite A Leaching behaviour
Malachite B Leaching kinetics
Cuprite Leaching behaviour
Chrysocolla Leaching behaviour
Chalcocite A Leaching behaviour
Chalcocite B Leaching kinetics
Chalcopyrite A Leaching behaviour
Chalcopyrite B Leaching kinetics
Copper-gold ore A Copper and gold leaching
Copper-gold ore B Copper and gold leaching
Copper-gold ore C Copper and gold leaching
Copper-gold ore D Copper and gold leaching
Table 3.2 List of different analytical grade reagents and gases used in this study
Reagent Formulae Purpose Purity

Glycine H2NCH2COOH Main lixiviant AR
Sodium hydroxide NaOH pH modifier AR
Lime Ca(OH)2 pH modifier Industrial grade
Hydrogen peroxide H2O2 Oxidizing agent AR
Oxygen O2 Oxidizing agent Industrial grade
Air Oxidizing agent Atmospheric
Sodium persulfate Na2S2O8 Oxidizing agent AR
Sodium nitrate NaNO3 Effect on Cu2S AR
leaching
Sodium chloride NaCl Effect on Cu2S AR
leaching
Sodium sulfite Na2SO3 Effect on Cu2S AR
leaching
Sodium hydrosulfide NaHS Precipitation reagent AR
Mextral 84H 2-hydroxy-5- Copper extractant AR
nonylacetophenone oxime
Mextral 54-100 1-benzoyl-2-nonyl ketone Copper extractant AR
DT-100 Diluent for extractant AR
Sulfuric acid H2SO4 Stripping agent AR
54
3.3 Procedures
3.3.1 Mineral and Ore Specimens Preparation
3.3.1.1 Minerals
Copper mineral specimens were to study their dissolution behaviour in alkaline glycine
solutions after crushing and grinding to 100 % passing 75 µm. Each sample was
representatively split and a portion of the sample was analysed by XRD to ensure that the
mineral sample contained only the copper mineral phase of interest (with or without other
metal phases). Upon confirmation of the copper mineral phase in the sample, another
portion from the sample was analysed by XRF to determine the elemental composition of the
mineral sample. Oxidation of the finely ground sulfide minerals was minimized by storing the
samples in a freezer.
Once the mineral phases were confirmed, samples were crushed and screened at different
size fractions for leaching kinetics studies. The sulfide samples were then stored in the freezer
to minimize oxidation.
3.3.1.2 Ores
Copper-gold ore specimens were also crushed and ground to 100 % passing 75µm and sub-
samples were analysed for mineralogical and elemental composition by XRD and XRF,
respectively. Samples with phase concentrations less than 1 %, which are generally not
detected by XRD, were analysed by Tescan Integrated Mineral Analysis (TIMA) technique to
detect any copper mineral phases at low concentrations.
Column leaching experiments were performed with two different copper-gold ore types. One
of the samples was a flotation tail and was used as received since more than half of it was
already agglomerated from drying. A representative sample was analysed for its mineralogy
and elemental compositions. The second sample was crushed and sieved to obtain a +1/-8
mm size fraction. Mineralogical and elemental analysis were also performed on a sub-sample
of this ore.
55
3.3.2 Leaching Behaviour of Copper Minerals
All solutions used in these experiments were prepared from reagent grade glycine, obtained
from Sigma Aldrich, and de-ionised water. Sodium hydroxide was used for solution pH
adjustments. The redox potential (Eh) of the leach solution was measured and reported
according to Ag/AgCl reference electrode and pH measurements were performed using a TPS
90FLMV field meter. Unless specified, all experiments were conducted in a 2.5 L Winchester
bottle ( OD 44 cm and L 30 cm ) using a bottle roller (The major advantage of bottle rolling is
that one can rapidly determine the effect of conditions (e.g. reagent concentration, pH, and
solid/liquid) by running simultaneous experiments (up to 15). The required mass of mineral
specimen was weighed to give the equivalent of 2.0 g total copper in the solid. The weighed
sample was then placed in the bottle and the leaching solution was added. The percentage
solids used for each mineral specimen is given in Table 3.3. Slurry agitation was provided by
immediately placing the bottle (sample and leaching solution) onto a bottle roller rotating at
100 rpm. To ensure that enough oxygen was available for the leaching reaction, the bottles
were capped with lids having a centered 5 mm in diameter hole. During the leaching
experiments, several intermediate samples were collected. This involved removing the
bottles from the roller, allowing to stand for one minute to allow the solids to partially settle,
and then withdrawing 3 mL of slurry and filtering by means of a syringe-membrane filter
(pore size 0.45 µm). An Atomic Absorption Spectrometer (AAS), Agilent 55B model was used
to determine the concentration of copper in the filtrate. For experiments showing a low
copper recovery, the leached residues were rinsed with deionised water, dried and observed
under a Scanning Electron Microscope (SEM) to understand the change in surface
morphology of the samples during leaching.
Table 3.3 Solid percentage used for the dissolution behaviour of copper mineral specimens
Ore Cu in ore,% Mass Cu, g Mass ore, g Solution, mL % w/v solids

Azurite 42.12 2.00 4.75 500 0.95
Chrysocolla 24.70 2.00 8.09 500 1.62
Cuprite 20.09 2.00 9.96 500 1.99
Malachite 41.55 2.00 4.81 500 0.96
Metallic copper 99.99 2.00 2.00 500 0.40
Chalcocite 78.8 2.00 2.54 500 0.51
Chalcopyrite 14.81 2.00 13.50 500 2.70
56
3.3.3 Copper Speciation
Copper speciation experiments were performed to determine if Cu(I) and/or Cu(II) ions are
dominant in the alkaline copper-glycine leach system. An Ultraviolet- Visible (UV-Vis)
spectrometer was employed to detect and determine the concentration of copper (II)-
glycinate species in solution. Cupric sulfate pentahydrate (CuSO4·5H2O) was used to prepare
synthetic solutions containing copper-glycinate complex. The influence of pH, glycine and
sulfate concentrations on the absorbance and wavelength position were also investigated by
varying their values in the solutions. Copper (I) chloride was also dissolved in the alkaline
glycine solution and samples collected immediately after addition to determine the presence
of any other peak apart from the Cu(II) peak.
Cupric sulfate pentahydrate was then used at different concentrations in alkaline glycine
solution to generate a calibration curve at different Cu(II) concentrations. The final solution
from leaching different copper minerals was analysed for total copper using AAS and for Cu
(II)-glycinate using UV-Vis spectrometer.
3.3.4 Leaching Kinetics Experiments

All kinetic experiments were conducted in a 500 mL jacketed glass reactor fitted with a
condenser, a mercury thermometer, an overhead teflon stirrer, and rubber stopper for the
sampling inlet. The reactor was filled with a 500 mL solution of the desired reagent
concentration and pH. For the leaching kinetics of chalcocite and chalcopyrite, the effect of
dissolved oxygen (DO) on copper extraction was investigated. In order to do that, a DO
controller system was set to measure the DO in solution and maintain a desired DO value by
controlling the oxygen flow through an automatic valve controller. The required solution
temperature was achieved and maintained with a digitally controlled heated circulating
water bath. On attaining the desired temperature, the required mass of copper mineral
sample was added to the solution and the stirring was started. After a specific leaching time,
the stirring was stopped, a one minute interval was allowed for the particles to settle and
3mL solution was extracted for copper concentration determination by atomic absorption
spectrometry. The percentage of copper extraction was calculated based on the copper
released into the solution per total expected. Figure 3.1 and Figure 3.2 illustrate the
apparatus setup for leaching kinetics.
57
Stirring speed
controller
Condenser
DO controller
DO probe
Oxygen sparger
Teflon coated stirrer
Oxygen cylinder
Re-circulating water bath
Figure 3.1 Diagram of leaching kinetics apparatus setup
Figure 3.2 Laboratory leaching apparatus setup
58
3.3.5 Leaching of Copper-Gold Ores
Experiments were conducted to investigated the effect of glycine and solution pH on the
leaching of copper from copper-gold ores in 2.5 L Winchester bottles opened to air, bottle
rolled at 100 rpm and room temperature. The required mass of the copper-gold ore sample
(Table 3.4) was placed in the bottle/reactor of leaching solution along with the required
amount of reagents at a predetermined initial pH. Afterwards, the bottles were immediately
placed on the bottle roller.
Table 3.4 Leaching vessel, ore type, solution volume and ore mass for leaching Cu-Au ores
Leaching vessel ore solution vol , mL sample mass, g

Bottle roller A 500 100
B 500 100
C 500 500
1 L reactor B 500 100
C 500 500
Effects of temperature, oxygen and pyrite addition were conducted in a 1000 mL jacketed
glass reactor. The reactor was equipped with a condenser, a thermometer, an overhead
stirrer, a fine oxygen sparger, and a sampling inlet with a rubber stopper. The solution
temperature was maintained by connecting a digitally controlled heated circulating water
bath to the reactor. Before the leaching was started, the solution (0.5 M gly, pH 11.5) was
oxygenated at the desired oxygen flow rate for 10 minutes at the selected temperature. The
ore sample was then added and the leaching time started.
At given leaching time intervals, sub samples were withdrawn from the leaching vessel and
filtered using a 0.45 µm filter paper. The solids were returned to the leaching vessel while
the filtrates were analysed for copper and gold by ICP-OES or ICP-MS. At the end of each
experiment, leach residues were thoroughly washed with distilled water, dried and analysed
by fire assay for gold and by XRF for base metals. Extraction percentages for both copper and
gold were determined from re-calculated head grades.
3.3.6 Column Leaching

Laboratory heap leach experiments are generally performed using columns. Column leaching
in the laboratory, with or without recirculation of leaching solution, simulates percolation
59
leaching operations because conditions are similar to those in the heap. The column may be
considered as the centre of the heap with same conditions for air and access to leaching
solution (Mousavi et al., 2008). Column experiments can provide useful information about
different process variables (particle size, mineral type, chemical reactant, leach conditions,
etc.).
Heap simulation experiments were performed in columns fabricated from 5 mm thick

plexiglass. The column height was 1000 mm while the internal diameter was 90 mm. The
bottom of the column had a support flat base with multiple holes for solution discharge while
holding the solids. The support base also contains an air inlet which distributes air through
0.5 mm holes inserted along the diameter of the column base. The column is equipped with
a lid to minimize solution loss. The lid contains 2 holes, one for solution inlet and the other
for air escape.
Crushed, washed and dried quartz was placed at the bottom of the column for support and
air distribution. The ore was then added to the column and quartz was again placed on top
of the ore to assist in the homogeneous distribution of the leaching solution. The leaching
solution was delivered to the top of the column by a peristaltic pump. Solution percolated
through the ore by gravity and into a collection container from where it was re-circulated
through a side loop by the pump. The solution re-circulation and aeration rates for different
columns are given in Table 3.5.
Table 3.5 Solution and aeration rates for leaching columns
Column Ore mass, g Solution flow rate, L/h Air flow, L/min
Cu-Au ore C
5000 0.21 0.1
(Column 1 & 2)
Cu-Au ore D 2697.7 0.864 0.1
60
Table 3.6 Column leaching experimental setup
3.3.7 Solvent Extraction

Copper extraction and stripping experiments were carried out by mixing the required
volumes of organic and aqueous phases in a volumetric flask, and then equilibrating by
shaking in a thermostatic water bath shaker for the required time and at the established
temperature. The mixture was transferred to a separating funnel and, after phase
disengagement, the raffinate was separated and the equilibrium pH was measured with a
TPS 90FLMV field meter. The aqueous solutions were analysed by AAS using a Varian
61
SpectraAA. The concentration of copper in the organic phase was calculated from the
difference between the initial copper concentration in the PLS and its concentration in the
raffinate at fixed organic to aqueous (O:A) phase ratios. Figure 3.4 shows the phase
separation setup after solvent extraction.
To determine the fate of glycine after extraction, an aqueous solution was obtained by
dissolving a known mass of glycine in deionised water to which copper sulfate was added to
complex with the glycine at 1:3 molar ratio in a 100 mL volumetric flask. A sample of this
solution was taken for glycine determination. Solvent extraction with both extractants was
then performed. Glycine concentration was again determined after extraction.
Determination of free glycine concentration before and after extraction was performed with
a high pressure liquid chromatography UV-Vis after hydrolysis with HCl, neutralization with
NaOH, and then pre-column derivatisation to form adjunct compounds with high UV-Vis
absorption range(Llames & Fontaine, 1994; Rowan et al., 1992).
Stripping of the copper from loaded organic was carried out with different concentrations of
sulfuric acid solutions. Aqueous solutions containing the main elements at concentrations to
that of a typical return (30 g/L Cu and 180 g/L H2SO4) electrolyte associated with a
conventional electrowinning tank house operation were then used to simulate a stripping
circuit as obtained in the industry.
62
Table 3.7 Phase separation after solvent extraction
3.3.8 Precipitation
Copper precipitation as sulfide from the alkaline glycine solution was investigated by the
addition of NaHS. During the precipitation tests, the required stoichiometric mass of dry
NaHS powder was weighed and added to the copper glycinate solution. Copper
concentration in solution before and after precipitation was measured using AAS. The
particle size distribution of the precipitated solids was determined by means of laser
diffraction. The precipitate was dried and analysed by XRD to determine its mineralogy.
3.4 Instrumental Analysis

A variety of analytical methods were used for both solid and solution analysis. These methods
are well established in both academia and industry. A brief overview of the different
analytical methods and instrumentation used in this study are given and described below.
63
3.4.1 X-Ray Diffraction (XRD)
XRD is a rapid analytical technique used for the identification and quantification of phases in
a crystalline material (Böttger et al., 2000; Jenkins, 2000). The copper minerals used in this
project were analysed by XRD to identify the interested copper mineral and impurities phases
in each mineral specimen. The samples were finely ground (micronised) and homogenized to
get representative results.
The XRD technique is based on the principle that crystalline substance can behave as a three
dimensional diffraction grating for X-ray wavelengths similar to the spacing of the atomic-
scale crystal lattice planes. Monochromatic radiation interacts constructively with the sample
to produce diffracted x-rays according to Bragg’s law (relates the wavelength of the
electromagnetic radiation to the diffraction angle and the lattice spacing in a crystalline
sample) as expressed in Equation 3.1
𝑛𝑛λ = 2dsinθ (3.1)
where n is the order of diffraction, λ is the wavelength of the incident X-ray, d is the
interplanar spacing of the crystal, and θ is the angle of incidence.
As each mineral has a unique (fingerprint) d-spacing, scanning a sample through a range of
2θ angles and comparing the processed data with standard reference patterns, the
mineralogical phases present in the sample can be identified.
Mineral phase determination for samples used in this project were performed using a D8
Advance Bruker X-ray spectrometer at the John de Laeter Centre for Isotope Research of
Curtin University. X-ray data obtained from the spectrometer was analysed with TOPAS
software. Quantitative analysis results are given in Chapters 4 and 5 and spectrograms are
given in Appendix A. Although XRD is a widely used analytical technique in the mineral
industry, it however has some limitations. Only about a tenth of a gram of sample specimen
that must be ground into a powder is required; implying that the sample must be a
homogenous representation of the bulk. In multiphase specimens, not only a confusion in
pattern similarities may arise but also, some observed phases may not be found on
International Centre for Diffraction data (ICDD) powder diffraction files (Jenkins, 2000). XRD
also has difficulties in identifying phases that are less than several tenths of one percent
depending on the crystalline material being examined.
64
3.4.2 X-Ray Fluorescence (XRF)
XRF is a technique for analysing the elemental composition of materials (solid, liquid and thin-
film samples). The principle of XRF is based on the fact that, when an external energy source
is shone on atoms, they become excited and emit x-ray photons of a characteristic energy or
wavelength. Identification and quantification of the elements present in the sample is
achieved by counting the number of photons of each energy level emitted by the sample. As
any other analytical technique, XRF has limitations and detection limits (Kadachia & Al-
Eshaikhb, 2012). The ability of most commercially available XRF instruments is limited in the
precise and accurate determination of the abundance of elements with atomic number less
than 11. XRF is limited in differentiating disparity between isotopes of an element, and ions
of the same element in different valence states (Gill, 1997).
The XRF technique on feed and residue mineral/ore samples for this project was conducted
at Bureau Veritas analytical laboratories in Perth, Western Australia.
3.4.3 TESCAN Integrated Mineral Analyser (TIMA)

TIMA is high performance analytical scanning electron microscope that is capable of
automatically measuring modal abundance, size-by-size liberation, grain size and minerals
associations on multiple samples of polished sections, and thin sections or grain mounts. The
instrument is based on the MIRA Schottky field emission or thermal emission microscope
that has been integrated with an energy dispersive spectroscopy (EDS) system for full
spectrum, ultra-fast data acquisition. The acquired data is analysed and presented using the
TIMA software.
TIMA analysis for different samples was done using the Tescan TIMA GM model at the John
de Laeter Centre (JDLC) of Curtin University. The main limitation of TIMA would be the size
of the grains being analysed versus the step size that is used. Ideally, 8-10 pixels per grain is
needed to ensure grains or inclusions are not missed and also that enough EDS is collected
to accurately match the mineral definition files.
3.4.4 UV-Visible (UV-Vis) Spectrophotometry

This technique is based on the absorption of radiation in the visible or ultraviolet region.
Transition metals such as copper have partially filled d-orbitals with electrons relatively free
to absorb energy and be promoted to a higher energy level. The degree of absorption by a
65
sample at different wavelengths is recorded by a spectrometer and displayed as a plot of
absorbance against the wavelength. Each element has a characteristic wavelength at which
maximum absorption occurs. According to Beer Lambert’s law, the intensity of a beam of
monochromatic light passing via an absorbing substance linearly decreases as the
concentration of the absorbing substance increases.
The visible absorption spectra of the copper (II)-glycinate solutions were detected with a
Varian, Carry 50 UV-Visible spectrometer interfaced with a compatible PC. This technique has
been used in Chapter 5 for copper speciation.
3.4.5 Particle Size Analysis (PSA)

For experiments in which the sample particle size was assumed to be less than 20µm, the
Malvern laser diffraction particle size analyzer (at CSIRO Perth) was used to determine the
particle size distribution of the sample. The instrument is based on the principle that every
particle size has its own characteristic scattering pattern (as predicted by the Fraunhofel
model) when it passes through a laser beam. The major components of this equipment are:
the transmitter for production of laser beam, the sample area, and the receiver which collects
and stores the information received from the scattering of the analyser beam as it passes
through the sample. The collected data is then sent to a computer system for analysis and
interpretation by the Malvern software.
3.4.6 Atomic Absorption Spectrometry (AAS)

Atomic absorption spectrometry (AAS) is a very reliable and common method for
determining the concentration of metals and metalloids in liquid phase. The principle of AAS
is based on the fact that electrons of atomized elements can absorb light of specific
wavelengths and get promoted to higher orbitals (Platte, 1968). The amount of light
absorbed is proportional to the number of atoms of the particular metal ions present in the
sample.
Generally, the apparatus consists of a light source, a sample atomizer, a spectroscope, a

photometer, and a recording system. There is also a background compensation system.
Metal ions in solution are atomised by means of a flame. The flame source is a mixture of
acetylene (1.5 dm3/h) and air (3 dm3/h) which is then ignited to burn together with an
aspirated liquid sample. A light beam from a lamp whose cathode is of the element being
66
determined goes through the spectroscope where the wavelength slit is adjusted per
particular element. The monochrome light passing through the flame falls on a
photomultiplier that records the light intensity. The amount of radiation absorbed by the
sample is compared to a calibration curve constructed by running standard solutions of the
metal under similar conditions and this enables the computer unit attached to the AAS to
calculate the concentration of the element of interest in the sample (Levison). In this project,
an Agilent 55B AAS spectrometer has been used to determine most of the copper and gold
concentrations in solutions.
3.4.7 Inductively Coupled Plasma Optical

Emission Spectrometry (ICP-OES) and
Inductively Couple Plasma Mass
Spectrometry (ICP-MS)
Both ICP-OES and ICP-MS were used for determining the concentration of elements in
solutions in this project. In both techniques, a very high temperature plasma 6000~ 10000K
is produced by the interaction of an intense magnetic field passing on a tangential flow of
argon through a concentric quartz tube. Initially, the argon gas is partially ionised by a high-
voltage spark generating electrons and cations which are accelerated by the magnetic field
resulting in elastic ions-neutral collisions and thus forming a stable, high temperature plasma.
The sample being analysed is converted to an aerosol and sprayed into the centre of the
plasma (Batsala et al., 2012; Olesik, 1996). ICP-OES and ICP-MS differ from this point forward.
(Tyler).
ICP-OES, uses a diffraction grating to separate the light emitted by the plasma and, as each
element has its own distinct wavelength, elements in the sample can be determined and
quantified comparing the amount of emitted light to a calibrated range in the instrument.
In ICP-MS, the ions generated by the plasma are directed through a quadrupole mass
spectrometer which identifies and quantifies elements based on their mass-to-charge ratio.
ICP-OES is useful for measuring higher concentrations of elements while ICP-MS provides
lower detection limits (Sakata et al., 2001; Stankova et al., 2011; Thompson et al., 2008). The
detection capabilities of ICP depends on the technique of sample introduction which allows
different quantities of sample to reach the ICP plasma. Detection limits can also depend on
the sample matrix which can be affected by the extent of ionization in the chamber (Batsala
et al., 2012)
67
ICP-MS was used to determine gold concentrations (ppb) from leached solutions resulting
from the leaching of low grade copper-gold ores. Concentration of metals during solvent
extraction experiments was determined exclusively by ICP as AAS efficiency is affected by
organic reagents. ICP was also used in the determination of dissolved total sulfur and other
impurities in the final leach solution. ICP analysis were performed at CSIRO AMRC, WA and
Bureau Veritas Laboratories of WA.
3.4.8 High Performance Liquid Chromatography

(HPLC)
HPLC is generally used to separate, purify, identify and quantify components of a complex
mixture (McMaster, 2006). The separation is based on molecular structure and molecular
composition of the mixed substances. The liquid mixture to be separated is injected under
pressure through a stationary phase in the column in which mixture components having
stronger interactions with the stationary move more slowly through the column as compared
to components with weaker interactions. As the analytes elute the chromatographic column,
detectors (UV-Vis, fluorescence, mass spectroscopy, electrochemical) located at the end of
the column detect the component and send a signal to a computer which integrates the
signal and presents it in a chromatogram for easy interpretation. The accuracy of HPLC
depends on the efficiency of the column and the sensitivity and selectivity of the detection
system (Lawrence, 1987).
In this project, HPLC was used to determine the concentration of free glycine before and after
solvent extraction and sulfur speciation for sulfide containing ore leach solutions. The HPLC
was outsourced to the ChemCentre of Western Australia. The HPLC instrument used for the
analysis was an Agilent, 1100 series model.
3.4.9 Scanning Electron Microscopy (SEM)

In SEM, high energy electrons impinged as a beam on the surface of a sample interact with
particles on the surface to produce signals that are used to generate information about
composition and topography of the surface. The major components of SEM are the electron
beam generator, column with electromagnetic lenses for electron travel, sample chamber
under vacuum, electron detector and computer display for image viewing (Egerton, 2005).
Surface qualitative and quantitative analysis were performed by the use of an Energy
68
Dispersive X-ray Spectrometer (EDS). As the sample is being bombarded with the electron
beam, vacancies created by ejected electrons are filled by electrons from a higher state. This
process emits an X-ray to balance the energy between the different electron states. The X-
ray energy is characteristic of the element from which it is emitted. The emitted X-ray is
detected by the EDS detector and the relative abundance of the X-rays versus their energy is
measured to evaluate elemental composition of the sample.
Most SEM instruments are limited in that samples must be analysed under a stable vacuum
of 10-5 to 10-6 torr. Also, many SEM instruments cannot detect elements whose atomic
numbers are less than 11. Electrically non-conductive samples being analysed in
conventional SEMs must be coated with a conductive coating to avoid electron build-up on
sample surface otherwise poor resolution results.
Scanning electron microscopy analysis was used to study the changes in the surface
morphology of some minerals during and after leaching. These analyses were performed at
The John de Laeter Centre of Curtin University using the NEON FIB-SEM, Zeiss manufactured
Neon 40ESM model. It was operated at 5.0 kV with a beam aperture size of 30.0 µm.
3.4.10 X-Ray Photoelectron Spectroscopy

X-ray photoelectron (XPS) spectroscopy is a surface sensitive analysis technique that uses the
photoelectric effect to identify and quantify elements on the surface of materials. This
analysis is sensitive to the first 2-5 nanometres of the sample. The instrument focuses an X-
ray beam at the target material; photoelectrons are ejected from the atoms of the material
with a specific kinetic energy depending on their atom of origin. By measuring this kinetic
energy, the identity of the origin atom is found and the number of electrons measured at
that energy provides information about how much of this element is present.
Two spectral regimes can be produced by XPS: survey spectra and high resolution spectra.
The survey spectra allow the identification and quantification of the elements on the surface;
whereas, the high resolution spectra allow the identification and quantification of the
bonding associated with an element.
XPS analysis in this project were performed using a Kratos AXIS Ultra DLD model at the John
de Laeter Centre (JDLC) of Curtin University. The electron take off angle was normal to the
sample surface. Spectra were interpreted using the software package CasaXSP.
69
3.4.11 Miscellaneous Analysis
Fire assay for gold content determination in the feed and residue of different gold-copper
samples was conducted by Bureau Veritas laboratories of Western Australia.
3.4.12 Auxiliary Equipment

One of the most important equipment used through out the research was the TPS 90FL-T
meter used for measuring both pH and the oxidation reduction potential of solutions. A
mercury thermomter was also important in measuring solution temperatures
70
Chapter 4 Differential Leaching
Behaviour of Copper
Minerals: Towards a
Geometallurgical Indicator
4.1 Chapter Objectives and Background
In Chapter 1, it was indicated that copper grades in common ore bodies are gradually
dwindling with copper content of less than 1.0 % no longer being the exception but the rule.
Moreover, the low copper grade is constituted of a multitude of copper minerals such as
chalcocite, covellite and chalcopyrite in the hypogene and supergene layers and many oxides
in the leached oxide cap. Processing of such complex ores challenges plant operators because
each mineral is likely to respond differently to comminution, flotation or leaching. It is well
known that copper minerals have different solubility in different leaching systems as was
obtained by Hedley and Tabachnick (1968) for cyanide solutions. Oraby and Eksteen (2014b),
using an alkaline glycine solution, reported that copper could be selectively leached from
gold in a copper-gold gravity concentrate. In both cases, it was established that the oxide
minerals were completely leached, while sulfide minerals were only partially leached. Oraby
and Eksteen (2014b), rather, used a bulk sample in which the phase concentrations of the
copper minerals was identified before and after the leaching process without further
research on the behaviour of individual mineral.
The main objective of this chapter is to investigate and understand the leaching behaviour of
individual copper minerals in alkaline glycine solutions at ambient temperature and
atmospheric pressure. The effects of reagent concentration and initial solution pH were also
investigated. To do this, it was imperative that each mineral specimen contained only a single
copper mineral phase (although other non-copper-bearing gangue minerals were
acceptable). The dissolution behaviour of azurite, malachite, cuprite, chrysocolla, metallic
copper, chalcocite and chalcopyrite in alkaline glycine solutions have been studied and
reported in order to discriminate amongst the leach behaviours of the different minerals
rather than study the detailed kinetics of each mineral. As such, it is a study of the
geometallurgical response of copper minerals in alkaline glycine solutions.
The dissolution procedure outlined in Chapter 3 indicates that all experiments in this chapter
71
were performed with a conventional bottle roll. Bottle rolls had the limitation that oxidation
(only air through neck of bottle) and temperature could not be controlled. The batch nature
experiments are generally limited as reactants get consumed to form products and
equilibrium concentrations may be reached whereas continuous product withdrawal and
reagent addition in real systems forces dissolution/leaching reactions. Bottle rolls are thus
inadequate for process set point determination or optimization. The following sections cover
the mineralogy and chemistry, the effect of glycine concentration, the effect of pH, and the
effect of oxidants on the leaching of each copper mineral in alkaline glycine solutions.
4.2 Azurite
Azurite is a secondary copper mineral often found in the oxidized zones of copper bearing
ore deposits. It is a copper-carbonate-hydroxide mineral with a chemical composition
2CuCO3·Cu(OH)2. Single crystals of azurite are dark, royal blue and the mineral exhibits a
brilliant azure blue colour when it is of dull or earthy luster.
4.2.1 Mineralogy and Elemental Composition

The azurite specimen obtained from a mineral collector in Australia was analysed for its
mineralogical and elemental composition. The XRD analysis of this mineral specimen
indicates that the specimen contains 65.0 % azurite which is the only copper mineral phase
present in the specimen. The elemental analysis of the azurite sample was done by XRF and
the results are shown in Table 4.1. It can be seen that the specimen has 42.1% copper and
the rest represents the impurities in the sample.
Table 4.1 Mineralogical and chemical composition of azurite
Phase Azurite Kaolinite- Muscovite- Quartz Amorphous

Mineralogy 1A 2M1 Content
wt % 65 3.4 6.2 7.4 18
Chemical Metal Cu (%) Al (%) Si (%) Zn (ppm) K (%)

composition Value 42.1 1.9 6.4 50 0.6
72
4.2.2 Effect of Initial Glycine Concentration
To evaluate the effect of glycine concentration on the dissolution of copper from azurite
mineral specimen, the initial solution pH was kept constant at 11.0 while glycine
concentration was varied based on a glycine to copper (Gly: Cu) molar ratio. Ratios were
chosen over molar concentration because the stable copper-glycine complex between pH 4
and 12 is Cu(H2NCH2COO)2, implying that a minimum of two moles of glycine are needed for
each mole of copper for the complex formation. The Gly:Cu ratios investigated were 2:1, 3:1,
4:1 and 8:1. This approach will be followed throughout this chapter. The grind for the azurite
specimen was 100 % passing 75 µm and the % solids was 0.95 w/v (Table 3.3). The influence
of the glycine concentration on copper extraction from azurite is shown in Figure 4.1. The
percentage of copper extraction is observed to increase as the Gly:Cu increases. When the
Gly:Cu is 2:1, the highest copper extraction is just 73.0 % over 48 hours, and when the ratio
is 8:1, 98.0 % copper is extracted in just over 2 hours (the copper concentrations at which the
stated extraction percentages are calculated from are given in Appendix H). From these
results, a Gly: Cu ratio of 4:1 was then chosen as for further investigations.
100
90
80
Cu extraction, %
70
60
50
Gly: Cu= 2:1
40
Gly: Cu= 3:1
30
Gly: Cu= 4:1
20
Gly: Cu= 8:1
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.1 Effect of initial glycine concentration on the dissolution of copper from azurite: pH 11,
P100 75 µm and % solids 0.95 % w/v
4.2.3 Effect of Initial Solution pH

To study the relationship between copper dissolution from azurite and the initial leach
solution pH, the initial pH was varied from 8.0 to 11.0 using sodium hydroxide. During the
73
duration of the experiments, the pH was monitored but uncontrolled. Initial Gly:Cu molar
ratio was kept constant at 4:1. Figure 4.2 shows that, after 1 hour, leaching at pH 10 has a
higher copper dissolution of 77.7 % compared to 66.3% at pH 11. However, after 3 hours of
leaching, copper extraction at pH 11 exceeded that of solution pH 10. It can actually be seen
that dissolved copper at pH 10 started to decrease as this was associated to a light blue
precipitate formation. The observed drop out of copper from solution could be attributed to
both the solution pH and the copper concentration in solution as shown in Figure 4.3. It is
supposed that the precipitate is a copper glycinate complex as it redissolved when the
solution was heated at 50 °C while mixing. The precipitation of Cu(Gly)2 has also been
reported by (Gyliene, 2001) when investigating the removal of heavy metals in solutions by
complexing them with glycine and EDTA. The metal complex was then reported to precipitate
after several hours or days. She also reported that the precipitation is influenced by
temperature, pH and concentration of components. The production of Cu-glycinate
powdered has been described to occur through the formation of a Cu-glycinate complex and
then causing it to precipitate by adding ethnol (Imamura et al., 1978). Thus, depending on
the temperature, pH and copper concentration, the Cu-glycinate complex has an upper limit
of solubility in alkaline solutions. It could thus be concluded that, for azurite, under the given
conditions: a copper concentration of more than 3.1 g/L, at pH 10.2 and at 25 °C, copper
precipitates as Cu(Gly)2.
100
90
80
70
Cu extraction, %
60
50
40
initial pH 10
30
20 Initial pH 11
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.2 Effect of initial leach solution pH on copper dissolution from azurite: Gly:Cu 4:1, P100 75
µm and % solids 1.95 % w/v
74
[Cu] at pH 10 [Cu] at pH 11 pH change from 10 pH change from 11
4.5
4.0 12.5
3.5
11.5
[Cu] ,g/L 3.0
2.5 10.5
pH
2.0
9.5
1.5
1.0
8.5
0.5
0.0 7.5
0 6 12 18 24 30 36 42 48
Time,h
Figure 4.3 Correlation between the change in copper concentration and pH change during leaching
of azurite: Cu:Gly 1:4, P100 75 µm and % solids is 0.95 % w/v
The general leaching reaction of azurite can be written as in Equation 4.1:
2(CuCO3)·Cu(OH)2 + 6(NH2CH2COO-) → 3[Cu(NH2CH2COO)2] + 4OH- + 2CO32- (4.1)
4.3 Malachite A
Malachite is a copper carbonate hydroxide mineral with the formula CuCO3.Cu(OH)2. It is
green, has a monoclinic crystalline structure and generally results from the weathering of
copper ores and often occurs together with azurite. It is a very common secondary copper
mineral in the oxidation zone of copper ore deposits and can also be associated with
limestone copper deposits (Henn & Milisenda, 2004).

The XRD of the malachite specimen A shows malachite as the only copper mineral present in
the tested specimen. Quantitative mineralogy of other mineral phases present and the
chemical composition of the sample is given in Table 4.2.
75
Table 4.2 Mineralogy and chemical composition of Malachite A
Mineralogy Chemical composition

Phase weight % Element %
Goethite 1.7 Cu 41.6

Hematite 3.3 Al 0.1
Malachite 66.0 K 0.1
Quartz 16.7 Mg 0.4
Amorphous Content 12.0 Fe 3.5
Ca 0.8

The effect of glycine on the dissolution of copper from Malachite A was investigated by
varying the Gly:Cu molar ratio from 2:1 to 8:1 while keeping the initial leach solution pH at
11. The mineral specimen was ground to a P100 of 75 µm and the solids content during
leaching was 1.62 % w/v. The results as illustrated by Figure 4.4 show that copper dissolution
increases as the Gly:Cu ratio increases. In the first hour of leaching, copper extraction at
Gly:Cu molar ratio of 2:1, 3:1, 4:1, and 8:1 was 52.0, 72.0, 81.0 and 87.0 %, respectively. This
is not surprisingly, as increasing the glycine concentration means more glycinate anions were
available on minerals surface to leach copper.
100
90
80
70
Cu extraction,%
60
50
Gly:Cu= 2:1
40
Gly:Cu= 3:1
30
Gly:Cu= 4:1
20
Gly:Cu= 8:1
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.4 Effect of initial glycine concentration on the dissolution of copper from malachite A: pH
11, P100 75 µm and % solids is 1.62 % w/v
76
The influence of initial leach solution pH was studied by varying the pH from 9.5 to 11 while
keeping the Gly:Cu molar ratio constant at 4:1. Higher copper dissolution was noted at higher
pH as shown in Figure 4.5. It was also observed that, at the lower pH of 9.5, copper
concentration begins to decrease after three hours of leaching as copper glycinate
precipitate is produced. As can be noticed in Figure 4.6, the precipitation of crystalline copper
glycinate from the leach solution at initial pH of 9.5 starts to occur at a copper concentration
of 2.5 g/L and at a pH of 9.26.
100
90
80
Initial pH 9.5
70
Cu extraction, %
60
Initial pH 11.0
50
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.5 Effect of initial solution pH on the dissolution of copper from malachite A: Gly:Cu 4:1,
77
[Cu] at pH 9.5 [Cu] at pH 11
pH change from 9.5 pH change from 11
4.5
12.5
4.0
3.5
11.5
3.0
[Cu] ,g/L
pH
2.5 10.5
2.0
9.5
1.5
1.0
8.5
0.5
0.0 7.5
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.6 Correlation between the change in copper concentration and pH change during the
leaching of malachite with glycine
The general leaching reaction of malachite can be written as in Equation 4.2
2(CuCO3).Cu(OH)2 + 6NH2CH2COO- → 2[Cu(NH2CH2COO)2] + 2OH- +

2CO32- (4.2)
4.4 Cuprite
Cuprite is an oxide mineral of copper with the formula Cu2O. It occurs in the oxidized zone of
copper deposits in association with tenorite, malachite, azurite, calcite, brochantite,
antlerite, atacamite, chrysocolla, iron oxides and clay minerals. Optically, it is transparent to
translucent with colors from cochineal-red, purplish red to nearly black. It is obtainable in
cubic, octahedral and dodecahedral crystals with an interrupted cleavage and conchoidal to
uneven fracture (Anthony et al., 1995). Cuprite notably occurs in USA, Africa, Chile, Australia
and Europe.

The mineralogy of the cuprite mineral specimen including other phases and the chemical
composition of the cuprite sample are presented in Table 4.3 as determined by XRD and XRF
78
Table 4.3 Mineralogy and chemical composition of cuprite
Mineralogy Phase Cuprite Dolomite Goethite Quartz Amorphous

Content
weight % 23.4 62.1 0.5 1.0 27.0
Chemical Element Cu Si Mg Fe Ca
composition
% 20.1 0.5 9.6 1.9 16

The effect of glycine concentration on copper dissolution was investigated by varying the
Gly:Cu molar ratio from 2:1 to 8:1 while keeping the initial leach solution pH constant at pH
11. Figure 4.7 shows that, as the Gly:Cu molar ratio increases, the percentage of copper
extracted increased. After 24 hours of leaching, it was found that there is no significant
difference between the amount of copper extracted at Gly:Cu ratios of 8:1 and 4:1 (85.6 %
and 84.2 %, respectively). The copper extraction was only 68.1 % and 75.9 % at Gly:Cu molar
ratios of 2:1 and 3:1, respectively.
100
90
80
70
60
Cu extraction,%
50 Gly: Cu= 2:1
Gly: Cu= 3:1

40
Gly: Cu= 4:1
30
Gly: Cu= 8:1
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.7 Effect of initial glycine concentration on copper dissolution from cuprite mineral
specimen: pH 11, P100 75 µm and % solids 1.99 % w/v

The effect of initial leach solution pH on copper dissolution was investigated at pHs 9.0, 10.0
and 11.0. The Gly:Cu molar ratio was at 4:1 for all experiments. The results, as shown in
Figure 4.8, indicate that the highest copper dissolution is obtained at pH 10, yieling 48.0 %
after one hour of leaching and 97.0 % after 48 hours. During the same period at pH 11, 33.1
79
% Cu dissolution was obtained in the first one hour and increased to 93.0 % after 48 hours. A
copper extraction of 40.0 % was obtained at pH 9.0 in the first hour of leaching and increased
to 72.0 % after 6 hours. After this point, the copper content in solution decreased to 45.0 %
after 48 hours presumably due to the precipitation of cupric glycinate. This is the same
observation noted for the azurite and malachite at lower pHs. Figure 4.9 continues to suggest
that copper precipitation at different pHs only occurs at a higher copper concentration (3.0
g/L for cuprite at pH 9).
100
90
80 Initial pH 9.0
70 Initial pH 10.0
Cu extraction, %
60
Initial pH 11.0
50
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.8 Effect of initial pH on copper dissolution from cuprite: Gly:Cu 4:1, P100 75 µm and %
solids 1.95 % w/v
[Cu] at pH 9 [Cu] at pH 10 [Cu] at pH 11
pH change from 9 pH change from 10 pH change from 11

4.5
4.0 12.5
3.5
11.5
3.0
[Cu], g/L
2.5 10.5
pH
2.0
9.5
1.5
1.0
8.5
0.5
0.0 7.5
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.9 Correlation between copper concentration and leach solution pH during the leaching of
cuprite with glycine
80
The general leaching reaction of cuprite can be written as in Equation (4.3)
Cu2O + 4NH2CH2COO- + 2H2O + 1/2O2 → 2[Cu(NH2CH2COO)2] + 4OH- (4.3)
4.5 Chrysocolla
Chrysocolla is a hydrous silicate copper mineral having the formula CuO·SiO·2H2O. It has a
green to sky-blue, non-crystalline structure and amorphous silica gel or a gelatinous
precipitate. Chrysocolla is relatively soft with a hardness of 2-4 on Mohs scale. It has no
cleavage and shows an uneven or conchoidal fracture which is typical of glassy, amorphous
materials. As with other oxidized copper minerals, it is found in the oxidized zones of copper
veins and occurs in association with azurite and malachite (Anthony et al., 2001).

XRD identified chrysocolla as the only copper phase. Rietveld refinement software could not
be used for the quantitative weight % analysis of the identified chrysocolla phase as its
inorganic crystal structure database (ICSD) file was not available. However, from the
percentage copper obtained from an XRF analysis and considering the chemical formula of
chrysocolla to be CuO·SiO2·2H2O, the percentage of chrysocolla in the sample was calculated
to be the whole 59.0 % of the amorphous phase. The mineralogical and chemical composition
of the chrysocolla sample is shown in Table 4.4
Table 4.4 Mineralogical and chemical composition of chrysocolla specimen
Mineralogy Elemental composition

Phase weight % Element %
Kaolinite-1A 6.0 Cu 24.7

Muscovite -1M 13.5 Si 21.6
Muscovite -2M 12.8 Al 3.0
Quartz 6.7 k 1.4
Rutile 1.8 Ti 0.1
Chrysocolla 59.0 Mg 0.4
81
Figure 4.1 shows the insignificant effect of glycine concentration on the dissolution of copper
from chrysocolla. P100 is 57 µm and % solids is 1.62 % w/v. An increase in Gly:Cu molar ratio
from 2:1 to 4:1 results in only 12.0 and 19.0 % of copper extraction respectively. The leaching
of chrysocolla has been reported to be generally slow requiring extended leaching times
(Davenport et al., 2002a)
100
90
80 Gly:Cu 2:1
Cu extraction, %
70
60 Gly:Cu 3:1
50
Gly:Cu 4:1
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.10 Effect initial glycine concentration on chrysocolla leaching; pH 11, P100 75 µm and %
solids is 1.62 % w/v
4.5.3 Effect of Initial solution pH

The effect of initial leach solution pH was studied by varying the pH from 8.0 to 11.0 while
Gly:Cu molar ratio was maintained at 4:1. The results in Figure 4.1 show that lower pH favors
copper dissolution with 26.0 % of copper dissolution at pH 8.0 as compared with 19.0 % at
pH 11. It was observed that the leaching of azurite, malachite and cuprite at lower pHs
resulted in copper precipitation. With these oxides, copper precipitation was noted to start
occurring at about 2.8 g/L copper in solution. Figure 4.12 shows that as the maximum copper
concentration in solution is 1.07 g/L at pH 8, there is no precipitation. This observation
confirms the proposition that copper precipitation is not only a function of pH alone but that
it would only occur when the concentration in solution is above a certain level (2.7 to 3 g/L
as previously observed).
82
100
90
80 initial pH 8.0
70
Cu extraction, %
Initial pH 9.5
60
Initial pH 11.0
50
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time,h
Figure 4.11Effect of initial leach solution pH on chrysocolla leaching: Gly:Cu 4:1, P100 75 µm and %
solids 1.62 % w/v
[Cu] at pH 8 [Cu] at pH 9.5 [Cu] at pH 11
change in pH from 8 change in pH from 9.5 change in pH from 11

4.5
4.0 12.5
3.5
11.5
[Cu],g/L
3.0
2.5 10.5
2.0
pH
9.5
1.5
1.0
8.5
0.5
0.0 7.5
0 6 12 18 24 30 36 42 48
Time,h
Figure 4.12 Correlation between [Cu] in solution and change in solution pH during glycine leaching
of chrysocolla
The very low dissolution of chrysocolla is not uncommon in alkaline lixiviants. Leaching of
chrysocolla in ammoniacal carbonate solutions reported only a 50.0 % of the total copper
content (Warren & Devuyst, 1973). Wei et al. (2010) noted that, of all the copper minerals
leached in ammonia-ammonium chloride solutions, copper silicates exhibited the poorest
propensity to be leached. SEM results of the unleached and leached chrysocolla specimen in
alkaline glycine solution (Figure 4.13) showed that the leach residue developed a spike-like
surface morphology. This can be attributed to the concept that as the copper from
chrysocolla is leached, an impervious layer of hydrated silica is left behind which restricts
further copper leaching (Tanda et al., 2017).
83
(a) (b)
Figure 4.13 SEM photographs of unleached (a) and partially leached (b) chrysocolla
The general leaching reaction of cuprite can be written as in Equation 4.4:
CuO·SiO2·2H2O + 2(NH2CH2COO-) → Cu(NH2CH2COO)2 + H2O + 2OH- +

(4.4)
SiO2
4.6 Metallic Copper

Metallic (native) copper can be found in association with copper minerals such as cuprite. In
addition, an important source of metallic copper is from urban mining through the recycling
of electrical and electronic equipment waste, demolished buildings, manufacturing offcuts
as they contain substantial amounts of iron, lead, copper and other metals (Ping et al., 2009).
Hydrometallurgy has been indicated as one of the best options for copper recovery and
precious metals from electronic waste as the metal occurs with impurity elements requiring
a selective leaching approach (Koyama et al., 2006).

Experiments to determine the influence of glycine concentration on the dissolution of
metallic copper were conducted by leaching 2 g of 100 % passing 75 µm pure copper in
solutions containing different initial concentrations of glycine at pH 11 for 48 hours.
Hydrogen peroxide at a concentration of 0.5 % was added to the leach solution to enhance
84
the oxidation process. Figure 4.14 shows that, as the Gly:Cu ratio increases from 2:1 to 4:1,
the copper concentration in solution over time also increases. After 48 hours of leaching, a
copper dissolution of 91.7, 89.2, and 82.8 % was recorded for Gly:Cu ratios of 4:1, 3:1 and
2:1, respectively.
100
90
80
70
Cu extaction, %
60
50 Gly:Cu 2:1
40
Gly:Cu 3:1
30
Gly:Cu 4:1
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.14 Effect of initial glycine concentration on metallic copper dissolution: pH 11, 0.5 % H2O2,

The effect of initial leach solution pH was investigated by varying the initial pH from natural
glycine pH (5.8), pH 8 and pH 11 with NaOH as a pH modifier. A Gly:Cu molar ratio of 4:1 and
0.5 % H2O2 concentration was maintained for all experiments. The results shown in Figure
4.15 illustrate that higher solution pHs favour the dissolution of metallic copper. At the
natural pH of 5.8, the percentage of copper dissolved gradually increases to a maximum of
51.4 % after 24 hours and then declines to 29.7 % at the end. For pHs 8 and 11, there is a fast
dissolution with 57.1 % and 59.8 % copper dissolution respectively in 6 hours. Copper content
in solution at pH 8.0 then decreased to 33.7 % and 26.4 % after 24 and 48 hours, respectively.
At pH 11, copper precipitation did not occur over the same period and the copper dissolution
reached 91.7% after 48 hours.
85
100
90
80
Initial pH 5.8
70
Cu extraction, % Initial pH 8.11
60
50 Initial pH 11.04
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.15 Effect of initial solution pH on metallic Cu dissolution; Gly:Cu 4:1, 0.5 % H2O2, , P100 75
µm and % solids 0.40 % w/v
4.6.3 Effect of Hydrogen Peroxide

The effect of hydrogen peroxide as an oxidising agent on the metallic copper dissolution was
studied by varying the initial peroxide concentration from 0 %, 0.1 %, 0.5 % and to 1.0 %. For
all experiments, Gly:Cu ratio was kept at 4:1 and the leach pH was kept at 11. Although a very
small improvement in copper dissolution was noted as H2O2 concentration increased in the
first hour of leaching, H2O2 had no significant overall effect on metallic copper dissolution as
shown in Figure 4.16. Initial hydrogen peroxide concentrations of 0, 0.1, 0.5 and 1.0 resulted
in 88.3, 92.2, 91.7 and 91.2 % copper leaching respectively. This observation implies that
oxygen from air entering the bottle provides sufficient oxidant for copper oxidation. It should
however be noted that hydrogen peroxide rapidly converts to ·OH radicals which have been
reported to oxidise glycine (Berger et al., 1999). The use of hydrogen peroxide should be
avoided since it has no significant effect on copper leaching but can rather degrade the
lixiviant.
86
100
90
80
70
Cu extraction, %
60
50
0% peroxide
40
0.1% peroxide
30
0.5% peroxide
20
1% peroxide
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.16 Effect of peroxide on metallic Cu dissolution: Gly:Cu 4:1, pH 11, , P100 75 µm and %
solids 0.40 % w/v
The general leaching reaction of metallic copper can be written as in Equation 4.5:
Cu + 2(NH2CH2COO-)+ 1/2O2 + H2O → Cu(NH2CH2COO)2 + 2OH- (4.5)
4.7 Chalcocite A
Chalcocite, copper(I) sulfide is a dark grey copper mineral which is commonly found in the
supergene enriched environment beneath the oxidized zone of porphyry copper deposits
due to copper leaching from the oxidized zone. Due to its high copper content and the
relative ease to separate sulfur, it is a very profitable copper mineral to mine (Frost et al.,
2007; Howard T. Evans, 1979). Most rich chalcocite deposits have generally been mined but
valuable deposits of chalcocite are found in Ely-Nevada, Morenci-Arizona, Butte-Montana
and Tsumeb-Namibia (Encyclopædia Britannica, 2016). A modern example of a chalcocite
deposit that is currently being mined is Las Cruces in Sevilla-Spain where open pit mining is
practiced. The ore is crushed and atmospherically leached in agitated reactors. This is
followed by solvent extraction and then electrowinning to produce copper cathode (First
Quantum Minerals; Tornos et al., 2017).
87
Table 4.5 shows the mineralogical and elemental composition of the chalcocite specimen
used for investigating the dissolution of chalcocite in alkaline glycine solution. The chalcocite
mineral specimen contains 98.2 % chalcocite as the only copper mineral peak indicated by
the Q-XRD analysis. Elemental composition of the specimen confirmed its high purity with a
percentage copper being 78.8 % and 20.2 % sulfur.
Table 4.5 Mineralogy and elemental composition of chalcocite A
Mineralogy Phase Chalcocite Quartz Amorphous content

weight % 98.2 0.6 0.2
Elemental Element Cu S Si
composition
% 78.8 20.2 0.2

The influence of glycine concentration on the chalcocite dissolution was studied by varying
the Gly:Cu molar ratio from 2:1 to 8:1 in a solution containing 0.5 % H2O2 at pH 11. Figure
4.17 shows that, at higher Gly:Cu molar ratio, the copper dissolution from chalcocite sample
was enhanced. After 48 hours of leaching, the maximum copper dissolution was 46.5 % at a
Gly:Cu ratio of 8:1. The observed results indicate that the initial leaching rate of chalcocite
(6 hours) in the alkaline glycine solution is very fast after which the rate is significantly slow.
Such leaching trends have also been reported during chalcocite leaching in both acidic and
alkaline solutions (Cheng & Lawson, 1991; Naderi et al., 2011; Salvador, 1978). It is generally
accepted that the first step involves the conversion of chalcocite at the surface to copper
ions and a covellite residue which leaches rather slowly as indicated in Equations 4.6 and 4.7.
88
100
90
80
Gly: Cu 2:1
70 Gly:Cu 3:1
60
Cu extraction, %
Gly:Cu 4:1
50 Gly:Cu 8:1
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.17 Effect of initial glycine concentration on the dissolution of chalcocite A: pH 11, 0.5 %
H2O2, P100 75 µm and % solids 0.51 % w/v
Cu2S + 2(NH2CH2COO-)+ 1/2O2 + H2O → Cu(NH2CH2COO)2 + CuS +

(4.6)
2OH-
CuS + 2(NH2CH2COO-)+ 2O2 + H2O → Cu(NH2CH2COO)2 + SO4 + 2OH- (4.7)

Figure 4.18 illustrates the dissolution behaviour of chalcocite under varied initial leach
solution pHs. Copper dissolution at pH 9 and 10 is 38.0 and 41.0 % after 1 hour of leaching
and does not change even after 48 hours of leaching. At pH 11, initial copper dissolution is
rather slow with just 19.0 % obtained after 1 hour. However, copper extraction gradually
increases over time up to 24 hours (38.0 %) at which it plateaus to 41.0 % at 48 hours. This
observation continues to indicate that surface chalcocite rapidly converts to copper ions and
residual covellite which leaches very slowly. At low solution pH, no copper precipitation is
observed as was observed with metallic copper and oxide ores. The absence of precipitation
during chalcocite leaching further confirms that copper precipitation would only occur at pH
lower than 9.5 when copper content in solution increases above ~ 3 g/L as seen in Figure
4.19.
89
100
90
pH 9
80
pH 10
70
pH 11
Cu extraction, % 60
50
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time,h
Figure 4.18 Effect of initial solution pH on the dissolution of chalcocite A: Gly:Cu 4:1, 0 % H2O2, P100
75 µm and % solids 0.51 % w/v

change in pH from 9 change in pH from 10 change in pH from 11
5.0 14
4.5
12
4.0
3.5 10
3.0 8
2.5
2.0 6
1.5 4
1.0
2
0.5
0.0 0
0 6 12 18 24 30 36 42 48
of chalcocite

The influence of hydrogen peroxide as an oxidising agent during chalcocite dissolution was
investigated by varying the initial peroxide concentration in the leaching solution. Figure 4.20
shows that, although the initial copper dissolution was higher with 0.5 % and 1.0 % peroxide,
i.e. 19.0 % compared to 7.0 % Cu at 0 % peroxide, copper dissolution was found to be
independent of peroxide concentration after 6 hours with all solutions resulting in 26.0 %
90
extraction. The final copper extraction for all solutions after 48 hours was between 42.0 %
and 43.0 %. The percentage copper extraction in the absence of hydrogen peroxide being
equal to that extracted in the presence of hydrogen peroxide after 6 hours of leaching could
be attributed to the hydrogen peroxide being used up or decomposed in the first few hours
of leaching. Rapid decomposition of hydrogen peroxide has been reported in the presence
of Cu2+ ions (Antonijević et al., 1997; Turan & Altundoğan, 2013). Further chalcocite oxidation
was accomplished by dissolved oxygen from air.
100
90
80
0% peroxide
70
0.5% peroxide
Cu extraction, %
60
50 1% peroxde
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.20 Effect of peroxide on chalcocite A dissolution: Gly:Cu 4:1, pH 11, , P100 75 µm and %
solids 0.51 % w/v
4.7.5 Effect of Additives

Various additives such as sodium chloride, sodium nitrate, sodium sulfite and persulfate have
been reported to enhance the dissolution of copper from chalcocite in acidic or alkaline
environments.
A review of the beneficial effect of chloride on the leaching of copper from sulfides in
oxygenated sulfuric acid (Senanayake, 2009) indicated that the presence of chloride leads to
the formation of a porous crystalline sulfur layer instead of a non-porous sulfur. Vračar et al.
(2003) investigated the influence of sodium nitrate on chalcocite leaching in sulfuric acid and
noted that the leaching rate increases as NaNO3 increases.
Persulfate has been used as a strong oxidant for the recovery of metals in alkaline solutions
91
(Liu et al., 2012c; W. Reed, 2004). The addition of persulfate during ammoniacal leaching of
copper from spent lithium batteries greatly enhances the leaching rate (Dun-Fang et al.,
2009).
The effect of all these additives on the dissolution of chalcocite in alkaline glycine was studied
at high and low values and the results are presented in Figure 4.21. As observed from the
results, none of the additives had a significant positive effect on copper dissolution from
chalcocite in alkaline glycine solutions. This observation suggests that the limited copper
dissolution when 40.0 % Cu has been extracted is not a consequence of surface precipitation.
It was, however, noted that Pb(NO3)2 had a large negative effect on copper leached into
solution. Oishi et al. (2008) remarked that metallic lead can be easily oxidised by Cu (II) ions
to Pb species in ammoniacal solutions. Also, with glycine having been reported to form
complexes with Pb (Maeda et al., 1979), some of the glycine that could have been available
to form Cu(Gly)2 or drive the forward reaction was used up to form the Pb(Gly)2 complex
while Cu (II) ions acting as oxidising agent were being reduced.
60
50
40
Cu extraction, %
30
No additives
20 10 g/L NaCl
10 g/L NaNO3
10 g/L Pb(NO3)2
10
Pre-condition_Na2SO3
Pre-Condition_persulfate
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78
Time, h
Figure 4.21 Effect of additives on copper dissolution from chalcocite A: Gly:Cu 4:1, pH 11, 0 %
H2O2, P100 75 µm and % solids 0.40 % w/v
92
4.8 Chalcopyrite A
Chalcopyrite with a general chemical formula of CuFeS2 is the most abundant copper bearing
mineral but it is also the most recalcitrant to leach (Parker et al., 2003). Chalcopyrite is a
golden yellow metallic mineral. It is the principal mineral of porphyry-copper deposits
occurring in hydrothermal veins and disseminations.

The mineralogical and elemental composition of the chalcopyrite sample was analysed by
XRD and XRF spectrometry with the results shown in Table 4.6. Chalcopyrite is the only
copper mineral as indicated by the spectrograph (appendix) composing 35.0 % by weight.
The percentage copper in the sample is 14.8 % and the presence of 30.8 % Fe mostly as pyrite.
Table 4.6 Mineralogical and elemental composition of chalcopyrite A
Mineralogy Elemental composition

Phase Wt % Element %
Chabazite 0.8 As 0.709
Chalcopyrite 35 Ca 0.307
Clinochlore 1.5 Cu 14.810
Pyrite 29.4 Fe 30.870
Quartz 0.9 Mg 1.079
Rutile 0.4 Pb 0.289
Amorphous Content 32 Si 3.641
S 32.400
Zn 4.950

The effect of glycine concentration was studied by varying the Gly:Cu ratio from 2:1, 3:1, 4:1
to 8:1. Initial solution pH and peroxide concentration were 11 and 0.5 % for all experiments
and the samples were leached extensively for over 800 hours on a bottle roller. The trend as
illustrated in Figure 4.22 shows that increasing the glycine concentrations results in higher
copper dissolution. A significant increase in copper extraction was observed after 266 hours
of leaching at which 38.0 % and 43.0 % of copper was dissolved at 4:1 and 8:1 Gly:Cu molar
ratio, while only 28.0 % and 22.0 % was obtained at 3:1 and 2:1, respectively. At the end of
864 hours of leaching, the highest copper dissolved was 71.0 % at Gly:Cu ratio of 8:1 while at
2:1 and 3:1 ratios copper extraction was 42.7 and 45.8 %, respectively. Over 55.1 % of copper
93
was extracted from the chalcopyrite sample at Gly:Cu ratio of 4:1.
100
90 Gly:Cu=2:1
80 Gly:Cu=3:1
70 Gly:Cu=4:1
Gly:Cu=8:1
Cu extraction, %
60
50
40
30
20
10
0
0 100 200 300 400 500 600 700 800 900
Time, h
Figure 4.22 Effect of glycine concentration on copper dissolution from chalcopyrite A: peroxide 0.5
%, pH 11, P100 75 µm and % solids 0.51 % w/v

It is well known that the leaching of chalcopyrite occurs in an oxidative environment (Koleini
et al., 2011; McDonald & Muir, 2007; Qiu et al., 2007). Although the bottles were opened to
air that will dissolve in solution and act as an oxidising agent, the effect of stronger oxidising
agent (hydrogen peroxide) was investigated by varying its concentration from 0 %, 0.1 %, 0.5
% and to 1.0 %. The results in Figure 4.23 show that peroxide does not have any valuable
influence on the dissolution of copper from chalcopyrite. As has been mentioned earlier in
Section 4.6.3, hydrogen peroxide could be used up or decomposed so fast that its effect will
become invisible after 12-24 hours. This then implies that, under the given conditions,
dissolved oxygen from the atmosphere provides the necessary oxidative environment. The
extent to which dissolved oxygen influences the dissolution behaviour of chalcopyrite has
been studied and reported in Chapter 5.
94
100
90
80
70
Cu extraction, %
60
50
0% peroxide
40
0.1% peroxide
30
0.5% peroxide
20
1% peroxide
10
0
0 100 200 300 400 500 600 700 800 900
Time, h
Figure 4.23 Effect of initial peroxide concentration on chalcopyrite A leaching: Gly:Cu 4:1, pH 11,

The effect of initial solution pH was studied at pH values of 9, 10 and 11. It is clearly illustrated
in Figure 4.24 that more copper is leached from chalcopyrite as the pH is increased. The
percentage of copper dissolved after 864 hours of leaching is 55.0, 44.0 and 20.0 % at pH 11,
10 and 9, respectively. Although the pH was not controlled during these experiments, it was
monitored and noted to decrease during the leaching process as shown in Figure 4.25. As
was the case with chalcocite leaching, no precipitation is noted when chalcopyrite is leached
at pH 11. What is common with the two systems in which copper precipitation does not occur
is that the copper concentration in solution is less than 2 g/L.
95
100
90 pH 9
80
pH 10
70
pH 11
60
Cu extraction, %
50
40
30
20
10
0
0 100 200 300 400 500 600 700 800 900
Time, h
Figure 4.24 Effect of initial leach solution pH on chalcopyrite A leaching: Gly:Cu 4:1, peroxide 0.5 %,
11.5 11.5
Gly:Cu=2:1 pH 9
11.0
11.0
Gly:Cu=3:1
10.5 pH 10
10.5 Gly:Cu=4:1
10.0 pH 11
Gly:Cu=8:1
10.0 9.5
pH
pH
9.5 9.0
8.5
9.0
8.0
8.5
7.5
8.0 7.0
0 500 0 500
Time, h Time, h
(a) (b)
Figure 4.25 Change in solution pH during the leaching of chalcopyrite A: (a) different glycine
concentrations, (b) different initial solution pH
96
pH 9 pH 10 pH 11
5.0 12
4.5
10
4.0
3.5
8
3.0
[Cu], g/L
2.5 6
pH
2.0
4
1.5
1.0
2
0.5
0.0 0
0 100 200 300 400 500 600 700 800 900
Time, h
of chalcopyrite A
Chalcopyrite leaching in alkaline glycine can be illustrated by Equation 4.8:
CuFeS + 2NH2CH2COO- + 4.5O2 + 2OH- → Cu(NH2CH2COO)2 + H2O +

(4.8)
FeO(OH) + 2SO42-
4.9 Dissolution of Impurities

As mentioned in Chapter 1, the traditional use of acids for the leaching of copper oxides leads
to the dissolution of a wide range of impurities (silicon, iron, magnesium, calcium, aluminium,
etc.) that may form precipitates and hamper solution flow in heaps and negatively influence
downstream processes such as solvent extraction (Ekmekyapar et al., 2015). The final leach
solutions from leaching the copper oxides and chalcopyrite mineral specimens were analysed
by ICP to establish the leachability of major impurity elements in the alkaline glycine system.
Although 247 mg/L Si was detected in solution during chrysocolla leaching, it only represents
7 % of total Si in the sample. If the sample was to be leached in acid medium, Si concentration
in solution would have been 3456 mg/L. Such a concentration would lead to the formation
of silica gel which is extremely difficult to separate from solution and thus creating processing
challenges (Cooper et al., 2000). Table 4.7 shows that most impurity elements from copper
oxides leaching dissolve to a very limited extent relative to copper. In the case of cuprite, in
particular, the high dolomite content (62.1%) remained unaffected by the alkaline glycine
solution. According to the data shown in Table 2.6, International Atomic Energy Agency
(2001) report, if acid was used to leach such a deposit, about 582 kg/ton acid would be
97
consumed, making the process uneconomical. This gives the alkaline glycine leach system a
further advantage over the acidic leaching of such copper oxide deposits.
Table 4.7 Concentration of copper and impurities in the final leach solutions and the calculated
degree of extraction from leaching copper oxides: Gly:Cu 4:1, pH 11, P100 75 µm
Mineral Item/metal Cu Al Si K Zn Mg Fe Ca
Azurite In soln, mg/L 3936.0 2.8 4.8 3.4 0.5 0.3 3.3
Extracted, % 98.4 1.5 0.8 5.9 99.8 1.8 34.8
Chrysocolla In soln, mg/L 769.0 0.2 247.0 12.2 0.2 4.1
Extracted, % 19.2 0.0 7.1 5.4 0.3 12.7
Cuprite In soln, mg/L 3766.0 0.1 4.4 2.7 27.3
Extracted, % 94.2 0.1 0.2 0.7 0.9
Malachite A In soln, mg/L 3884.0 0.4 11.2 3.1 0.7 0.7 3.0
Extracted, % 97.1 3.4 1.4 31.8 1.9 0.2 3.9
The dissolution of impurity elements from chalcopyrite A specimen as shown in Figure 4.27
indicates the extent to which the dissolution of elements can be controlled by the leaching
conditions. Arsenic and lead are observed to dissolve more at pH 9 and 10. Zinc leaching
follows the same trend as that of copper with higher extraction noted as the pH increased. A
zinc extraction of 60.0 % occurred at pH 11 while only 20.0 % zinc was obtained at pH 9. Zinc
dissolution from poorly soluble salt was reported to be significantly enhance by the addition
of glycine (Sobel et al., 2008). Under all conditions, less than 1.0 % Si and Mg were leached.
Except for when pH is 9, less than 6 % Fe was leached under the other investigated conditions.
It can then be concluded that, from a polymetallic chalcopyrite specimen, alkaline glycine
solution with pH above 11 favours copper leaching (and Zn, if present) while rejecting most
impurity metals in the leach residue.
98
75
70
65
60
Element extracted, % 55
50
45
40
35
30
25
20
15
10
5
0
0% 0.1% 0.5 % 1% Gly:Cu Gly:Cu Gly:Cu
pH 9 pH 10 pH 11
H2O2 H2O2 H2O2 H2O2 2:1 4:1 8:1
Cu 55.7 53.4 54.1 55.1 42.7 54.1 71.3 20.1 44.3 54.1
As 18.7 16.8 18.7 14.3 2.7 18.7 18.4 57.0 50.2 18.7
Ca 8.2 8.0 8.2 7.3 5.3 8.2 8.4 45.2 19.1 8.2
Fe 5.3 4.8 5.1 3.9 0.6 5.1 6.5 13.0 6.3 5.1
Mg 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.8 0.5 0.1
Pb 5.1 4.9 5.7 4.4 0.8 5.7 5.2 28.4 28.9 5.7
Si 0.1 0.1 0.1 0.1 0.0 0.1 0.1 0.4 0.3 0.1
S 35.2 29.8 33.6 34.1 23.2 33.6 41.6 11.9 22.8 33.6
Zn 48.8 48.7 49.1 49.3 21.0 49.1 60.7 20.6 35.6 49.1
Leaching conditions
Figure 4.27 Comparative degree of extraction of Cu and impurity elements in final leach solutions
of chalcopyrite A
4.10 Summary
The dissolution behaviour of azurite, malachite, cuprite, chrysocolla, metallic copper,
chalcocite and chalcopyrite have been investigated at different Gly-Cu molar ratios, initial
solution pH, and peroxide concentration (in case of metallic copper and sulfide minerals). It
was observed that higher Gly-Cu ratios favor copper dissolution in all the minerals. Initial
solution pH of 11.0 was noted to be the optimum for the dissolution of the all tested copper
minerals specimens.
Leaching solution pHs lower than 9.5 could lead to the precipitation of copper-glycinate when
the copper concentration in solution approached or exceeded 3 g/L. With copper oxides and
metallic copper, the pH of the leaching solution increases during the first part of the leaching
afterwhich it starts to decline. On the other hand, the solution pH continuously decreased
99
with sulfide mineral leaching.
Peroxide that was speculated to act as a strong oxidising agent during the leaching of metallic
copper and the copper sulfide minerals had no significant influence. Dissolved oxygen from
air acted as a good enough oxidising agent under the given leaching conditions.
Figure 4.28 compares behaviour of the different copper minerals, i.e., an indication of the
geometallurgical response of copper minerals to alkaline glycine solutions at ambient
pressure and temperature. It can be seen that with the exception of chrysocolla, azurite and
malachite are easily leached in the alkaline glycine solution. Metallic copper has the same
dissolution behaviour as cuprite which both show moderate initial dissolution rates.
Chalcocite dissolution is higher than that of chalcopyrite but lower than that of cuprite.
Copper dissolution from malachite plateaus between 40.0 and 50.0 % due to the supposed
formation of slow leaching covellite on the mineral. Copper dissolution from chalcopyrite is
the lowest but increases steadily with up to 71.0 % copper being dissolved after 800 hours of
leaching at 8:1 Gly:Cu molar ratio and initial solution pH of 11.
Alkaline glycine leaching was found to leach copper selectively over gangue minerals such as
Fe, Ca, Mg and Si as these impurities dissolved to a very limited extent relative to copper.
100
90
80 Azurite
Malachite
70 Cuprite
Chrysocolla
60
Cu extraction,%
Metallic copper
Chalcocite
50
Chalcopyrite
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 4.28 Comparative dissolution behaviour of copper minerals in the alkaline glycine solutions:
Cu:Gly 1:4, pH 11, room temperature.
Finally, from the results and general observations in this chapter, a procedure for rapid
evaluation of the response of any copper ore in alkaline glycine solution can be proposed.
The equipment for the proposed procedure, reagents and their concentrations, and
100
experimental conditions are outlined below:
• Bottle Roll leaching experiments are to be conducted at room temperature at a

revolution of 100 rpm. The leaching solution should be opened to air via an inlet on the
cap of the bottle;
• Glycine molar concentrations, must be twice that of the total copper in the ore specimen.
to ensure that there is enough glycine to complex all of the copper due to theformation
of Cu(gly)2;
• Deionised water should be used to ensure that no unwanted ions are introduced into the
system;
• Ore specimens should be ground to 100 % passing 75 µm to make sure that the copper
minerals present in the ore are sufficiently in contact with the leaching agent;
• Percentage solids in the leaching solution should be chosen such that, if complete copper
leaching occurs, the copper content in solution does not exceed 3 g/Lin order to avoid
that copper precipitatig as copper-glycinate; and
• Sodium hydroxide should be used to modify solution pH. An initial solution pH of 11
should be used during the investigation of other variables. The solution pH is not to be
controlled during leaching but monitored to determine the ore’s influence on solution
pH.
With all the above conditions met, the required mass of ore is added to the leaching solution
in the bottle which is then immediately placed on the bottle roller. Timely (30 minutes in first
2 hours) sub-samples should be taken to determine the extent of copper leaching.
Additionally, solution pH and potential should be monitored during sub-sampling.
This method only serves to characterise the leachability of the ore, or ore domain. It is
accepted that, once leachability has been demonstrated, the next step would be to optimise
leaching conditions to align with the proposed leaching method (e.g. heap leaching,
concentrate leaching, etc.) by changing the % solids and temperature and by seeking to
maintain DO, pH levels and control reagent conditions throughout. This would normally
require a well-controlled agitated reactor where mass transfer conditions can be improved
and oxygen micro-bubbles can be sparged under controlled conditions. A system which
removed the copper continuously (e.g. through precipitation) would prevent copper
accumulation and potential reprecipitation.
101
Chapter 5 Mechanisms and Kinetics
of Leaching Malachite,
Chalcocite, and
Chalcopyrite in Glycine
Solutions
5.1 Chapter Objectives and Background
The main objective of this chapter is to study the leaching mechanisms and kinetics of the
dissolution of malachite, chalcocite and chalcopyrite minerals in alkaline glycine solutions.
These minerals are the most predominant minerals in the oxide cap, supergene and
hypogene zones as one progresses deeper into a conventional copper deposit (porphyry).
Leaching, as indicated in Chapter 2, is a key unit operation in the hydrometallurgical

processing of minerals as its’ efficiency has a pivotal influence on the economics of the metal
extraction business (Crundwell et al., 2011). Optimising the efficiency of the leaching process
and the overall hydrometallurgical operation requires an accurate understanding of the
dissolution mechanisms and particularly the kinetics of dissolution (Crundwell, 2013).
Leaching kinetics are of prime concern to hydrometallurgists beacause they seek to
determine what controls the rate of leaching reactions in order to be able to manipulate and
improve the hydrometallurgical process with confidence.
Leaching reactions are generally heterogeneous in that reactions occur at the interface of a
solid phase and a solute in an aqueous solution. Some processes such as gold cyanidation
and pressure oxidation of sulfides involve a gaseous third phase. A simplified representation
of such reactions is shown in Equation 5.1:
A(fluid)+ bB(solid) → Products (fluid or solid or fluid and solid) (5.1)
While the general expression for the reaction rate can be defined by Equation 5.2:
102
𝑑𝑑𝑑𝑑𝐵𝐵
= −𝑆𝑆𝑆𝑆𝑘𝑘0 𝑘𝑘 ′ [𝐴𝐴]𝑚𝑚 (5.2)
𝑑𝑑𝑑𝑑
Where dNB/dt is the reaction rate in moles per unit time, S is the solid surface area, b is the
stoichiometric number of moles of the solid reacting with one mole of the solute, [A]
represents the concentration of the solute in solution, k’ is the rate constant, ko is the
concentration of reactive surface sites (in moles per unit area), and m is the reaction order
with respect to [A].
Based on the general rate expression, several models including the shrinking core model
(SCM), shrinking particle model, and progressive-conversion model have been developed to
study the reaction kinetics of such heterogeneous leaching processes. The shrinking core
model is seen to reasonably represent reality in a broad variety of leaching situations
(Levenspiel, 1999) and has been used extensively to describe leaching kinetics of most
minerals (Li et al., 2013a). The model was first developed by Yagi and Kunii in 1955 who
visualized that the leaching process progresses in five successive steps for particles of
unchanging size (Park & Levenspiel, 1975):
• Diffusion of reactant “A” through the film surrounding the particle to the surface of the
solid
• Penetration and diffusion of reactant “A” through the blanket of ash to the surface of
the unreacted core
• Reaction of reactant “A” with solid at the reaction surface
• Diffusion of products through the ash back to the exterior surface of the solid
• Diffusion of products through the gas film back into the main body of fluid
These five main steps are illustrated in Figure 5.1.
103
Figure 5.1 Representation of concentrations of reactants and products for a particle of unchanging
size (Levenspiel, 1999).
In some processes, some of the steps do not occur and thus have no contribution to the
resistance of the reaction. The resistance of different steps to reaction vary; however,that
with the highest resistance (slowest step) becomes the rate-controlling step. A reaction is
said to be diffusion controlled if the slowest step is diffusion ( steps 1 and 2). If the reaction
at the surface of the solid is the slowest step, then the reaction is said to be chemically
controlled. Finally, a reaction is said to be “product-layer diffusion controlled” if resulting
aqueous products increase concentrations at the surface due to resistance of their diffusion
from the surface. The rate controlling step for a given reaction may change if conditions
change. For example, if the concentration of a reactant is increased, the reaction may change
from mass transfer to chemically controlled as more reagent is available to diffuse to the
reaction surface (Marsden & House, 1992). It is worth noting that some anomalous reactions,
such as precipitation and passivation of particle surfaces, may also control the overall
reaction rates (Free, 2013). In such leaching processes in which passivation is observed to
occur on the reacting mineral surface, models such as initial reaction theory are applied
rather than simple kinetic models (Zhang, 2004).
Levenspiel (1999) used the shrinking core model to develop mathematical expressions where
the various steps are rate controlling. In the case of spherical particles, the integrated
expressions are shown in the following Equations:
Film diffusion controlled: 𝑘𝑘𝑙𝑙 𝑡𝑡 = 𝑥𝑥 (5.3)
104
2�
Product layer diffusion controlled: 𝑘𝑘𝑑𝑑 𝑡𝑡 = 1 − 3(1 − 𝑥𝑥) 3 + 2(1 − 𝑥𝑥) (5.4)
Reaction controlled: 𝑘𝑘𝑟𝑟 𝑡𝑡 = 1 − (1 − 𝑥𝑥)1/3 (5.5)
where x is the conversion fraction of the solid particles, kl, kd and kr are the apparent rate
constants for the different controlling steps, and t is the reaction time.
In reactions in which no product layer is formed (such as burning of pure charcoal), only the
following three steps are assumed to occur: diffusion of reactant “A” through the liquid film
to the solid surface, the reaction at the surface between solid and reactant “A” and thirdly
the diffusion of the reactant products from the solid surface through the liquid film into the
main body solution. If the process is surface chemical reaction controlled, the behaviour is
like that of the unchanging size implying Equation 5.5 is applicable. Liquid film resistance at
the particle surface depends on factors such as relative velocity between particle and fluid,
size of particle, and fluid properties. When the liquid film diffusion controls, the integrated
rate expression is as shown in Equation 5.6:
𝑘𝑘𝑙𝑙 𝑡𝑡 = 1 − (1 − 𝑥𝑥)2/3 (5.6)
where kl is the apparent rate constant for liquid film diffusion controlled when product layer
is not formed.
In order to determine which step is controlling for a given leaching reaction, experimental
data is used to plot a graph of the right hand side of the rate expressions against time. A
correlation of the kinetic data with the models is then assessed by using a correlation
coefficient (R2). A correlation value of reasonably closest one indicates that the actual
leaching process is in agreement with the proposed model. The slopes of the plots are the
respective apparent rate constants.
Many researchers have, however, noted that diffusion controlled or chemical reaction
controlled models fail to represent the rate-controlling step of some leaching reactions
(Ekmekyapar et al., 2003; Feng et al., 2015; Liu et al., 2012a). This is generally the case when
leaching rates depend on temperature and concentration of reagents (Saxena & Mandre,
1992). Levenspiel (1999) stated that, in a scenario whereby not only a single step controls
the reaction rate throughout, the individual rate equations could be combined in order to
determine the extent to which individual steps contribute to limiting the leaching rate at any
105
given stage. This approach has been used by Sultana et al. (2014) to show that the leaching
of iron oxide in oxalic acid is controlled by both diffusion through the product layer and
chemical reaction models with the diffusion controlled process being the more dominating
reaction. Another approach that simultaneously considers all three possible rate controlling
mechanisms to determine the rate controlling stage is by applying a constrained multi-linear
regression using the least square techniques (Nazemi et al., 2011). The advantage of this
technique is not having to test individual rate controlling step formulas against the
experimental data to establish the best fit data and then predict the rate controlling step.
This new approach is also advantageous in that it avoids the scenario whereby close
correlation coefficients (for fitted data) values make it difficult to determine the rate
controlling process. Equation 5.7 is a combination of individual rate controlling model
equations:
t = klx + kd[1-3(1-x)2/3 + 2(1-x)] + kr[1-(1-x)1/3 (5.7)
The constants kl, kd, and kr can be determined by a multi-linear regression analysis using the
least square method. To avoid negative values for the constants, a constrained least square
technique as expressed in Equation 5.8 is used:
Φ= ∑ [klx + kd(1-3(1-x)2/3 + 2(1-x)) + kr[1-(1-x)1/3 -ti ]2 (5.8)

i
Min Φ subject to kl, kd and kr > 0. (5.9)
Equation 5.9 can then be solved by any optimization technique to determine the values of kl,
kd and kr. The results from the solve equation will estimate the time needed to complete a
leaching process controlled by any limiting mechanism/step.
The two most important factors that influence the rate of leaching reactions are the
concentration of reagents and temperature. These two factors are linked to the order of the
reaction and the EA as described Equation 5.10 (Crundwell, 2013):
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = 𝐾𝐾[𝑐𝑐]𝑛𝑛 𝑒𝑒𝑒𝑒𝑒𝑒E𝐴𝐴 ⁄RT (5.10)
where K represents the rate constant, [c] is the concentration of reagent, n the order of the
reaction, EA the activation energy, R the gas constant, and T the temperature (Kelvin).
For reactions to occur, molecules must first collide with sufficient energy. This implies that
reaction rates are related to collision frequency and collision energy. The Arrhenius equation
106
expresses the rate constant in terms of collision frequency factor and collision energy
illustrated in Equation 5.11 (Free, 2013):
𝑘𝑘𝑓𝑓 = 𝐴𝐴𝑒𝑒 𝐸𝐸𝐴𝐴 ⁄𝑅𝑅𝑅𝑅 (5.11)
It is generally accepted that systems with Ea more than 40 kJ/mol are controlled by chemical
reaction while those with activation energy less than 40 kJ/mol are controlled by transport
processes (Levenspiel, 1999). Also, for leaching processes that are chemically controlled,
reaction kinetics are significantly improved by small increments in temperature (Dreisinger
& Abed, 2002). However, some researchers have reported Ea’s higher than 40 kJ/mol for
diffusion controlled reactions (Baba et al., 2009; Vračar et al., 2000). Olanipekun (1999)
suggested that the rate controlling mechanisms of heterogeneous dissolution reactions are
sometimes better determined from kinetic equation plots rather than from Ea’s.
Unfortunately activation energy does not give any more information on the reaction route.
The order of the reaction on the other hand describes the dependency of the reaction rate
on the reagent concentration.
The kinetics and the extent to which a leaching reaction proceeds are also influenced by
particle characteristics, such as particle size, shape and porosity as these factors control the
surface area available for reaction with a solution phase reactant (Li et al., 2014; Marsden &
House, 1992). The influence of these parameters on the leaching kinetics of malachite,
chalcocite, and chalcopyrite will be studied in this chapter.
5.2 Copper Speciation in Alkaline Glycine

Solutions
Copper is known to form both Cu(I)-glycinate and Cu(II)-glycinate complexes (Section 2.6.1).
To propose leaching mechanism/routes for copper minerals in the alkaline glycine solutions,
it is necessary to determine if both Cu (I) and Cu (II) ions are present and stable in the leach
system. Cu (II) sulfate was dissolved in an alkaline glycine solution at pH 11 and the complex
solution was scanned at different wavelengths using a UV-Vis spectrometer. The maximum
absorbance of the Cu (II) glycinate complex solution was observed at 635nm. This is in
agreement with published data which reported Cu (II) in an aqueous alkaline glycine solution
forms a deep blue complex which has a peak at a wavelength around 624-640 nm (Darj et al.,
1996; Fernandes et al., 1997). Cu (I) chloride was also dissolved in alkaline glycine solution at
107
pH 11. As the dissolution of CuCl in the alkaline system is rather slow compared to that of
CuSO4·5H2O, solution samples were taken immediately after mixing at 2.5, 5, and 13 minutes
for scanning with the UV-vis spectrometer at different wavelengths. The maximum
absorbance for all the time interval samples also occurred at around the 635 nm wavelength
as noted for the Cu (II) sulfate (Figure 5.2). This observation indicates that the Cu (I) ions are
rapidly oxidized to Cu (II) ions which then form the stable Cu (II) glycinate complex. It should
be recalled that according to Aksu and Doyle (2001) and, as shown in Table 2.7, the logK of
the Cu2+ complex with glycine (CuL2) is the most stable copper species in copper-glycine
solutions.
0.7
0.6 Copper(II) sulphate

CuCl_start
0.5 CuCl_ 2.5 minutes
CuCl_ 5 minutes
Absorbance
0.4 CuCl_13 minutes
0.3
0.2
0.1
0
450 500 550 600 650 700 750 800 850 900 950
Wavelength (nm)
Figure 5.2 UV-Vis spectrum of Cu (II) sulfate and Cu (I) chloride dissolution in alkaline glycine at pH
11, Gly:Cu 3:1.
The final leach solutions for the different copper minerals were also scanned by using the
UV-Vis spectrometer. Figure 5.3 shows the wavelength scan of the Cu (II) glycinate complex
of leaching solutions of azurite, chrysocolla, cuprite, malachite, chalcocite and chalcopyrite.
It can be seen that UV-Vis spectra from all minerals show a single peak at a wavelength of
635 nm which is the same position obtained for the standard Cu (II) glycinate complex.
108
1.6
chalcopyrite
1.4
chalcocite
1.2 copper sulphate
1 azurite
malachite
Absorbance
0.8
cuprite
0.6
chrysocolla
0.4
0.2
0
0 200 400 600 800 1000
-0.2
Wavelength (nm)
Figure 5.3 UV-Vis spectrum of Cu (II) sulfate (with alkaline glycine), azurite, chrysocolla, cuprite,
chalcopyrite, and chalcocite in aqueous alkaline glycine of pH 11
To further confirm that only Cu(II) ions form the copper glycinate complex in alkaline glycine
solutions, the concentration of Cu (II) ions determined by the UV-Vis spectrometer for
copper sulfate, copper chloride and the different minerals was compared to the total copper
in solution determined by AAS analysis. By comparing the Cu (II) concentration from the UV-
Vis to the total copper concentration obtained from AAS analysis, a correlation line with R2
of 0.9957 was obtained as illustrated in Figure 5.4. This confirms that the Cu (II) glycinate
complex is the only copper species in the leach solution from all investigated copper minerals
at alkaline medium. From these results, it can be concluded that Cu (I) minerals such as
cuprite dissolve in an aqueous alkaline glycine system through the oxidation of Cu (I) to Cu
(II) which then forms a stable Cu (H2NCH2COO)2 complex.
109
2500
R² = 0.9957
2000
Cu [mg/L] by UV-VIS
1500
1000
500
0
0 500 1000 1500 2000 2500
Cu [mg/L] by AAS
Figure 5.4 Correlation between Cu (II) concentration with UV-Vis and total copper by AAS
5.3 Sulfur Speciation from Copper Sulfides

Leaching
Mineral sulfides are well known to form different sulfur species during their dissolution in
common lixiviants (Breuer et al., 2008; Marsden & House, 1992). In order to predict and
propose leaching reactions for sulfide minerals in the alkaline glycine solutions, a sulfur
speciation on a chalcopyrite leachate was performed using an HPLC. The results presented in
Table 5.1 show that up to 90.0 % of the sulfur in the solution is in the form of sulfate. From
this observation, it can be concluded that sulfur in copper sulfide minerals is oxidised to the
sulfate form during alkaline glycine leaching.
Table 5.1 Sulfur speciation for a copper sulfide (chalcopyrite) leached solution
Species name Species formula In solution, mg/L % of total S

Sulfate SO42- 1142 89.8
Sulfite SO32- 74.0 7.2
Thiosulfate S2O32- 22.2 3.0
Sulfide S2- <0.1 -
110
5.4 Leach Residue Analysis
5.4.1 Chalcocite
It has been well established that chalcocite leaching in both acidic and alkaline mediums
proceeds in two stages with the formation of covellite (CuS) as an intermediate product
(Cheng & Lawson, 1991; Duda & Bartecki, 1982; Konishi et al., 1991). During the first stage,
chalcocite is converted to Cu (II) ions leaving behind a copper deficient residue in the form of
covellite. Senanayake (2007) suggested that as the covellite is formed on the outer surface,
it begins to react and proceed in parallel with the first stage, but at a much lower rate and
only becomes significant after 40.0 % dissolution of the initial copper.
Un-leached and leached chalcocite samples were then analysed by XPS and SEM-EDS in order
to determine the type of product formed on the residue surface. The analysis involved the
collection of a survey spectrum and a high resolution spectra for copper and sulfur. The
survey spectrum was collected so that the elements on the surface of the mineral particles
could be identified and quantified while the high resolution spectra collected for copper and
sulfur allowed the determination of their oxidation states. The survey spectrum shows the
major elements detected on the surface of the sample represented by a labelled peak.
Additional unlabelled peaks correspond to minor photoelectron emission and auger peaks.
Figure 5.5 shows the survey spectrum of un-leached and leached chalcocite samples. Figure
5.5 also shows a generated table of elements detected and their calculated atomic
concentration (At%). The generated table shows that the At% ratio of Cu: S in the un-leached
chalcocite is 22:4 while that in the leached chalcocite is 22: 29. The At% ratio of Cu:S in the
leached sample is similar to that obtained in pure covellite (CuS) as reported in National
Institute of Standards and Technology database. Also, the positions (binding energy) of Cu
2p3/2 and S 2p3/2 in the un-leached and leached chalcocite (Table 5.2) are comparable to
those of pure chalcocite and covellite given in the XPS reference pages (Naumkin et al., 2012;
X-ray Photoelectron Spectroscopy (XPS) Reference Pages, 2016). The results shown in Figure
5.5 and Table 5.2 clearly indicate that covellite is a product of chalcocite leaching in the
alkaline glycine solution.
111
Figure 5.5 The survey spectrum of un-leached and leached chalcocite samples.
Figure 5.6 The high-resolution spectra for copper from un-leached and leached chalcocite samples
Table 5.2 Binding energies of chalcocite and covellite from NIST database and from un-leached and
leached chalcocite
Species Cu 2p3/2 B.E.(eV) S 2p3/2 B.E.(eV)

NIST database Cu2S 932.5 161.9
CuS 932.3 162.1
Experimental Un-leached chalcocite 932.52 161.8
leached chalcocite 932.17 162.1
112
SEM-EDS analysis of un-leached and leached chalcocite (Figure 5.7) shows that the ratio of
Cu:S in the leached sample is 1:1 as opposed to the 2:1 ratio noted for the un-leached
chalcocite. With the atomic formula of chalcocite being Cu2S and covellite CuS, the SEM-EDS
analysis indicates the presence of covellite as an intermediate product in the alkaline glycine
leaching system. This observation confirms the report by Konishi et al. (1991) that the
leaching kinetics of natural chalcocite leaching in alkaline Na4EDTA occurs in two consecutive
stages with solid covellite being the product of the first stage and then reacting the second
stage at a rate 10 times lower than the first stage.
Unleached chalcocite Leached chalcocite
Figure 5.7 SEM-EDS spectra for unleached and leached chalcocite
5.4.2 Chalcopyrite
The surface analysis of chalcopyrite leached residues have shown that the presence of a
range elemental species and compounds are precipitated on the surface (Harmer et al.,
2006; Klauber, 2008; Klauber et al., 2001; Li et al., 2010; McIntyre & Zetaruk, 1977; Parker et
al., 2003). Some of these species such as elemental sulfur and iron-hydroxide compounds
have been suggested to passivate the chalcopyrite layer (Ghahremaninezhad, 2012).
Generally, the nature of the species formed depends on the solution pH.
In order to determine the type of species formed during chalcopyrite leaching in alkaline
glycine solution and thus predict reaction routes, un-leached and leached samples were
analysed by XPS and SEM-EDS.
The surface atomic concentrations calculated from the XPS survey spectra (Appendix D2)
indicated the absence of elemental sulfur on leached residue surface (Table 5.3). This is in
agreement with results obtained on the sulfur speciation of a chalcopyrite leachate
demonstrating that sulfur is completely oxidised to sulfate when leached in the alkaline
113
glycine solution (Section 5.3). The deconvolution of the high oxygen resolution spectra
(Figure 5.8) identified that the percentage of lattice hydroxide significantly increased from
13.5 % in the un-leached sample to 79.9 % in the leached sample. With most copper being
dissolved into solution as copper glycinate, the high lattice OH- concentration is most likely
to be associated with an Fe oxyhydroxide species (Fe(III)-O-OH) at 711 eV as shown in Figure
5.9. Iron oxyhydroxide surface species have also been observed on leached chalcopyrite
surfaces (Li et al., 2010; McIntyre & Zetaruk, 1977).
Table 5.3 Elemental surface concentrations of un-leached and glycine leached chalcopyrite sample
calculated from their relative XPS survey spectra.
Element At %
Un-leached Leached
O 1s 49 39.1
C 1s 11.29 38.43
Na 1 s - 1.22
N 1s - 10.48
Cu 2p 11.85 9.31
Fe 2p 4.69 1.55
S 2p 10.76 0.00
Si 2p 11.56 -
Figure 5.8 High-resolution spectra of oxygen from un-leached and glycine leached chalcopyrite
specimen
114
Fe 2p/7
105
100
Un-leached
95
Intensity x 10-1 90
85
80
75
70
65 Leached
60
55
745 740 735 730 725 720 715 710 705 700
Binding Energy (e V)
CasaXP S (Thi s st ring can be edit ed in CasaXP S.D EF/P rintFootN ote.txt)
Figure 5.9 The high resolution spectra of un-leached and leached chalcopyrite specimen
By analysing both chalcopyrite samples by SEM-EDS analysis, the absence of oxygen atoms
on the chalcopyrite surface as illustrated in Figure 5.10 suggests that the goethite product
obtained during the leaching of chalcopyrite does not form a passivation layer on the
chalcopyrite surface.
Unleached chalcopyrite Leached chalcopyrite
Figure 5.10 SEM-EDS spectra for un-leached and glycine leached chalcopyrite
115
5.5 Proposed Leaching Equations
From observations and predictions made from Sections 5.2, 5.3 and 5.4, the following overall
leaching reactions for azurite, malachite, cuprite and chrysocolla can be presented as shown
in Equations 5.12, 5.13, 5.14, and 5.15, respectively. Chalcocite leaching is illustrated by
Equation 5.16 given that covellite is an intermediate product.
2(CuCO3)·Cu(OH)2 + 6NH2CH2COO- = 3[Cu(NH2CH2COO)2] + 2OH- +

(5.12)
2CO32-
(CuCO3)·Cu(OH)2 + 4NH2CH2COO- = 2[Cu(NH2CH2COO)2] + 2OH- +

(5.13)
CO32-
Cu2O + 4NH2CH2COO- + 2H2O +1/2O2 = 2[Cu(NH2CH2COO)2] + 4OH- (5.14)
CuO.SiO2·2H2O + 2NH2CH2COO- = Cu(NH2CH2COO)2 + SiO2 +H2O +

(5.15)
2OH-
Cu2S + 2NH2CH2COO- + 1/2O2 + H2O = Cu(NH2CH2COO)2 + CuS + (5.16)

2OH-
With the confirmation of sulfate as the major sulfur species from sulfide minerals leaching
and goethite formation during chalcopyrite leaching, Equation 5.17 could then be proposed
to illustrate the chalcopyrite leaching in alkaline glycine solutions.
CuFeS2 + 2NH2CH2COO- + 4.5O2 + 2OH- = Cu(NH2CH2COO)2 + FeO(OH)

+ 2SO42- + H2O (5.17)
5.6 Leaching Kinetics of Malachite,

Chalcocite and Chalcopyrite
5.6.1 Malachite B
Malachite is an abundant copper oxide mineral found in the Democratic Republic of the
Congo, Gabon, Zambia, Namibia, Mexico, Australia ( Broken Hill, New South Wales) , France
(Lyon), Israel (Timna Valley), and the Southwestern United States, most notably in Arizona
(Anthony et al., 2001; Mindat.org, 2016). The kinetic analysis of malachite is important since
malachite is the most common copper oxide mineral.
116
5.6.1.1 Mineralogy and Elemental Composition
XRD analysis to determine the mineralogy of the specimen indicated that malachite makes
99.0 % of the sample while the remaining 1.0 % is cristobalite. Chemical composition of the
sample was performed by XRF and the results showed a copper content of 56.0 %. The
mineral sample was crushed, ground and then sieved using standard test sieves into four size
fractions (+20-38, +38-53, +53-75 and +75-106 µm). With the exception of experiments
investigating the effect of particle size, all other experiments were carried out with the +53-
75 µm size fraction.
5.6.1.2 Effect of Initial Glycine Concentration

The effect of glycine concentration on the leaching kinetics of malachite was studied by
varying the initial glycine concentration from 0.1, 0.2 and 0.4 to 0.8 M in 500 mL of solution
at pH 10. Other process variables such as stirring speed (SS), temperature, and particle size
(PS) were fixed at 350 rpm, 25°C, and 53-75 µm, respectively. Since the formation of the
copper-glycine complex needs two moles of glycine for every one mole of copper (Aksu &
Doyle, 2001; Eksteen et al., 2016), the minimum glycine concentration of 0.1 M ensured that
the required glycine to copper ratio of 2:1 in solution is obtainable if complete mineral
dissolution occurs. Figure 5.11 shows that copper dissolution increases with increasing
glycine concentration. When glycine concentration is increased from 0.1 to 0.2 M, the
percentage copper dissolved after three hours increased from 67.6 to 91.3%. At a glycine
concentration of 0.4 M, 98.0 % Cu was dissolved under 2 hours of leaching. At 0.8 M glycine
concentration copper extraction was similar to the copper extracted at 0.4 M. This indicates
that glycine concentration has an upper limit at which further increments have no positive
effect on the leaching rate.
117
100
90
80
70
Cu extraction, % 60
50
40 0.1 M Gly
30 0.2 M Gly
0.4 M Gly
20
0.8 M Gly
10
0
0 20 40 60 80 100 120 140 160 180
Time, mins
Figure 5.11 Effect of glycine concentration on copper dissolution from malachite B: 25 °C, +53-75
µm, 350 rpm and 0.36 %w/v solids
5.6.1.3 Effect of Temperature

The relationship between temperature and copper dissolution rate is shown in Figure 5.12.
During the leaching process, the initial glycine concentration, stirring speed, particle size was
maintained at 0.4 M, 350 rpm and 53-75 µm respectively while the solution temperature was
varied from 25 to 50 °C. The results indicate that temperature has a profound effect on the
copper dissolution rate. At 50 °C, 83.6 % copper dissolution occurs in 5 minutes while 22.3
% copper is dissolved at 25 °C, over the same time. Complete copper dissolution was noted
in under 30 minutes of leaching at 50 °C, after 2 hours at 40 °C and only after 3 hours at 25
°C. Although higher temperatures significantly improve malachite leaching rates, raising the
leaching temperature may be limited by increased capital and operating costs. Thus, 25 °C
was maintained during the evaluation of the other parameters.
118
100
90
80
70
Cu extrn, % 60
50
40 25 °C
30 30 °C
40 °C
20
50°C
10
0
0 20 40 60 80 100 120 140 160 180
Time, mins
Figure 5.12 Effect of temperature on copper dissolution from malachite B: [Gly] 0.4 M, +53-75 µm,
350 rpm, and 0.36 %w/v solids.
5.6.1.4 Effect of Stirring Speed

In order to examine the influence of stirring speed on the leaching rate of malachite,
experiments were carried out at various stirring speeds (150, 350, 550 and 800 rpm) at 25 °C
in solutions containing 0.4 M Gly at an initial pH of 10. The results as shown in Figure 5.13
indicate that leaching rate increases as stirring speed is increased from 150 to 350 rpm.
However, increasing the stirring speed from 350 to 800 rpm does not result in significant
improvement in copper dissolution. This observation suggested that the leaching kinetics
might not be controlled by diffusion through the liquid film. However, the result still indicates
that fluid flow rate is important. This is particularly significant in vat, heap and in-situ leaching
where an optimum leaching solution flow rate is required to carry reagents to and products
from the mineral surface. The fluid flow should be optimum to ensure adequate reaction
contact time between the reagent and the solids.
119
100
90
80
70
60
Cu extrn, %
50
40 150 rpm
30 350 rpm
550 rpm
20
800 rpm
10
0
0 20 40 60 80 100 120 140 160 180
Time, mins
Figure 5.13 Effect of stirring speed on copper dissolution from malachite B: [Gly] 0.4 M, 25 °C, +53-
75µm and 0.36 %w/v solids.
5.6.1.5 Effect of Particle Size

The influence of particle size on the leaching of malachite in 0.4 M glycine at pH 10 and 25 °C
was investigated and the results are shown in Figure 5.14. The particle size ranges of +20-38
µm, +38-53 µm, +53-75 µm, +75-10 µm were leached for 180 minutes. Rapid dissolution rates
were obtained at smaller particle sizes although no noticeable difference was obtained
between +20-38 and +38-53. After 60 minutes of leaching, copper extraction for +75-106 and
+53-75 µm was 82.8 and 89.5 %, respectively, while 99.0 % copper was extracted at +20-38
and +38-53 µm fractions. Leaching fine particles increases the leaching rate by providing
larger contact surface areas for contact with the leaching solution. According to Li et al.
(2014), if the leaching rate is significantly dependent on particle size, then it is an indication
that the kinetics is controlled by diffusion through the product layer. Thus, the insignificant
difference between the copper leaching rates from +20-38 and +38-53 µm size fractions even
though the surface area was increased by finer grinding can be explained by assuming that
below a particular particle size (-53 µm in this case), malachite leaching rate is predominantly
influence/limited by chemical reaction rather than by diffusion models.
120
100
80
Cuextrn, %
60
+20-38 µm
40
+38-53µm
+53-75µm
20
+75-106µm
0
0 20 40 60 80 100 120 140 160 180
Time, mins
Figure 5.14 Effect of particle size on copper dissolution from malachite B: [Gly] 0.4 M, 25 °C, 350
rpm and 0.36 %w/v solids
5.6.1.6 Kinetic Analysis

As malachite leaching at 50 °C is completed within 30 minutes, the leaching kinetics have
been investigated for the initial 30 minutes. According to the shrinking model equations
(Equations 5.3, 5.4, 5.5 and 5.6) given in Section 5.1, if the leaching is controlled by any of
the kinetic models, plotting the right hand side of the equation against time should give a
straight line with the regression correlation coefficient values close to 1. The slope of the
straight line represents the apparent rate constant. The regression correlation coefficient
values from the plotted kinetic models have been determined and shown in Table 5.4.
121
Table 5.4 Correlation coefficient values of shrinking core kinetic models for malachite B
Variables Correlation coefficient for evaluated models: R2

Diffusion Diffusion through Chemical No product layer
through product layer reaction formation- Film
liqiuid film controls controls diffusion at
controls particle surface
controls
x 1-3(1-x)2⁄3+2(1-x) 1-(1-x)1/3 1-(1-x)2/3
Gly concentration
0.1 0.9824 0.9710 0.9878 0.9852
0.2 0.9553 0.9898 0.9731 0.9647
0.4 0.9581 0.9753 0.9906 0.9774
0.8 0.9336 0.9803 0.9766 0.9579
Temperature
25 0.9581 0.9753 0.9906 0.9774
30 0.8476 0.9754 0.9245 0.8880
40 0.7970 0.9909 0.9592 0.8833
50 0.5218 0.8161 0.7659 0.6200
Stirring speed
150 0.9539 0.9868 0.9782 0.9671
350 0.9581 0.9753 0.9766 0.9766
550 0.9282 0.9847 0.9906 0.9564
800 0.9166 0.9887 0.9633 0.9395
Particle size, µm
20-38 0.857 0.9995 0.9878 0.9821
38-53 0.8351 0.9996 0.9422 0.9770
53-75 0.9581 0.9753 0.9906 0.8931
75-106 0.9737 0.9576 0.9915 0.9119
On comparing the correlation coefficients values for the fitted rate controlling models, it can
be noted that it is difficult to predict which model controls the leaching rate of malachite
given that the R2 values for all models under different process conditions are very similar. The
new approach of a constrained multi-linear regression analysis using the least square
technique as proposed by Nazemi et al. (2011) was then applied to determine the rate
controlling step in order to determine the contribution of each rate model at any stage of the
process.
122
Table 5.5 shows the calculated results of fitted experimental data to Equation 5.8 and solving
Equation 5.9 by the constraint least square technique. It can be deduced from the results
that the leaching rate (first 3 hours) of malachite is controlled only by diffusion through the
product layer.
Table 5.5 Data showing the rate-controlling model of malachite B at different temperatures using
the least square technique of constrained multi-linear analysis
Temperature °C Kl (min) Kd (min) Kr (min) R2

25 0 162.15 0 0.9777
30 0 137.18 0 0.9115
40 0 38.27 0 0.9954
50 0 25.73 0 0.9035
The apparent rate constant, k, at various leaching temperatures were obtained from
linearised plots. The apparent rate constant values were then plotted against temperature
according to the Arrhenius equation (Equation 5.11). The plot of lnK vs. 1/T shown in Figure
5.15 was a straight line with its gradient being –Ea/R from which the apparent Ea could be
estimated. The apparent Ea was determined to be 48.26 kJ/mol. The high Ea is unexpected
for a diffusion controlled reaction.
1/T *10-3
0
3.05 3.1 3.15 3.2 3.25 3.3 3.35 3.4
-1
-2
Ln Kd
-3
-4
-5 y = -5.8043x + 14.761
R² = 0.9738
-6
Figure 5.15 Arrhenius plot for product layer diffusion controlled malachite leaching
123
Using Kd values obtained for each investigated process variable, plots of Kd versus ln[Gly],
ln[SS], ln[PS] were obtained. The slope of the straight line in each plot shows the calculated
order of the reaction with respect to glycine, stirring speed and particle size. The order of the
reaction with respect to glycine concentration, stirring speed, particle size were found to be
1.36, 0.64, and -0.96, respectively.
5.6.2 Chalcocite B
Chalcocite, as earlier mentioned in Section 4.7, is a secondary copper sulfide mineral and very
profitable to mine due to its high copper content. This necessitates investigations to
understand its leaching kinetics in this project.
5.6.2.1 Mineralogy and Chemical Composition of

chalcocite B
The chalcocite specimen used in this study was obtained from GeoDiscoveries, a bulk
minerals supplier in Australia. The mineral was ground and sieved to obtain five different size
fractions: less than 20 µm, +20-38 µm, +38-53 µm, +53-75 µm and +75-106 µm. Q-XRD
diffraction of the ground sample showed that the sample contains 82.0 % chalcocite (Cu2S)
and 18.0 % djurleite (Cu1.938S). The copper concentration of the various size fraction was
determined by XRF analysis. Results are as shown in Table 5.6.
Table 5.6 Copper content in each particle size fraction of chalcocite B
Size fraction, µm P80 18.92 20-38 38-53 53-75 75-106

Cu, % 78.4 79.2 78.5 78.6 77.6

Figure 5.16 shows the influence of glycine concentration on the leaching kinetics of
chalcocite. It can be seen that copper extraction increases as glycine concentration increases.
It is, however, clear that there is an upper limit above which any further glycine addition does
not lead to higher copper extraction. Under the given experimental conditions (25°C, 400
rpm, DO 8 ppm), 0.5 M was selected as an optimum glycine concentration as similar copper
extraction (43.0 %) was extracted at 1.0 M Gly in 48 hours.
124
50
45
40
35
30
Cu extraction, %
25
0.1 M Gly
20
0.3 M Gly
15
0.5 M Gly
10
1.0 M Gly
5
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 5.16 Effect of glycine concentration on chalcocite B leaching kinetics: 25°C, 400 rpm, DO 8
ppm, PS 38-53 µm, 0.25 %w/v solids.

The effect of stirring speed was studied by varying the speed from 200 to 800 rpm. It can be
clearly seen from the results shown in Figure 5.17 that, as the stirring speed is increased from
200, 400 and 600 rpm, copper extracted after 48 hours also increased from 23.8, 43.3 and
52.4 % respectively. The results also show that copper extraction at 800 rpm was lower than
at 600 rpm (44.1 % Cu after 48 hours). This observation indicates that agitation at 800 rpm is
too high to establish an optimum contact between the chalcocite particles and the leach
solution.
125
60
200 rpm
400 rpm
50
600 rpm
40 800 rpm
Cu extraction, %
30
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 5.17 Effect of stirring speed on chalcocite B leaching kinetics: 0.5 M Gly, 25°C, DO 8 ppm, PS
38-53 µm, 0.25 %w/v solids.

The effect of particle size on chalcocite leaching rate was studied using five different particle
size fractions: P80: 18.88 µm [d(0.5): 8.4 µm], +20-38, +38-53, +53-75, and +75-106 µm. P80:
18.88 µm [d(0.5): 8.4 µm] indicates a size fraction of 80 % passing 18.88 µm and 50 % of
particles less than 8.4 µm. As shown in Figure 5.18, the effect of particle size is quite evident
after 6 hours. It can be expectantly noted that copper extraction increases as the particle size
decreases. Leaching for 48 hours resulted in 78.2 % Cu extraction from P80 18.88 µm size
fraction while particle size fractions of +20-38 and +38-53 both resulted in 43.0 % Cu
extraction and the size fractions of +53-75 and +75-106 both resulted in only 31.0 % Cu
extraction. The significant improvement in Cu extraction with fine grinding is an indication
that product layer diffusion might be the rate limiting step during chalcocite leaching in
alkaline glycine solutions.
126
90
P80 18.88 µm
80 +20-38 µm
+38-53µm
70 +53-75µm
+75-106µm
Cu extraction, % 60
50
40
30
20
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 5.18 Effect of particle size on chalcocite B leaching kinetics: 0.5 M Gly, 25 °C, 400 rpm, DO 8
ppm, 0.25 %w/v solids.
5.6.2.5 Effect of Dissolved Oxygen (DO) Concentration

The effect of DO on the leaching rate of chalcocite was studied at 8, 15, 20 and 25 ppm. The
results are plotted in Figure 5.18. As shown in Figure 5.19, increasing the DO concentration
generally leads to increases in copper extraction. After 6 hours of leaching, at 25 ppm DO,
copper extraction plateaued at 44.5 % while copper extraction at 15 and 20 ppm DO
increased to 49.8 and 54.0 %, respectively, after 48 hours. The reason for this is not well
understood, but could be attributed to some form of copper alteration products on the
mineral surface under such high DO conditions or glycine degradation. As it was indicated in
Section 5.4.1, covellite, which is an intermediate product during chalcocite leaching, might
quickly form on the surface under high DO and this consequently slows down the leaching
rate.
127
60
50
40
Cu extraction, %
30
8 ppm
15 ppm
20
20 ppm
10 25 ppm
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 5.19 Effect of dissolved oxygen on chalcocite B leaching kinetics: 0.5 M Gly, 25 °C, 400 rpm,
and +38-53 µm, 0.25 %w/v solids.

The effect of temperature on chalcocite leaching is presented in Figure 5.20. The results show
that the leaching rate generally increases as temperature increases. This observation is clear
in Figure 5.20 where leaching for 6 hours at 25, 35, 45, and 55 °C resulted in copper
extractions of 24.1, 31.8, 32.1, and 39.0 %, respectively. After 24 hours of leaching at 45 and
55 °C, copper extraction rate continued to increase steadily while extractions at 25 and 35 °C
showed a decrease in the copper extraction rate. As it has been shown earlier that chalcocite
leaching occurs in two stages with the second dominated by covellite leaching formed from
the first stage (Section 5.4.1), the observed steady increase in Cu extraction rates at 45 and
55 °C after 24 hours suggest that covellite leaching may be improved at higher temperature.
128
60
50
Cu extraction, % 40
30
25 °C
35 °C
20
45 °C
10 55°C
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 5.20 Effect of temperature on the leaching kinetics of chalcocite B: 0.5 M Gly, 400 rpm, DO 8
ppm, 38-53 µm, 0.25 %w/v solids.

Assuming that the chalcocite particles are spherical, the shrinking core model and its rate
controlling equations as previously outlined in Section 5.1 can be applied to determine the
rate limiting steps during leaching. Using the experimental data, the right hand side of each
rate controlling equation was plotted against reaction time for each variable. The kinetic
model that gives the best fit results for the experimental data would then be the rate limiting
step. Table 5.7 shows the correlation coefficients, R2-values of the fitted data for the first 6
hours of leaching. By comparing all of the R2-values for the different experimental variables
in Table 5.7 , it could then be predicted that the initial leaching rate (0-6 hours) of chalcocite
in aqueous alkaline glycine solutions is controlled by diffusion through the product layer since
the R2-values for this model are closest to 1.0.
129
Table 5.7 Correlation coefficient values of shrinking core kinetic models for chalcocite B
Variables Correlation coefficients for evaluated models, R2

Diffusion through Diffusion through Chemical reaction
film control product layer control control
x 1-3(1-x)(2⁄3)+2(1-x) 1-〖(1-x)〗^(1/3)
Gly concentration
0.1 0.9426 0.9518 0.9483
0.2 0.8911 0.9513 0.9034
0.4 0.9569 0.9393 0.9632
0.8 0.9579 0.9372 0.9641
Temperature
25 0.9569 0.9393 0.9632
35 0.9419 0.9953 0.9576
45 0.9021 0.9905 0.9247
55 0.9133 0.9964 0.9367
Stirring speed, rpm
200 0.8546 0.9961 0.8659
400 0.9569 0.9393 0.9632
600 0.9467 0.9405 0.9887
800 0.9855 0.9908 0.9575
Particle size, µm
20-38 0.9493 0.9942 0.9617
38-53 0.9569 0.9393 0.9631
53-75 0.9138 0.9932 0.9237
75-106 0.9595 0.9936 0.9650
Dissolved oxygen, ppm
8 0.7899 0.9393 0.8393
15 0.9361 0.9881 0.9079
20 0.7198 0.9289 0.7832
25 0.8621 0.9831 0.9345
Diffusion through the product layer as the rate controlling step during the leaching of
chalcocite was also confirmed by applying the constrained multi-linear regression using the
least square technique on experimental data as shown in Table 5.8. It could be noted that,
130
as one moves from the first leaching stage (0-6 hours) to the second leaching stage (24-48
hours), the resistance to leaching increases as demonstrated by the higher estimated time
needed to complete the leaching process.
Table 5.8 Rate-controlling model of chalcocite leaching determined for 0-6, 6-48 hours and the
overall leaching data at different temperatures using the least square technique of constrained
multi-linear analysis
Temperature °C Kl (min) *103 Kd (min) *103 Kr (min) *103 R2

0-6 hours leaching
25 0 8.3821 0 0.9855
35 0 7.0068 0 0.9993
45 0 6.3407 0 0.9958
55 0 5.5667 0 0.9982
6-48 hours leaching
25 0 11.428 0 0.9086
35 0 10.296 0 0.9147
45 0 8.6874 0 0.9878
55 0 6.7736 0 0.97734
Whole leaching process
25 0 29.892 0 0.9556
35 0 22.875 0 0.9331
45 0 20.619 0 0.9763
55 0 17.617 0 0.9554
Using the apparent rate constants derived by application of Equation 5.4, the Arrhenius plot
(ln kd vs 1/T(K) was obtained for the first and second leaching stages as shown in Figure 5.21.
The calculated apparent activation energies are 25.36 kJ/mol and 108 kJ/mol for the first and
second leaching processes respectively.
131
1/T, *10 -3 1/T *10-3
0 0.0
3.00 3.10 3.20 3.30 3.40 3.00 3.10 3.20 3.30 3.40
-1 -1.0
-2.0
-2
lnK
-3.0
-3
lnK
y = -3.0514x + 4.6799
R² = 0.8906 -4.0
-4
-5.0
y = -13.066x + 38.068
-5 R² = 0.9839
-6.0
-6
-7.0
Figure 5.21 Arrhenius plot for product layer diffusion controlled chalcocite leaching
Using Kd values obtained for each investigated process variable, plots of Kd versus ln[Gly],
ln[O2], ln[SS], ln[PS] for the first leaching stage were obtained. The slope of the straight line
in each plot shows the calculated order of the reaction with respect to glycine, oxygen,
stirring speed and particle size. The order of the reaction with respect to glycine
concentration, dissolved oxygen concentration, stirring speed, particle size were estimated
to be 0.48, 1.11, 0.95 and -1.39, respectively.
5.6.3 Chalcopyrite B
Chalcopyrite mineral makes up about 70 % of the world’s copper resources (Harmer et al.,
2006). Determining the leaching kinetics of chalcopyrite is thus as important as the mineral
in order to have full understanding of copper extraction in alkaline glycine solutions.
5.6.3.1 Mineralogy and Chemical Composition of

Chalcopyrite B
The chalcopyrite specimen used in this study was obtained from a local mineral collector in
Perth, Australia. The mineral was ground and then sieved to obtain five different size
fractions, less than 20 µm, +20- 8 µm, +38-53 µm, +53-75 µm and +75-106 µm. The sample
fraction below 20 µm was further pulverized with a ring mill and a P80 of 8.56 µm (laser
particle size analyser) size fraction obtained. Q-XRD analysis of the ground sample showed
that the bulk sample contains 67.0 % chalcopyrite, 10.0 % pyrite and 14.0 % ankerite as major
132
phases (Table 5.9). The elemental composition of the different size fractions was determined
by XRF analysis and the results are as shown in Table 5.10.
Table 5.9 Mineralogical composition of chalcopyrite B
Phase Pyrite Chalcopyrite Ankerite Siderite Pyrrhotite Sepiolite Quartz

% mass 10 67 14 5 1 1 1
Table 5.10 Elemental composition of different size fractions of chalcopyrite B
Size fraction/ 75-106 µm 53-75 µm 38-53 µm 20-38 µm -20 µm

Element
Ag (ppm) 28.50 26.00 23.50 21.00 30.00
Fe (%) 31.40 31.51 31.16 30.97 30.48
SiO2 (%) 2.09 1.64 1.63 1.75 2.98
MnO (%) 0.10 0.10 0.10 0.11 0.10
CaO (%) 2.20 2.16 2.00 1.79 1.72
S XRF (%) 33.10 33.30 32.60 32.30 31.40
MgO (%) 1.59 1.54 1.53 1.54 1.84
Zn (%) 0.17 0.17 0.15 0.15 0.19
Pb (%) 0.07 0.07 0.05 0.04 0.06
Cu (%) 26.60 27.20 27.20 27.20 26.20
As (%) 0.03 0.03 0.02 0.02 0.03
LOI1000 16.27 16.04 15.87 16.19 17.10

The effect of glycine concentration on the leaching kinetics of chalcopyrite was studied by
varying the glycine concentration in the range of 0.1 to 1.0 M. The particle size range of +20-
38 µm was used for the investigation of the effects of other process variables unless particle
size was being investigated. Stirring speed of 400 rpm, temperature at 50 °C, dissolved
oxygen concentration (DO) at 15 ppm were kept fixed. The initial solution pH used for all
experiments was 11.5. The results shown in Figure 5.22 indicate that an increase in glycine
concentration results in an increase in copper extraction over time. This observation can be
clearly noted after 96 hours at which 0.1, 0.3, 0.5 and 1.0 M glycine resulted in 17.4, 24.6,
28.2 and 28.5 % Cu extraction, respectively.
133
30
25 gly 0.1 M
Gly 0.3 M
20 Gly 0.5 M
Cu extraction, %
Gly 1.0 M
15
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 5.22 Effect of glycine concentration on the leaching kinetics of chalcopyrite B: pH 11.5, [O2]
15 ppm, PS 20-38 µm, 50 °C, SS 400 rpm, and 0.76 %w/v solids

Some researchers have reported that chalcopyrite oxidation is independent of stirring speed
(Antonijević & Bogdanović, 2004; Dutrizac, 1981). During the leaching of chalcopyrite in
peroxide-glycol system, increasing stirring speeds to above 100 rpm led to a decrease in
copper dissolution (Mahajan et al., 2007). Similarly, Sokić et al. (2009) also reported a slight
decrease in chalcopyrite leach rate with increasing stirring speed which has been attributed
to reduced contact between the particles and the oxidant. To investigate the effect of stirring
speed on chalcopyrite leaching in the alkaline glycine system, the speed was varied from 200
to 800 rpm while glycine concentration was 0.5 M. Figure 5.23 shows that the dissolution
rate of chalcopyrite increases with stirring speed. The highest copper dissolution after 96
hours of 39.25 % occurred at 800 rpm. This observation is an indication that diffusion is
significant in the leaching kinetics of chalcopyrite.
134
45
40
200 rpm
35
400 rpm
600 rpm
30
800 rpm
Cu extraction, %
25
20
15
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 5.23 Effect of stirring speed on the leaching kinetics of chalcopyrite B: [Gly] 0.5 M, pH 11.5,
[O2] 15 ppm, PS 20-38 µm, 50 °C and 0.76 %w/v solids

In industrial leaching operations, reactor design and power consumption significantly depend
on the particle size range being leached (Dreisinger & Abed, 2002). The shrinking core kinetic
model and its application depend on the type and size of particle being leached (Li et al.,
2014). If the leaching rate is significantly dependent on particle size, then it is an indication
that the kinetics is controlled by diffusion through a product layer.
Figure 5.24 shows the effect of various size fractions (-10, +20-38, +38-53, +53-75 and +75-
106 µm) on chalcopyrite leaching rate. The results illustrate that varying the particle size has
no significant influence on chalcopyrite dissolution rate. The results show that, after 96 hours
leaching, copper extraction of 32.0 % was achieved for all size fractions ranging from +20-38
to +75-106 µm. Surprisingly, over the same period, about 90.0 % of Cu was extracted from
the 100 % passing 10 µm size fraction. It was also observed that the initial copper dissolution
rate from the -10 µm fraction was remarkably high with up to 46.8 % copper extracted in just
6 hours as compared to 1.7 % for all other size fractions. This significant difference in the
dissolution rates as a result of particle size reduction is an indication that diffusion plays a
role in limiting the leaching process since fine grinding increases particle surface layer and
reduces the diffusion barrier. Another main reason for the significant improvement in
leaching rate of the -10 µm size could be attributed to the mechano-chemical activation of
135
the mineral caused by extended grinding. Mechano-chemical activation according to Juhász
and Opoczky (1990,) comprises the structural and physiochemical changes (as well as
chemical reactions) which are induced in solids by deformation, disintegration and dispersion
due to the application of mechanical energy. These activations induce defects on the
crystalline structure of the mineral. Leaching kinetics have been reported to be greatly
enhanced by mechano-chemical activation (Balaž, 2000).
100
90
80
70 -10 µm
60 20-38 µm
Cu extraction, %
50 53-75 µm
40 75-106 µm
30
20
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 5.24 Effect of particle size on the leaching kinetics of chalcopyrite B: [Gly] 0.5 M, 50 °C, pH
11.5, [O2] 15 ppm, SS 400 rpm, and 0.76 %w/v solids.
5.6.3.5 Effect of Dissolved Oxygen (DO) Concentration

The effect of different DO concentrations on copper dissolution from chalcopyrite B is shown
in Figure 5.25. Copper dissolution generally increases with increased DO concentration up to
48 hours at which copper dissolution at 25 ppm levels off at 25.4 %. Copper dissolution at DO
8 and 15 ppm was observed to increase steadily with both eventually reaching 31.50 % after
96 hours of leaching. The flattening of the extraction curve after 48 hours of leaching with
25 ppm DO could be attributed to the rapid depletion of surface copper, and by so doing,
increasing the diffusion barrier for further reagent and product diffusion. This may also be
attributed to glycine degradation which has been reported to occur at such high oxidation
conditions (Berger et al., 1999). Other amino acids have also been reported to be oxidised by
oxygen based radicals (Chen et al., 2012)
136
35
30
[O] 8 ppm
25
[O] 15 ppm
Cu extraction, %
20 [O] 25 ppm
15
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 5.25 Effect of dissolved oxygen on the leaching kinetics of chalcopyrite B: [Gly] 0.5 M, pH
11.5, 40 °C, PS 20-38 µm, SS 400 rpm, and 0.76 %w/v solids

With temperature being the key process variable used to determine the leaching rate
controlling step, and given that two types of curves are noted when the effect of particle size
was investigated (Figure 5.24), the effect of temperature on dissolution rate of copper from
chalcopyrite B was investigated using the - 10 µm and +20-38 µm size fractions.
Leaching +20-38 µm Size Fraction
Temperature dependence experiments for chalcopyrite dissolution rate were carried out in
range of 40 to 70 °C in solutions containing 0.5 M Gly and DO concentration of 15 ppm for 96
hours. The results shown in Figure 5.26 indicate that copper dissolution increases as the
temperature increases with final extraction values of 14.1, 31.6, 39.1 and 42.1 %, at 40, 50,
60 and 70 °C, respectively. Although copper dissolution increases as temperature increases,
it is quite noticeable that increasing the temperature from 40 to 50 °C doubles the copper
extraction. However a temperature increase from 50 to 60 °C and from 60 to 70°C has less
effect on copper extraction.
137
45
40 °C
40
50 °C
35
60 °C
Cu extraction, % 30 70 °C
25
20
15
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 5.26 Effect of temperature on the leaching kinetics of 20-38 µm chalcopyrite B: [Gly] 0.5 M,
DO 15 ppm, pH 11.5, PS 20-38 µm, SS 400 rpm and 0.76 %w/v solids
Leaching -10 µm size fraction
The kinetics of heterogeneous reactions such as leaching is not only determined by contact
area but also by mineral structure which can be altered by intensive grinding (Baláž et al.,
1992; Pourghahramani & Forssberg, 2006). Assuming that the ultrafine grinding of
chalcopyrite (in order to obtain the -10 µm fraction) might have altered it leaching kinetics
significantly by mechano-chemical activation as shown in Figure 5.24, investigating effect of
temperature on the leaching of -10 µm was investigated to see if it influenced the rate
controlling model. The temperature was varied from 30, 40, 50 to 60 °C under the following
leaching conditions: 0.5M Gly, stirring speed 500 rpm, and DO 10 ppm. The results of the
effect of temperature on copper extraction from the -10 µm are shown in Figure 5.26. Higher
copper dissolution was clearly noted with an increase in the leaching temperature. However,
the rate of copper dissolution from 10 µm was significantly higher (72.6 % Cu at 60 °C after
24 hours) when compared to that from +20-38 µm size fraction (Figure 5.25) at the same
temperature (13.1 % Cu at 60 °C after 24 hours). The leaching curves in Figure 5.27 are rather
parabolic as opposed to the straight lines obtained when leaching 20-38 µm. This difference
and its effect on the rate controlling model will be determined in Section 5.6.3.7
138
80
70
60
50
Cu extraction, %
40
30 °C
30 40 °C
20 50 °C
60 °C
10
0
0 6 12 18 24 30 36 42 48
Time, h
Figure 5.27 Effect of temperature on the leaching kinetics of < 10 µm chalcopyrite B size fraction:
[Gly] 0.5 M, DO 10 ppm, pH 11.5, PS < 10µm, SS 500 rpm

The rate constants and their correlation coefficients for each process variable were
determined from plots of the various shrinking core kinetic models. Table 5.11 shows the
determined R2-values for the different models and variables.
139
Table 5.11 Correlation coefficient values of shrinking core kinetic models for chalcopyrite B
Variables Correlation coefficients for evaluated models, R2
Diffusion through Diffusion through Chemical

film control product layer control reaction control
x 1-3(1-x)2⁄3+2(1-x) 1-(1-x)1/3
Gly concentration, M
0.1 0.9898 0.9742 0.9924
0.3 0.9939 0.9136 0.9928
0.5 0.9979 0.9110 0.9959
1 0.9917 0.9646 0.9957
Temperature
25 0.9896 0.9615 0.9906
40 0.9996 0.9310 0.9996
50 0.9858 0.9180 0.985
60 0.9932 0.9700 0.9971
70 0.9950 0.9530 0.9992
Stirring speed, rpm
200 0.9890 0.9720 0.9932
400 0.9801 0.9749 0.9875
600 0.9888 0.9847 0.9934
800 0.9984 0.9295 0.9983
Particle size, µm
20-38 0.7246 0.9293 0.8496
38-53 0.9806 0.9742 0.9878
53-75 0.9980 0.9207 0.997
75-106 0.9917 0.9652 0.9959
Dissolved oxygen, ppm
8 0.9968 0.8691 0.9838
15 0.9806 0.9264 0.9878
25 0.8959 0.9742 0.9017
As was noted with the kinetic analysis of malachite, the regression coefficients obtained by
fitting the experimental data to the shrinking core models are too close to deduce the rate
controlling mechanism of copper dissolution from chalcopyrite. On applying the constrained
multi-linear regression analysis using the least square technique, it was possible to identify
140
the rate controlling mechanism for both +20-38 µm and <10 µm particle size fractions.
The calculated results, as shown in Table 5.12, indicate that chalcopyrite leaching of +20-38
µm size fraction in alkaline glycine solution is controlled by both liquid film diffusion and
diffusion through the product layer. However, diffusion through the product layer is the more
dominant rate limiting step as estimated time contribution at different temperatures are far
higher than those of fluid diffusion controlled model.
Table 5.12 Data showing rate-controlling model for 20-38 µm size fraction chalcopyrite B at
different temperatures using the least square technique of constrained multi-linear analysis
Temperature °C Kl (min)*104 Kd (min) *104 Kr (min) *104 R2
40 3.77 6.97 0 0.9970

50 0.96 7.21 0 0.9989
60 0.96 3.37 0 0.9992
70 0.98 2.13 0 0.9998
On the other hand, when the constrained multi-linear regression analysis using the least
square technique is applied on the leaching data of < 10 µm (Table 5.13), the leaching kinetics
is controlled by the diffusion through the product layer for temperature values of 40 °C and
above are considered. When leaching is conducted at 30 °C, both diffusion through the
product layer and chemical reaction control the leaching process. However, chemical
reaction’s contribution was very limited and eliminated when temperature was elevated to
40 °C.
Table 5.13 Data showing rate-controlling model for < 10 µm size fraction chalcopyrite B at different
temperatures using the least square technique of constrained multi-linear analysis
Temperature °C Kl (min)*104 Kd (min) Kr (min) R2

*104 *104
30 0 1.8708 0.3858 0.9993
40 0 1.5124 0 0.9736
50 0 1.2872 0 0.9841
60 0 0.7063 0 0.9408
The apparent rate constants obtained from the plots of 1-3(1-x)(2⁄3)+2(1-x) versus time at
investigated temperatures were used to construct an Arrhenius plots for both +20-38 µm
141
and < 10 µm size fractions. From the data shown in Figures 5.28 and 5.29, the apparent EA’s
were calculated to be 36.25 kJ/mol for +20-38 µm and 29.62 kJ/mol for the < 10 µm size
fraction. The lower activation value for the < 10 µm size fraction can be attributed to the
mechano-chemical activation of the mineral surface when subjected to ultrafine grinding.
1/T *103
0
2.80 2.90 3.00 3.10 3.20 3.30 3.40
-1
-2
-3
-4
lnKd
-5
-6
-7
-8 y = -4.3594x + 6.476
R² = 0.9751
-9
Figure 5.28 Arrhenius plot for product layer diffusion controlled leaching of chalcopyrite B
1/T* 103
0
2.95 3.00 3.05 3.10 3.15 3.20 3.25 3.30 3.35
-1
-2
-3
lnK
-4 y = -3.563x + 5.7078
R² = 0.9635
-5
-6
-7
Figure 5.29 Arrhenius plot for product layer diffusion controlled leaching of <10 µm chalcopyrite B
fraction
In order to obtain reaction orders with respect to process variables for chalcopyrite leaching,
Kd values determined for each process variable were used to make plots of lnKd versus ln[Gly],
ln[O2], ln[SS], ln[PS]. The slope of the straight line in each plot shows the calculated reaction
142
order with respect to the variable. The order of the reaction with respect to glycine
concentration, dissolved oxygen concentration, stirring speed, particle size were 0.21, -0.87,
0.31, and -0.12, respectively.
5.7 Summary
Copper speciation from malachite, azurite, cuprite, chrysocolla, chalcocite and chalcopyrite
leachates by UV-Vis and AAS established that only Cu(II) ions are available in the pregnant
leach solutions to form the stable copper-glycinate complex Cu(H2NCH2COO)2.
Sulfur speciation of the chalcocite and chalcopyrite leachate showed that sulfate species
make up 90 % of the total sulfur in solution.
The dissolution of chalcocite occurs in two stages. The first stages involves the conversion of
Cu2S to covellite (CuS) and Cu ions. The CuS formed in the 1st stage is then leached in the
second stage at a rather slower rate when compared to the fast conversion rate of Cu2S in
the first stage.
During chalcopyrite leaching, goethite was reported as one of the main by-products.
However, SEM-EDS analysis of the leached residure indicated that the goethite does not form
a passivation layer on the chalcopyrite surface given that no oxygen atoms were identified
on the mineral surface after leaching.
Kinetic analysis of malachite and chalcocite showed that the leaching processes are both
controlled by diffusion through product layer. Chalcopyrite leaching on the other hand is
controlled by liquid film diffusion and diffusion through the product layer (dominant) when
+20-30 µm size fraction was considered. For the < 10 µm chalcopyrite size fraction, the
leaching is also controlled by diffusion through the product layer for temperatures above 30
°C.
143
Chapter 6 Leaching of Copper-Gold Ores
6.1 Chapter Objectives

The main objective of this chapter is to study the effect of process variables (reagent
concentration, pH, temperature, oxygen concentration, galvanic effect) on the dissolution of
copper and gold from different copper-gold ores.
Three copper-gold ore specimens (A, B, and C) were used to investigate the effect of process
variables on the dissolution of copper and gold from these ores. All samples were crushed,
milled and screened to achieve 100 % passing 75 µm.
Heap leaching simulation experiments were conducted with sample C and sample D
(flotation tail). Sample C was crushed and screened to obtain a size fraction of 1-8 mm. The
flotation tail specimen (dry) was leached as received (42.4 % of particles >2mm and 57.6 %
<2mm).
6.2 Copper- Gold Ore A
6.2.1 Mineralogical and Elemental Composition

The XRD analysis of Cu-Au ore A showed chalcopyrite as the only copper mineral and pyrite
as the major gangue phase (Table 6.1). Gold content determination by fire assay showed that
the sample contains 1.96 ppm gold and XRF analysis showed a copper concentration of 3.56
%. According to literature, such an ore would normally not be processed by conventional
cyanidation as huge amounts of cyanide would be consumed by copper dissolution. A more
feasible approach would be to float and smelt. It is, however, important to understand the
behaviour of such ores when leached in the alkaline glycine system.
145
Table 6.1 Mineralogy and elemental composition of Cu-Au ore A
Mineral phase Mass % Element value
Clay mineral 6 Au (ppb) 1960
Kaolinite 2 Al (%) 1.74
Clinochlore 9 As (%) 0.048
Talc 2 Ca (%) 0.63
Annite - biotite - phlogopite 1 Co (%) 0.048
Muscovite - sericite 1 Cu (%) 3.56
Amphibole 1 Fe (%) 32.90
Alpha quartz 6 K XRF (%) 0.18
Calcite 2 Mg (%) 1.58
Dolomite - ankerite 4 Mn (%) 0.24
Siderite 1 Ni (%) 0.01
Chalcopyrite 9 Pb (%) 0.47
Covellite 11 Si (%) 5.96
Pyrite 38 Sn (%) 0.01
Pyrrhotite 4 S XRF (%) 30.20
Magnetite 5 Zn (%) 4.97
U XRF (%) 0.03
Cl (%) 0.01
6.2.2 Effect of Glycine

Experiments to study the effect of glycine on copper and gold leaching from Cu-Au ore A
were conducted by varying the initial Gly:Cu molar ratios from 2:1, 4:1, and 8:1 and bottle
rolled at 100 rpm. The Cu-Au sample was ground to 100 % passing 75 µm and 100 g was
added to 500 ml of leaching solution making 20 % w/v solids. Figure 6.1 shows that copper
leaching increases with increasing Gly:Cu ratio. After 168 hours of leaching, 50.4, 46.7 and
37.4 % Cu was leached at Gly:Cu ratios of 8:1, 4:1 and 2:1, respectively. The observed linear
relationship between copper extraction and time indicates that there is no passivation on the
ore surface.
146
60
50
Cu:gly 1:2
Cu:gly 1:4
40 Cu:gly 1:8
Cu extraction, %
30
20
10
0
0 20 40 60 80 100 120 140 160 180
Time, h
Figure 6.1 Effect of glycine concentration on Cu leaching from ore A: pH 11, 0 % H2O2, P100 75 µm,
25°C, and 20 %w/v solids.
Gold leaching from the ore was not monitored during sub-sampling since, according to Oraby
and Jacques (2014a, 2014b), copper should be selectively leached over gold under the given
conditions (room temperature). Literature on dissolution of gold in alkaline ammonia (Meng
& Han, 1996) also states that gold dissolution only becomes significant above 60 °C . At the
end of the leaching experiment, 168 hours, gold concentration in the leach solution was
determined to establish if gold leaching occurred. On discovering the presence of gold in
solution, the percentage of gold leached was determined by comparing gold concentration
in solution to the re-calculated head grade. Figure 6.2 indicates that gold leaching decreases
as the Gly:Cu ratio increases. After 168 hours of leaching, 40.5, 42.3 and 50.3 % of Au was
leached at Gly:Cu ratios of 8:1, 4:1 and 2:1, respectively. The reason for the observed gold
leaching in the glycine solution at room temperature is yet to be understood but can be
linked to galvanic interactions between gold and the sulfide minerals present in the ore. Such
interactions have been noted to significantly improve gold leaching rates in different leaching
solutions (Aghamirian & Yen, 2005; Jeffrey et al., 2006; Lorenzen et al., 1994). The influence
of galvanic interactions on gold leaching in alkaline glycine solutions will be investigated in a
subsequent section in this chapter.
147
Cu:gly 1:2 Cu:gly 1:4 Cu:gly 1:8
60
50
50.34
Au extraction,% 40
42.33
40.54
30
20
10
Figure 6.2 Effect of glycine concentration on Au leaching from Cu-Au ore A: pH 11, 25 °C, 0 % H2O2,
168 h, P100 75 µm and 20 %w/v solids.

Figure 6.3 shows the effects of initial leach solution pH on the copper extraction from Cu-Au
ore A. It can be noted that there was no difference between the amount of copper leached
at pH 11 and 12. However, at pH 10 the percentage of copper leached was reduced as a
maximum of 31.4 % was obtained after 168 hours compared to 46.5 % at pH 11 and 12. In
the case of gold, Figure 6.4 shows that an increase in the initial solution pH led to a slight
decrease in gold leaching. The experiment with an initial pH of 10 resulted in 51.4 % gold
leaching while leaching at pH 11 and 12 resulted in 42.3 % and 39.6 % gold extraction
,respectively. This observation is an indication that the Au-glycinate complex has a higher
stability at low pH. Determination of the stability region (pH-Eh) of Au-Gly is beyond the
scope of this project.
148
50
45
40 pH 10
35 pH 11
pH 12
30
Cu extraction, %
25
20
15
10
0
0 20 40 60 80 100 120 140 160 180
Time, h
Figure 6.3 Effect of initial solution pH on Cu leaching from Cu-Au ore A: Gly:Cu 4:1, 0 % H2O2, P100
75 µm and 20 %w/v solids.
pH 10 pH 11 pH 12
60
50
51.44
40
Au extractionn,%
42.33
39.61
30
20
10
Figure 6.4 Effect of initial solution pH on Au leaching from Cu-Au ore A: Gly:Cu 4:1, 25 °C,
0 % H2O2, P100 75 µm, 20 %w/v solids, 168 hours.

The effect of hydrogen peroxide on copper and gold leaching from Cu-Au ore A was studied
at zero and 1 % peroxide in the leaching solution. Figures 6.5 and 6.6 show that the presence
of peroxide has a slight positive effect on copper leaching but has a negative effect on gold
leaching over the same period. In the absence of peroxide, 42.3 % Au was leached while just
4.7 % Au was obtained at 1 % peroxide. The reason for this is rather unclear as earlier
investigations by Eksteen and Oraby (2015a) reported that peroxide enhanced gold in glycine
from a pure gold foil. With the rate of peroxide decomposition being affected by its
149
concentration, temperature as well as impurities (Dougherty & Anslyn, 2005), the use of
peroxide on a “dirty” ore such as Cu-Au ore A could lead to the oxidation of impurity metals
and would be excluded in the next investigations.
50
45
40
35
30
Cu extraction, %
25
20
0% peroxide
15
1% peroxde
10
0
0 20 40 60 80 100 120 140 160 180
Time, h
Figure 6.5 Effect of peroxide on Cu leaching from Cu-Au ore A: Gly:Cu 4:1, pH 11, 25 °C, P100 75 µm
and 20 %w/v solids.
0% peroxide 1% peroxide
45
40
35
Au extractionn, %
30
25
20
15
10
Figure 6.6 Effect of peroxide on Au leaching from ore A: pH 11, Cu:Gly 1:4, P100 75 µm, 25 °C, 20
%w/v solids, 168 hours.
150
6.3 Copper - Gold Ore B

Copper- gold ore B was analysed for its mineralogical and elemental composition by Q-XRD
and XRF spectroscopy, respectively. Gold content in the ore was determined by fire assay.
The copper phase in the ore could not be determined by XRD as it was assumed to be less
than 1 % (Macchiarola et al., 2007). The ore sample was then further analysed by Tescan
Integrated Mineral Analysis (TIMA) at the John de Leader Centre of Curtin University to
identify and quantify mineral phases. Both the mineralogical and elemental composition of
copper-gold ore B are shown in Table 6.2. The copper phase was determined to be <1 %
cuprite. Elemental analysis showed that the ore contains 13.2 ppm gold and 0.04 % copper.
The occurrence of copper in this ore is at a nuisance level to the cyanidation of gold, meaning
that the presence of copper adds additional treatment costs without bringing any additional
revenue (Sceresini, 2005).
Table 6.2 Mineralogical and elemental composition of Cu-Au ore B
Phase % Element value Element value
Cuprite <1 Au (ppm) 13.2 S XRF (%) 0.09
Quartz 86 Ag (ppm) 123 K XRF (%) 0.52
Mica 7 Al (%) 2 Na (%) 0.04
Rutile <1 Fe (%) 0.54 Mn (%) 0.01
Kaolin 6 Pb (%) 0.07 Ti (%) 0.42
Ca (%) 0.02 Zn (%) 0.03
Mg (%) 0.06 P XRF (%) 0.02
S XRF (%) 0.09 Cu (%) 0.04
Ba (%) 0.01 S LECO 0.10

Increasing the glycine concentration from 0.1 to 1.0 M has no effect on copper extraction
from this ore as shown in Figure 6.7. This may be due to the high stiochimetry of glycine with
respect to the low copper content (0.04 %). The Cu leaching curve shows that, at all glycine
concentrations, about 75 % copper is leached after 3 hours with no further changes noted.
This rapid dissolution of copper in the first hour of leaching confirms the presence of an oxide
151
ore which has been reported to quickly dissolve in alkaline glycine solutions (Tanda et al.,
2017). Under these conditions, gold is barely leached as the highest extraction is 0.36 %
(Figure 6.8). The reason for the insignificant gold dissolution from Cu-Au B as compared to
that from Cu-Au A is the absence of galvanic interactions since Cu-Au B does not contain any
sulfide minerals that can initiate such interactions. From the above observation, such an ore
(Au-Cu oxide) could be processed in two stages. In the first stage, ambient conditions are
maintained to selectively leach copper over gold. In the second stage conditions could be
changed to optimise gold leaching. If selective recovery of copper or gold from the PLS
containing both Cu and Au is possible, finely ground pyrite (for galvanic interactions) can be
added to the ore before leaching. A single stage leaching would then be implemented.
100
90
80
70
60
Cu extraction, %
50
0.1 M Gly
40
0.3 M Gly
30 0.5 M Gly
20 1.0 M Gly
10
0
0 50 100 150 200 250 300 350 400
Time, %
Figure 6.7 Effect of glycine on Cu leaching from Cu-Au ore B: pH 11.5, 25 °C, P100 75 µm and 20
%w/v solids.
152
0.4
0.1 M Gly
0.35
0.3 M Gly
0.5 M Gly
0.3
1.0 M Gly
0.25
Au extraction, %
0.2
0.15
0.1
0.05
0
0 50 100 150 200 250 300 350 400
Time, h
Figure 6.8 Effect of glycine on Au leaching from Cu-Au ore B: pH 11.5, 25 °C, P100 75 µm and 50
%w/v solids.

The effect of initial solution pH on the leaching of copper and gold from Cu-Au ore B was
investigated by varying the pH from 8 to 11. Figure 6.9 shows that the initial solution pH has
no effect on copper leaching from the ore as the percentage Cu extraction of 72-76 % for all
pHs was obtained during the entire leaching time. In the case of gold, Figure 6.10 shows that
gold leaching is insignificant at all pHs as less than 0.3 % Au was dissolved.
100
90
80
70
60
Cu extraction, %
50 pH 8
pH 9
40 pH 10
pH 11
30
20
10
0
0 50 100 150 200 250 300 350 400
Time, h
Figure 6.9 Effect of initial pH on Cu leaching from Cu-Au ore C: [Gly] 0.5 M, 25 °C, P100 75 µm and 20
%w/v solids.
153
0.3
pH 8
0.25 pH 9
pH 10
pH 11
Au extraction, % 0.2
0.15
0.1
0.05
0
0 50 100 150 200 250 300 350 400
Time, h
Figure 6.10 Effect of initial pH on Au leaching from Cu-Au ore B: [Gly] 0.5 M, P100 75 µm and 20
%w/v solids.
6.3.4 Effect of Temperature

The effect of temperature on copper and gold dissolution from Cu-Au ore B was studied using
a glass reactor and at the following leach conditions: 25 or 60 °C with solutions containing
0.5 M glycine, pH 11.5, stirring speed 250 rpm, and oxygen flow rate of 0.2 L/min. Figure 6.11
shows that initial copper extraction at 60 °C was higher than that at 25 °C but the extraction
after 75 hours was 80 % for both systems. Au dissolution from the ore as shown in Figure
6.12 is strongly dependent on temperature with a 32.2 % extraction at 60 °C compared to
only 0.45 % at 25 °C. It should also be noted that, at the higher temperature, the rate of Au
dissolution starts to increase sharply after 24 hours. This confirms the results obtained by
Oraby and Eksteen, (2014) stating that, even at elevated temperature, gold leaching in
alkaline glycine solution only starts after 24 hours.
154
100
90
80
70
60
Cu extraction, %
50
25°C 60 °C
40
30
20
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.11 Effect of temperature on Cu leaching from Cu-Au ore B: [Gly] 0.5 M, pH 11.5, O2 0.2
L/min, P100 75 µm and 20 %w/v solids.
35
30 25°C
60 °C
25
20
Au extraction, %
15
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.12 Effect of temperature on Au leaching from Cu-Au ore B: [Gly] 0.5 M, pH 11.5, O2
0.2L/min, P100 75 µm and 20 %w/v solids.
6.3.5 Effect of Oxygen

Figure 6.13 shows that the higher oxygen flow rate of 0.2 L/min had a slight positive effect
on copper dissolution from Cu-Au ore B in the first 48 hours of leaching. After this point, both
155
oxygen flow rates had a Cu extraction of 77. 7 %. After 96 hours, the copper extraction from
0.05 L/min measures 80.3 % which is slightly higher than the 74.5 % from 0.3 L/min oxygen
flowrate experiment. This difference can be attributed to glycine oxidation under the given
conditions. This observation agrees with results in Chapter 4 indicating that copper oxide
minerals easily dissolve in alkaline glycine solutions without addition of air or oxygen.
However, Au dissolution, as can be noted in Figure 6.14 increases with increase in oxygen
flow rate since gold in its natural state must be oxidised to gold ions in order to complex with
glycine.
100
90
80
70
60
Cu extraction, %
50 0.05 L/min
40
0.2 L/min
30
20
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.13 Effect of oxygen on Cu leaching from Cu-Au ore B: [Gly] 0.5 M, pH 11.5, 60 °C, P100 75
µm and 20 %w/v solids.
156
35
30
0.05 L/min
25
0.2 L/min
20
Au extraction, %
15
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.14 Effect of oxygen on Au leaching from Cu-Au ore B: [Gly] 0.5 M, pH 11.5, 60 °C, P100 75
6.3.6 Effect of Galvanic Interactions

Galvanic interactions, which are caused by the difference between rest potentials of minerals
that are in contact during electrochemical leaching, have been reported to improve the
dissolution of metals from their ores (Li et al., 2013b). Sarveswara Rao et al. (1992) reported
that galvanic interaction by means of pyrite addition during ammonia leaching of multimetal
sulfides enhanced chalcopyrite dissolution. The effect of galvanic interactions on the
dissolution of copper and gold from Cu-Au ore C was studied by adding different amounts of
pure pyrite. The effect of galvanic interactions on the dissolution of copper and gold from
Cu-Au ore B was investigated by comparing experiments with no pyrite to 5 kg/t and 20 kg/t
pyrite additions. Figure 6.15 shows that, within the initial 48 hours of leaching, pyrite addition
led to a slight improvement in copper dissolution. After this point, Cu extraction for all
experiments remained at around 80 %. The influence of galvanic interactions is more
significant during gold leaching as shown in Figure 6.16. The addition of 20 kg of pyrite per
tonne of ore improved both the rate of gold dissolution (43.23 % Au extracted in 24 hours)
and the extent of gold extraction with the highest gold extraction of 60.4 %. Final Au
extraction in the presence of 5 kg/t pyrite and with no pyrite were 42.95 and 23.4 %,
respectively.
157
100
90
80
70
60
Cu extraction, %
50
No pyrite addition
40
pyrite 5kg/t
30
pyrite, 20kg/t
20
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.15 Effect of galvanic interactions on Cu leaching from Cu-Au ore B: [Gly] 0.5 M. pH 11.5, 60
°C, O2 0.05 L/min, P100 75 µm and 20 %w/v solids.
100
90
80 No pyrite addition
pyrite 5kg/t
70
pyrite, 20kg/t
60
Au extraction, %
50
40
30
20
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.16 Effect of galvanic interactions on Au leaching from Cu-Au ore B: [Gly]
0.5 M. pH 11.5, 60 °C, O2 0.05 L/min, P100 75 µm and 20 %w/v solids.
6.4 Copper-Gold Ore C
6.4.1 Mineralogical and Elemental Composition

TIMA analysis of the Cu-Au ore C indicated the presence of chalcopyrite at 0.23 % as shown
in Table 6.3. XRF analysis showed the copper concentration in the ore to be 0.136 %. The gold
158
content determined by fire assay is 510 ppb. Cu- Au ore C is thus a typical example of a low
grade copper-gold ore with huge deposits relatively abundant as mentioned in Chapter 2.
Table 6.3 Mineralogical and Major Elemental composition of Cu-Au ore C
Minerals Mass [%] Minerals Mass [%] Element Mass %

Actinolite 2.45 Ilmenite 0.05 Au (ppb) 510
Albite 0.01 Kaersutite 0.71 Cu (%) 0.15
Ankerite+clay(Fe) 0.01 Magnesiogedrite 0.77 As (%) 0.01
Anorthite 0.32 Muscovite 0.68 Fe (%) 3.64
Apatite 0.22 Orthoclase 4.63 Mg (%) 1.74
Biotite 4.64 Plagioclase 50.03 Al (%) 7.99
Calcite 0.02 Pyrite 0.21 Si (%) 30.3
Chalcopyrite 0.23 Pyrrhotite 0.27 Ca (%) 3.22
Ferro-Actinolite 0.05 Quartz 32.12 S (%) 0.37
Ferrosaponite 0.08 Rutile 0.02 K (%) 1.39
Garnet - Pyrope 0.86 Scheelite 0.01
Hematite/Magnetite 0.14 Zircon 0.03
Titanite 0.71 The rest 0.04
Tschermakite 0.68 Total 100
Hornblende 0.01

The effect of glycine on the leaching of copper and gold was investigated by varying the
glycine concentration from 0.1 to 1.0 M. Figure 6.17 shows that copper leaching increases by
increasing the glycine concentration. The highest copper extraction was 65.1 % after 528
hours at 1.0 M glycine. Glycine concentrations of 0.5 M, 0.3 M and 0.1 M resulted in 55.6 %,
46.0 % and 20.8 % copper extraction, respectively. Gold leaching, as shown in Figure 6.8, was
also noted to be improved as the glycine concentration increased. A significant improvement
in gold extraction occurs after 192 hours at 1.0 and 0.5 M glycine when the percentage of
gold leached jumped from 13.5 to 40.5 %. After 361 hours of leaching, gold extraction was
only 7.7 % at 0.1 M glycine and increased to 13.1 % at 0.5 M glycine at same leaching time.
After 528 hours of leaching, gold extracted from 1.0 M Gly solution was 53.1 % while that
from 0.1 M Gly solution was only 5.5 %.
159
100
90
80 0.1M Gly
0.3M Gly
70 0.5M Gly
1.0M Gly
60
Cu extraction, %
50
40
30
20
10
0
0 100 200 300 400 500 600
Time, %
Figure 6.17 Effect of glycine on Cu leaching from Cu-Au ore C: pH 11.5, 25 °C, P100 75 µm and 50
%w/v solids.
100
90
80 0.1M Gly
0.3M Gly
70 0.5M Gly
1.0M Gly
60
Au extraction, %
50
40
30
20
10
0
0 100 200 300 400 500 600
Time, h
Figure 6.18 Effect of glycine concentration on Au leaching from Cu-Au ore C: pH 11.5, 25 °C, P100 75

Figure 6.19 shows that copper leaching from Cu-Au ore C is increased by the initial leaching
solution pHbeing raised. After 528 hours of leaching, 55.6 % Cu was leached at pH 11 while
160
18.9 % was leached at pH 8. During the same time, 51.8 % and 41.8 % Cu was leached at pH
10 and 9, respectively. With regards to gold, Figure 6.20, shows that higher pH also favours
its leaching. It was, however, noted that, after 192 hours, there was a significant jump in gold
dissolution at pH 11 as opposed to very modest changes at the other pHs. After 528 hours
of leaching, 37.6 % Au was leached at pH 11 while the closest was 7.8 % at pH 10. The
response of gold to different initial solution pH in this ore is contrary to what was observed
with Cu-Au ore A in which a lower pH of pH 10 led to higher gold leaching compared to pH
11 and 12. The mineralogy of individual ores could be the reason for the disparity in their
response to process conditions.
100
90
80 pH 8
pH 9
70 pH 10
pH 11
60
Cu Extraction, %
50
40
30
20
10
0
0 100 200 300 400 500 600
Time, h
Figure 6.19 Effect of initial solution pH on Cu leaching from Cu-Au ore C: [Gly] 0.5 M, 25 °C, P100 75
161
100
90
80 pH 8
pH 9
70
pH 10
60 pH 11
Au extraction, %
50
40
30
20
10
0
0 100 200 300 400 500 600
Time, h
Figure 6.20 Effect of initial solution pH on Au leaching from Cu-Au ore C: [Gly] 0.5 M, 25 °C, P100 75

The effect of temperature on copper and gold dissolution from Cu-Au ore C was studied at
25 and 60 °C. The glycine concentration was kept at 0.5 M and oxygen flow rate was
maintained at 0.3 L/min. Figure 6.21 shows that higher temperature favoured copper
dissolution with a 65.96 % copper extraction at 60 °C while 40.67 % was dissolved at 25 °C.
Gold dissolution was also noted (Figure 6.22) to be improved with the temperature increase:
15.39 % gold extraction was achieved at 60 °C and 8.52 % at 25 °C after 96 hours.
162
100
90
80
70
60
Cu extraction, %
50
40
30 25°C
20
60 °C
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.21 Effect of temperature on Cu leaching from Cu-Au ore C: [Gly] 0.5 M, pH 11.5, O2 0.3
18
16
14
12
Au extraction, %
10
6
25°C
4
60 °C
2
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.22 Effect of temperature on Au leaching from Cu-Au ore C: [Gly] 0.5 M, pH 11.5, O2 0.3
6.4.5 Effect of Oxygen

The effect of oxygen on copper and gold dissolution from Cu- Au ore C was examined at 0.05
and 0.3 L/min. Figure 6.23 shows that a higher oxygen flow rate led to a higher copper
extraction. By comparison, Figure 6.24 rather shows that the higher oxygen flow of 0.3 L/min
resulted in a lower gold dissolution of 15.38 % as opposed to 24.91% obtained with a 0.05
L/min after 96 hours of leaching.
163
100
90
80 0.3 L/min
70
0.05 L/min
60
Cu extraction, %
50
40
30
20
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.23 Effect of oxygen on Cu leaching from Cu-Au ore C: [Gly] 0.5 M. pH 11.5,60 °C, P100 75
30
25
20
Au extraction, %
15
10 0.3 L/min
0.05 L/min
5
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.24 Effect of oxygen on Au leaching from Cu-Au ore C: [Gly] 0.5 M. pH 11.5, 60 °C
6.4.6 Effect of Galvanic Interaction

The results in Figure 6.25 indicate that galvanic interactions, which might be occurring
between chalcopyrite and pyrite, resulted in about a 10 % improvement in copper
dissolution. Figure 6.26 shows that the effect of galvanic interactions on gold dissolution is
rather unclear as experiment with no pyrite addition had the highest gold dissolution of 44.93
164
%. Gold extraction in the presence of 8 kg/t and 4 kg/t pyrite was 29.70 and 21.35 %,
respectively. The trendless results could be a consequence of the varying concentrations of
pyrite in the sample as the ore initially contained about 0.2 % pyrite.
100
90
4 kg/t pyrite
70
8 kg/t pyrite
60
Cu extraction, %
50
40
30
20
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.25 Effect of galvanic interactions on Cu leaching from Cu-Au ore B: [Gly] 0.5 M, pH 11.5, 60
°C, O2 0.05 L/min, P100 75 µm and 50 %w/v solids.
50
45
4 kg/t pyrite
35
8 kg/t pyrite
30
Au extraction, %
25
20
15
10
0
0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96
Time, h
Figure 6.26 Effect of galvanic interactions on Au leaching from Cu-Au C: [Gly] 0.5 M,
pH 11.5, 60 °C, O2 0.05 L/min, P100 75 µm and 50 %w/v solids.
165
6.5 Heap Leach Simulation
The heap leaching technique (discussed in Section 2.6) is the most economical method for
processing low grade ores due to their high gangue content. The essence of the heap
simulation experiments in this research was not to determine optimum conditions for heap
application but to investigate the possibility of extracting copper and gold by heap leaching
using alkaline glycine solutions from such low grade copper-gold ores. The leaching process
was monitored by measuring the concentration of copper and gold in the PLS collected at
the base of the columns.
6.5.1 Copper-Gold ore C

The mineralogical composition of the Cu-Au C ore used for the column test was given in
Section 6.3.1. The ore is a low grade chalcopyrite containing gold. A particle size range of 1-
8 mm was selected in order to avoid any clogging that reduces percolation which is critical in
heap leach operations (Lwambiyi et al., 2009). The size distribution of the ore is given in Table
6.4. Elemental analysis of the ore used is shown in Table 6.5.
Table 6.4 Particle size distribution for column leaching of Cu-Au ore C
Size range, mm mass, g Percentage Cumm. %

+1-1.40 79.5 13.73 13.73
+1.4-2.0 73.51 12.70 26.43
+2.0-2.8 83.36 14.40 40.83
+2.8-3.35 53.91 9.31 50.14
+3.35-40 62.21 10.75 60.88
+4-5.6.7 130.68 22.57 83.46
+5.6-6.7 62.2 10.74 94.20
+6.7-8.0 33.58 5.80 100.00
166
Table 6.5 Elemental composition of Cu-Au ore C used for heap simulation
Element Value Element Value

Au (ppb) 782 Rb (%) 0.015
Al (%) 8.2 Si (%) 30.08
Ba (%) 0.022 S XRF (%) 0.23
Ca (%) 3.47 Sr (%) 0.02
Co (%) 0.002 Ti (%) 0.38
Cr (%) 0.02 V (%) 0.008
Cu (%) 0.095 Y (%) 0.008
Fe (%) 3.39 Zn (%) 0.008
GA_X (%) 0.002 Zr (%) 0.021
K XRF (%) 1.29 U XRF (%) 0.007
Mg (%) 1.73 Cl (%) 0.013
Mn (%) 0.05 W XRF (%) 0.007
6.5.1.1 Copper and Gold Dissolution

Two different glycine concentrations (0.1 M and 0.5 M) were used for leaching. A mass of 5
kg ore was loaded in each column and caustic was used to control the leach solution at pH
11. The solution was circulated from a 4.5 L container at a rate of 33 L/m2/h. Copper and gold
recoveries from the ore were determined based on solution assays and head grades. The
corresponding copper recovery curves are plotted in Figure 6.27. As expected, copper
dissolution was improved by higher glycine concentration with 6 % extracted after 36 days
for 0.5 M and 3.5 % with 0.1 M glycine. Although copper dissolution is slow, the steady
increase over time as shown by the curves indicate that the closed circuit leaching can be
lengthened in order to get more extraction. Gold dissolution, as can be seen in Table 6.6, was
rather slow with 1.61 % achieved after 159 days for 0.1 M glycine and 0.99 % gold after 103
days of leaching with 0.5 M glycine.
The slow Cu and Au dissolution could be attributed to insufficient contact between host
minerals and lixiviant due to the relatively large particle size or poor permeability of ore
(Zanbak, 2012)
167
12
10
Cu extraction, % 8
[Gly] 0.1 M
4
[Gly] 0.5 M
2
0
0 12 24 36 48 60 72 84 96 108 120 132 144 156 168
Time, days
Figure 6.27 Column Cu leaching from Cu-Au ore C, pH 11, 25 °C, 33 L/m2/h
Table 6.6 Column Au leaching from Cu-Au ore C, pH 11, 25 °C, 33 L/m2/h
[Gly] Time, days Au extraction, %
0.1 M 87 0.54
111 1.46
159 1.61
0.5 M 36 0.31
60 0.54
103 0.99
6.5.2 Copper-Gold ore D

Copper-gold ore D was a flotation tail from a copper processing plant in Western Australia.
The dry Cu-Au ore as received was partly and naturally agglomerated (during drying). It was
screened at 2 mm screen size and found that about 57.56 % of the ore was below 2 mm while
the remaining 42.4 % was made up of particles with diameters >2 mm.
6.5.2.1 Mineralogy
Mineralogical analysis of the ore by TIMA revealed that chalcopyrite is the only copper phase
and makes up < 1 % by mass as shown in Table 6.7. The major gangue phases were pyrite and
quartz at 43 % and 32 %, respectively. The gold content of the ore was 648 ppb as determined
168
by fire assay. XRF analysis showed that the ore contains 0.37 % copper. This is another typical
example of a low grade copper-gold ore with heap leaching being the most economical
technique for such ores. A column leaching experiment was thus conducted to simulate a
heap leaching technique.
Table 6.7 Mineralogy and elemental composition of Cu-Au ore D
Phase % Element value Element value

Chalcopyrite <1 Au (ppb) 648 K XRF (%) 0.11
Pyrite 43 Ag (ppm) 12 Na (%) 0.14
Spinel group 2 Al (%) 2.08 Mn (%) 0.16
Quartz 32 Fe (%) 23.75 Ti (%) 0.09
Chlorite 10 Pb (%) 0.11 Zn (%) 1.13
Gypsum 10 Ca (%) 1.13 P XRF (%) 0.03
Mica 2 Mg (%) 1.46 Ba (%) 0.02
S XRF (%) 19.20 Cu (%) 0.37
Ni (%) 0.01 S LECO (%) 19.70
6.5.2.2 Copper and Gold Dissolution

The experiment was conducted according to the procedure outline in Chapter 3 and at
ambient temperature. The leaching solution at pH 11 containing a glycine concentration of
0.5 M was circulated at a rate of 135 L/m2/h. Air was injected at the bottom of the column at
a rate of 0.1 L/min. The results as shown in Figure 6.28 indicate that copper dissolution
increased steadily throughout the 48 days of leaching with 53.6 % Cu extracted. Gold
dissolution was noted to be very slow with 7.6 % Au leached after 48 days (Table 6.8).
60
50
40
Cu extraction, %
30
20
10
0
0 6 12 18 24 30 36 42 48 54
Time, days
Figure 6.28 Column Cu leaching from Cu- Au ore D: pH 11, 25 °C, 135 L/m2/h
169
Table 6.8 Column Au leaching from Cu-Au ore D: pH 11, 25 °C, 135 L/m2/h
Time, days [Au], mg/L Au extraction, %
40 1.15 5.032
49 1.32 7.548
6.5.3 Improving heap leaching rates

Heap leaching, which is generally accepted as the most economical method for processing
low grade ores has however, been hampered by low recoveries and long leaching times as
much as 1-2 years, if not more (Ghorbani et al., 2013). As was noted with the heap leaching
of Cu-Au B, copper recoveries were very low with only 9 % in over 156 days. The rock was
observed to be quite competent (not friable and not porous), indicating that only the mineral
grains on the surface were exposed to the lixiviant. It has been suggested that leaching rates
are closely linked to the method by which the ore was crushed prior to leaching (Watling,
2006). Comminution by high pressure grinding rolls (HPGR) introduces cracks at grain
boundaries (Unland & Szczelina, 2004) leading to mineral liberation and higher exposure of
mineral grains to leach solutions (Ghorbani et al., 2013). The results of research conducted
by (Daniel, 2007) on energy efficient mineral liberation using HPGR showed a higher gold
leachability when the ore was crushed by HPGR compared to conventional crushing. Thus,
for ores such as Cu-Au ore B with high competency, leaching rates could be significantly
improved by crushing the ore with HPGR grinding before leaching.
In Sections 6.3.4 and 6.4.4, it was realised that elevated temperature of 60 °C significantly
improved the extent of copper and gold extraction. In heap leaching, such temperatures
could be achieved by the use of solar heating systems to heat leaching solutions and black
piping for the transport of heated solutions to the top of the heap. Investigations on the
potential for solar thermal energy in the heap bioleaching of chalcopyrite showed that
copper extraction increased from 67 % to 85 % by heating the leach solution through the
solar heating system. It was further reported that the net present values and internal rates
of return of the project were positive (Murray et al., 2017).
Oxidation is an important part of chalcopyrite and gold leaching. It was noted in Sections
6.3.5 and 6.4.5 that higher oxygen flow rates significantly improve both copper and gold
leaching as this increases the concentration of dissolve oxygen in the leach solution. In some
170
industrial applications, air is pumped into the heap from the bottom (Wu et al., 2009) and as
illustrated by Figure 3.3. Tests conducted to explore ways of increasing heap leaching
efficiency by the addition of oxygen to the leaching solution have shown major improvement
in metal extraction rates (Kenney et al., 1987). Thus in the leaching of some sulfide minerals
in which the need for high DO is critical, oxygen can be injected directly into the barren leach
solutions.
6.6 Summary
Copper dissolution from the gold-copper oxide ore (Cu-Au ore B) was not influenced by
glycine concentration, initial solution pH, temperature, oxygen flow rate and galvanic
interactions as the overall percentage of copper dissolved under all conditions was around
75 %. However, gold dissolution from the gold-copper oxide ore (Cu-Au ore B) was influenced
by temperature, oxygen and galvanic interactions. At 60 °C, gold dissolution reached 32.2 %
mean while only 0.5 % Au was extracted at 25 °C. Galvanic interactions through the addition
of finely ground natural pure pyrite resulted in a significant improvement in gold dissolution
from the gold-copper oxide ore as 60.4 % was dissolved with the addition of 20 g/t pyrite. In
the absence of these galvanic interactions (i.e., no pyrite addition), only 23.4 % gold was
extracted.
The extent and rate of copper and gold dissolution from the gold-copper sulfide ores was
more dependent on process variables than the oxide ore. Copper and gold dissolution from
Cu-Au ore C increases as the glycine concentration increases. At 1.0 M glycine, copper and
gold extraction were 65.1 % and 53.1 %, respectively, after 500 hours of leaching by a bottle
roll technique. Higher temperature favoured copper dissolution with a 65.96 % obtained at
60 °C after 96 hours of leaching as opposed to 40.67 % at 25 °C. The oxygen flow rate of 0.3
L/min positively affected copper dissolution but unexpectedly affected gold dissolution
negatively.
The major difference between the behaviour of gold-copper oxide ore and gold-copper
sulfide ore is the simultaneous dissolution of gold and copper from the copper-gold sulfide
ores at room temperature. The significant improvement in gold dissolution from the gold-
copper oxide ore emanates from the addition of pyrite. Thus, gold dissolution from the
copper-gold sulfide ores at room temperature could be attributed to the presence of galvanic
interactions between the gold and the inherent pyrite in the ore.
171
Chapter 7 Recovery of Metals from
Alkaline Glycine Pregnant
Leach Solutions
7.1 Chapter Overview and Background
In order to consider the feasibility of any new leaching system, it is imperative to study both
the leachability of valuable metals from their different resources and the recovery of these
metals from the leach solutions (Awakura et al., 1991). Alkaline glycine solutions have been
shown to be an effective lixiviant system for copper and precious metals from various
mineralised sources including oxides, native and sulfide mineral forms (Oraby and Eksteen,
2014a and 2014b; Eksteen et al., 2016). The leaching behaviour of copper oxides in aqueous
alkaline glycine solutions studied by Tanda et al. (2017) confirmed the selective dissolution
of copper over impurity elements, in particular of iron, magnesium, aluminium and silicon. It
has also been confirmed in Section 5.2 that, during the leaching of copper minerals with
alkaline glycine/glycinate solutions, only cupric ions form the stable complex with glycine
[Cu(H2NCH2COO)2]. With leachability of copper having been studied and reported in the
previous chapters, the next main objective of this work will be to investigate methods for
recovering copper from the alkaline glycine PLS. Two methods, the versatile solvent
extraction and metal sulfide precipitation will be investigated.
Solvent extraction (SX), since its introduction in the mineral industry in the 1940s, has
become a major unit processing step in hydrometallurgy due to its versatility in the
extraction, separation/purification and recovery of metals from aqueous solution (Cox, 2004;
Junior et al., 2012). The continuous popularity of SX in hydrometallurgy the development of
new extractants with improved selectivity, faster kinetics and phase disengagement times,
and efficient equipment with less area and reagent inventory, means that the technique can
be applied to lower value metals. Leaching/Solvent extraction/Electrowinning (L/SX/EW)
process generally portray lower capital and operating cost compared to traditional
floatation/smelting approaches. L/SX/EW can obtain copper at a low cost from low-grade
overburden that needs to be mined but which would not be otherwise processed by
float/smelt routes (Kordosky, 2002). For any extractant to be used commercially, it must
meet the criteria of availability at low cost, low solubility in aqueous and high solubility in
organic diluents, and high selectivity to form complexes with target metals and from which
172
the metal can easily be recovered while the extractant is recycled (Gupta & Mukherjee,
1990).
A variety of solvent extraction reagents have been investigated for the recovery of copper
from pregnant leach solutions. Oximes and β-diketone extractants have been extensively
studied and applied commercially in the extraction of copper from acidic and alkaline
aqueous solutions (Ackerley et al., 1977; Alguacil, 1999; Mickler et al., 1992; Reddy et al.,
2005; Sarangi et al., 2007; Tinkler et al., 2009). The oximes do have higher extraction strength
that might lead to low stripping efficiencies. In acidic medium, the β-diketones are less
effective than the oximes but pose an advantage in the alkaline medium such as ammonia
solutions as they do not co-extract ammonia. Another advantage of β-diketones is their
ability to transfer higher amounts of copper from the leached solutions which can then be
easily stripped as compared to oxime extractants (Cox, 2004). To exploit the advantages
presented by oxime and β-diketones, they are used together for the extraction of metals.
Common commercially available oxime and β-diketone extractants are LIX 84I (2-hydroxy-5-
nonylacetophenone oxime) and LIX 54-100 (1-phenyldecane-1, 3-dion), respectively
(Kordosky, 2002). LIX 84 is a popular extractant for copper (Sengupta et al., 2007) and LIX 54-
100, which was specifically developed for the recovery of copper from ammoniacal leaching
solutions (Alguacil & Alonso, 1999; Fu et al., 2010), is being used in the industry for the
recovery of copper from its leached solutions (Kordosky et al., 1999). Recently, Mextral 84H
and Mextral 54-100, which were used as extractants in this research project, were
synergistically used for the solvent extraction of zinc from an ammoniacal/ammonium sulfate
solutions with sulfonated kerosene as diluent (Tang et al., 2016). Mextral 84H has the same
active component (2-hydroxy-5-nonylacetophenone oxime) as LIX 84I.
In the copper solvent extraction of Cu-glycinate solution, the extractant can extract the metal
of interest from the solution by replacing the glycine ligands and, by so doing, form a copper-
extractant complex. Alternatively, the whole Cu-glycinate complex can be picked up by the
extractant as is the case with Cu- cyanide complex and LIX 7950 extractant (Xie & Dreisinger,
2010).
The general extraction process can be represented as in Equation 7.1 while that for stripping
is given by Equation 7.2.
2RH(org) + Cu(H2NCH2COO)2 (aq) = R2Cu(org) + 2H2NCH2COOH (aq) (7.1)
173
R2Cu(org) + 2H+(aq) = 2RH(org) = Cu2+(aq) (7.2)
The rich electrolyte solution from the stripping stage is fed into an electrowinning unit to
produce high purity copper at the cathode as depicted by Equation 7.3.
Cu2+(aq) + 2e- = Cu(s) (7.3)
Metal precipitation is also an essential unit process in the hydrometallurgical industry. It is

based on the solubility or actually the lack of it in the precipitated product. In practice,
precipitation can be done by hydroxide (CaO or Ca(OH)2, Mg(OH)2, NaOH and NH4OH), sulfide
(FeS, CaS, Na2S, NaHS, (NH4)2S, H2S, Na2S2O3) or carbonate. Although hydroxide precipitation
is commonly applied in the industry, metal sulfide precipitation presents advantages such as
lower solubility of metal sulfides, fast precipitation rates, better settling properties and the
stability of the metal sulfides formed (Lewis & van Hille, 2006; Lewis, 2010). Metal sulfide
precipitation from synthetic copper alkaline glycine solutions and from actual leach solutions
using NaHS as a precipitant will be explored in this chapter. H2S and Na2S may also be
considered, but the chemistries are likely similar and was therfore considered to be beyond
the scope of this work.
7.2 Solvent Extraction of Copper from

Synthetic Copper Glycinate Solution
7.2.1 Effect of Aqueous pH

The effect of pH on copper extraction by Mextral 84H, a mixture of ketoxime (2-hydroxy-5-
nonylacetophenone oxime) with a high flash point hydrocarbon diluent and Mextral 54-100,
a β-diketone (1-benzoyl-2-nonyl ketone) in a mixture with high flash point hydrocarbon
diluent) was determined using an aqueous solution containing 2 g/L Cu and 7.1 g/L glycine to
yield a glycine-to-copper (Gly:Cu) molar ratio of 3:1. The initial aqueous pH was varied with
sodium hydroxide from 9 to 12. The extractions were carried out by mixing the organic phase
composed of 10 % extractant in DT 100 diluent at an A:O ratio of 1:1 for 15 minutes at 20 °C.
The results shown in Table 7.1 indicate that initial pH of the aqueous phase does not
significantly influence copper extraction by Mextral 84H as the percentage of copper
extracted exceeds 99 % for all pH values evaluated. However, for Mextral 54-100, when the
174
pH is raised from 9 to 12, a slight increase in the copper extracted from 97.3 to 99.5 % is
noted.
Table 7.1 Effect of pH on copper extraction. Experimental conditions: Gly:Cu 3:1, A:O 1:1, 20°C
Extractant/pH pH 9 pH 10 pH 11 pH 12
Mextral 84H 99.49 99.47 99.66 99.68
Mextral 54-100 97.29 98.08 98.66 99.48

Extraction experiments were carried out using an aqueous solution containing 2 g/L Cu at
Gly:Cu molar ratio of 3:1 and pH 11. The different phases were allowed to attain the set
temperature (15 to 55 °C) and then contacted at an A:O 1:1 for 15 minutes at the set
temperatures. Results in Table 7.2 show that, within the studied temperature range, there is
no significant influence on the copper extracted by either of the extractants as the
percentage extracted stayed between 99.67 to 99.89 % and 97.36 to 97.89 % for Mextral 84H
and Mextral 54-100, respectively.
Table 7.2 Effect of temperature on copper extraction. Gly:Cu 3:1, A:O 1:1, 20°C.
Extractant / Temperature (°C) 15 30 40 55

Mextral 84H 99.67 99.63 99.79 99.83
Mextral 54-100 97.36 97.67 97.89 97.32
7.2.3 Effect of Contact Time

The impact of contact time between the aqueous and organic phases was studied using an
A:O ratio of 1:1, pH 11.0 and at 20 °C for different contact periods ranging from 2 to 30
minutes. The results shown in Table 7.3 indicate that copper extraction is very rapid as
equilibrium is reached within 2 minutes. A mixing time of 10 minutes was then selected for
the rest of the extraction experiments to ensure equilibrium is attained.
Table 7.3 Effect of mixing time on copper extraction. Gly:Cu 3:1, pH 11, A:O 1:1, 20°C.
Extractant/ Time(mins) 2 5 10 30
Mextral 84H 99.88 99.88 99.88 99.89
Mextral 54-100 97.53 97.56 97.58 97.60
175
7.2.4 Effect of Glycine Concentration
The influence of glycine, which is the main leaching agent for this system, was investigated
by varying the Gly:Cu ratio in the aqueous phase from 2:1 to 16:1 while the aqueous copper
content was kept at 2g/L and pH 11. The organic phases from either extractant (10 % v/v
extractant) were then contacted with the aqueous phases at an A:O ratio of 1:1 at 20°C for
10 minutes. The results presented in Table 7.4 show that increasing the Gly:Cu ratio from
2:1 to 16:1 has no significant effect on the copper extractability by Mextral 84H as
percentages stay above 99.9 % at all ratios. With Mextral 54-100, a drop in copper extraction
from 97.86 to 93.02 % was noted as the Gly:Cu ratio is increased from 2:1 to 16:1.
Table 7.4 Effect of glycine concentration on copper extraction: pH 11, A:O 1:1, 20°C
Extractant/Gly:Cu 2:1 3:1 8:1 16:1

Mextral 84H 99.97 99.93 99.94 99.94
Mextral 54-100 97.86 97.05 96.35 93.02
7.2.5 Effect of Extractant Concentration

The effect of the extractant concentration was studied by varying the content of extractant
in the diluent (2.5 to 30 % v/v). The aqueous phase composed of 2 g/L Cu at a molar ratio of
3:1 Gly:Cu at pH 11 was mixed with the organic phases at an A:O ratio of 1:1 for 10 minutes
at 20 °C. After phase separation, the equilibrium pH values were within 9.38-10.12 for
Mextral 84H and 9.34 to 9.55 for Mextral 54-100. The raffinates were analysed and the
percentage copper extracted was plotted against extractant concentration as shown in
Figure 7.1. For Mextral 84H, when the extractant concentration was increased from 2.5 % to
5 %, the percentage copper extracted increased from 57 to 99 % with no change with further
increments of extractant concentration up to 30 %. Although 2.5 % Mextral 54-100 led to a
78.44 % copper extraction, the percentage copper extracted plateaued at 97 % with 10 %
extractant and above.
176
Figure 7.1 The effect of extractant concentration on copper extraction: Gly:Cu 3:1 A:O 1:1, 20 °C,
10 minutes
7.2.6 Loading Capacity of Mextral 84H and

Mextral 54- 100
The loading capacity of an extractant is an important factor in its commercial application as
it indicates the maximum metal concentration that the extractant can contain under specific
conditions (Srivastava et al., 2015). The loading capacities can either be determined by
varying the organic to aqueous phase ratios or by recontacting the organic phase with fresh
aqueous phase until saturation is reached (Ritcey, 2004). The recontacting method has been
used for these studies.
An aqueous phase containing 2 g/L Cu complexing at a 1:3 mole ratio with glycine at pH 11
was contacted with the organic phases (10 % v/v of either extractants in DT100) at a 1:1
phase ratio, 20 °C and mixed for 10 minutes. The organic phases were repeatedly contacted
with a fresh aqueous phase and after 5 cycles, Mextral 54-100 contained 10.16 g/L copper
while Mextral 84H contained 5.43 g/L. The extractants concentrations were raised to 30 %
and the copper content on loaded Mextral 54-100 was noted to be 29.65 g/L as opposed to
just 15.33 g/L obtained in Mextral 84H. These results indicate that, for the same
concentration of extractant, the amount of copper loaded on Mextral 54-100 doubles that
on Mextral 84H. This observation supports the reported potential of betadiketones having
higher copper net transfer than their oxime counterparts (Hu et al., 2010; Kordosky et al.,
1999).
177
7.2.7 Extraction Distribution Isotherm
In solvent extraction, an extraction isotherm is generally constructed to determine the
number of stages needed to efficiently extract the metal of interest at a given phase ratio.
The organic phases of 5 % Mextral 84H and 10 % Mextral 54-100 were mixed with the
aqueous phase at different A:O ratios within 10:1 to 1:4 and pH 11 at 20 °C for 10 minutes.
The copper content of the aqueous and organic phases after phase disengagement was
determined. The results showed that at an A:O ratio of 2:1, 99.90 % Cu was extracted by 5
% Mextral 84 while 95.87 % copper extraction was attained with 10 % Mextral 54-100.
The McCabe-Thiele plot as shown in Figure 7.2 has been constructed at an operating A:O
phase ratio of 2:1 indicated that copper can be completely extracted in one stage with 5 %
Mextral 84H and two stages with and 10 % Mextral 54-100.
Figure 7.2 Extraction isotherm of copper with 5% Mextral 84H and 10% Mextral 54-100. Conditions
operating A:O 2:1, 20 °C, for 10 minutes.
7.2.8 The Fate of Glycine during Solvent

Extraction
It is well known that some extractants co-extract lixiviants together with the metals of
interest during the extraction process. LIX 64N (an oxime extractant), studied for the
extraction of copper and nickel from an ammoniacal-ammonium carbonate solution, has
been noted to transfer ammonia; requiring a scrubbing step to remove the transfered
178
ammonia (Sandhibigraha & Bhaskara Sarma, 1997). Similarly, LIX 7950 extracts the complete
copper cyanide complex (Xie & Dreisinger, 2010) implying that acidic stripping cannot be
done for Cu-CN systems since it would lead to the production of toxic HCN gas. Thus in this
study, there is the need to establish if Mextral 84H or Mextral 54-100 transfers glycine from
the leached solution to the organic phase. 10 % Mextral 84H and 10 % Mextral 54-100 were
used to recover copper from the aqueous solution at an A:O of 1:1 and 20 °C. HPLC-UV/Vis
analysis for free glycine/glycinate in the aqueous phase after extraction showed that neither
extractants transferred glycine/glycinate into the organic phases.
7.2.9 Sulfuric Acid Stripping of Copper Loaded

Organics
The copper loaded organic phases of 5 % Mextral 84H and 10 % Mextral 54-100 were stripped
with different concentrations of sulfuric acid solutions (10-200 g/L) at an A:O ratio of 1:1 and
20 °C for 10 minutes of mixing time. From Table 7.5, Mextral 84H copper stripping increased
from 54.0 to 97.7 % with increasing acid concentration from 10 to 120 g/L. However, copper
was readily stripped with sulfuric acid solution from Mextral 54-100 with > 97 % stripping
using 10 g/L sulfuric acid solution. This is an indication that copper tends to form stronger
complexes with Mextral 84H, a ketoxime, than with Mextral 54-100, a di-ketone.
The stripping of copper from an oxime type extractant, Acorga M5397, has also been
reported to be completed at high sulfuric acid concentrations of 2.0 M (Amari et al., 2013).
During the stripping of copper from loaded LIX 54, a ketone extractant, Qi-wen et al. (2011)
reported that copper can be efficiently stripped at low acid concentration (96.70 % Cu at 100
g/L H2SO4).
Table 7.5 Stripping of copper loaded 5% Mextral 84H and 10% Mextral 54-100 with various H2SO4
concentrations. Conditions: A:O ratio 1, 20°C.
[H2SO4], g/L % Cu stripped

Mextral 84H Mextral 54-100
10 54.02 97.34
30 86.00 99.95
50 96.57 100.00
80 59.14 100.00
120 97.62 100.00
150 97.32 100.00
180 97.27 100.00
179
7.2.10 Stripping Isotherm and Counter Current
Stripping Simulation
To determine the number of stripping stages and the operating A/O ratio, a stripping
isotherm for each extractant was constructed with the stripping solution bearing similar
conditions to that of a spent electrolyte (SE) exiting an electrowinning operation of 30 g/L Cu
and 180 g/L H2SO4 (Sarangi et al., 2007). The loaded organic phases containing 2g/L Cu were
contacted with the SE at various A:O ratios (2:1 to 1:10) at 40 ° C for 10 minutes. At an A:O
ratio of 1:10, 99.59 % copper is stripped from loaded Mextral 54-100. Under the same
conditions, only 79.95 % copper was stripped from Mextral 84H.
The McCabe-Thiele plot in Figure 7.3 illustrates that that three stages will be needed to
effectively strip copper from the loaded Mextral 84H at the A:O ratio of 1:10 while just one
stage is needed for Mextral 54-100.
Figure 7.3 Stripping isotherm of copper loaded organic. Conditions: 30 g/L Cu and 180 g/L H2SO4,
A:O= 10:1, at 40°C
7.3 Solvent extraction from Malachite

leachate and stripping of Cu from
Extractant
The mineralogical and elemental analysis of the malachite ore specimen, leached to provide
a feed solution for the SX study, is shown in Table 7.6. Malachite is the only copper mineral
in the ore specimen.
180
Table 7.6 Mineralogical and elemental composition of copper oxide (malachite) specimen
Phase Goethite Hematite Malachite Quartz Amorphous Content

Wt % 1.7 3.3 66 16.7 12
Element Cu Al Si K Mg Fe Ca
% 41.55 0.13 8.49 0.11 0.38 3.53 0.81
The malachite sample was bottle rolled for 24 hours at pH 11 at a Cu-Gly molar ratio of 1:4.
The leachate had a copper concentration of 2.620 g/L and a final pH of 12. Copper extractions
were carried out using 5 % Mextral 84H and 10 % Mextral 54-100 at different organic to
aqueous ratios.
Table 7.7 shows the percentage copper extracted at different organic to aqueous ratios. For
both extractants, 99 % copper was extracted at an O:A ratio of 2:1. Any increments in
aqueous volume resulted in lower copper extractions for both reagents. The fate of
impurities was determined by ICP analysis of the aqueous raffinate derived from the O:A ratio
1:1 extraction.
Table 7.7 Percentage copper extractions from malachite by 10 % Mextral 54-100 and Mextral 84H
at different O:A ratios
Organic: Aqueous Ratio Mextral 54-100 Mextral 84H

% Cu extraction % Cu extraction
2:1 99.39 99.93
3:2 99.27 99.82
1:1 98.90 99.14
1:2 95.64 44.53
1:4 76.13 13.53
The results shown in Table 7.8 indicate that both extractants selectively extract copper from
the leached solutions. The results also confirm the selectivity of leaching copper with alkaline
glycine solutions (Tanda et al., 2017).
181
Table 7.8 Elemental analysis of malachite leachate and raffinate before and after solvent
extraction respectively with 10 % Mextral 54-100 and Mextral 84H at an O:A ratio of 1:1
Leachate before and after SX Concentration, mg/L

Cu Fe Mg Ca Si Al pH
Leachate before SX 2620 <0.2 <0.2 0.85 3.65 0.237 12.00
Raffinate after SX with Mextral 54-100 24.9 <0.2 <0.2 0.88 3.64 0.240 9.76
Raffinate after SX with Mextral 84H 19.4 <0.2 <0.2 1.22 3.58 <0.2 10.00
The results of the stripping test are presented in Table 7.9. The loaded organic phases derived
from the malachite leachates were contacted with the spent electrolyte solution (30 g/L Cu,
180 g/L H2SO4) at various O:A ratios (2:1 to 1:10) at 40 ° C, for 10 minutes. At an O:A ratio
of 10:1, about 99.3 % of the copper was stripped from loaded Mextral 54-100 extractant.
Under the same conditions, only 78.3 % copper was stripped from the loaded Mextral 84H
extractant. At an O:A stripping ratio of 1:1, the spent electrolyte proxy solution could strip
the loaded Mextral 54-100 extractant from 99.96 % of its copper, while it only strips 90.01 %
copper from the loaded Mextral 84H organic phase.
Table 7.9 Stripping of copper from loaded Mextral 54-100 and Mextral 84 H ( Cu loaded from
malachite leachate) using a proxy spent electrolyte solution (30 g/L Cu, 180 g/L H2SO4) at various
organic to aqueous ratios: 40 °C, 10 mins.
Organic:Aqueous Cu stripped from loaded Mextral 54- Cu stripped from Mextral loaded
Ratio 100, % 84H, %
10:1 99.32 78.30
4:1 99.82 86.29
2:1 99.98 88.77
1:1 99.96 90.01
1:2 99.99 90.64
7.4 Solvent Extraction of Copper from

Chalcopyrite B Leachate and Cu Stripping
from Extractant
The mineralogy and elemental composition of the chalcopyrite specimen is given in Table
7.10. A “dirty” concentrate consisting of low grade chalcopyrite with significant impurities
was used to obtain the proxy pregnant leach solution.
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Table 7.10 Mineralogical and elemental composition chalcopyrite B specimen
Mineral Chaba- Chalco- Clino- Pyrite Quartz Rutile Amor-

Phase zite phous
pyrite chlore
Wt % 0.8 35.0 1.5 29.4 0.9 0.4 32.0
Element As Ca Cu Fe Mg Pb Si S Zn
Wt % 0.709 0.31 14.8 30.9 1.08 0.29 3.64 32.4 4.95
The chalcopyrite specimen was leached in a glass reactor at 60 °C and DO concentration of

20 ppm at pH 11.8 for 24 hours. The final leach solution contained 2.288 g/L Cu at pH of 10.5.
Copper extraction experiments using 5 % Mextral 84H and 10 % Mextral 54-100 were carried
out at different organic to aqueous ratios. Copper extractions of 93.20 % and 95.57 %, for 10
% Mextral 54-100 and 5 % Mextral 84H, respectively, were obtained at an O:A ratio of 2:1
(Table 7.11). The lower copper extraction obtained for chalcopyrite leachate as compared to
that from synthetic solutions could be attributed to the partial co-extraction of other base
metals. The influence of the leached impurities on the copper SX process was monitored by
analysing the concentration of copper and impurities in leachate before and after SX.
Table 7.11 Percentage copper extractions from chalcopyrite B leachate by 10 % Mextral 54-100
and Mextral 84H at different O/A ratios
Organic/Aqueous ratio Mextral 54-100 Mextral 84H

% Cu extraction % Cu extraction
2:1 93.20 95.57
3:2 92.66 92.70
1:1 91.01 86.66
1:2 87.92 83.01
1:4 78.45 55.12
Table 7.12 shows that, although some impurity elements are leached along with copper
(though to lower extent), the extractants selectively extracted copper from the leached
solution.
183
Table 7.12 Elemental analysis of chalcopyrite B leachate and raffinate before and after solvent
extraction respectively with 10 % Mextral 54-100 and Mextral 84H at an O:A ratio of 1:1
Leachate before and after Leachate Raffinate after SX Raffinate after

SX before SX with Mextral 54- SX with Mextral
100 84H
Concentration , mg/L Cu 2288 205 304
Zn 699 584 709
Fe 3.5 14 14.2
Mg 1.66 2.12 2.05
As 1.17 2.07 1.76
Ca 5.5 5.33 6.05
Pb <0.2 <0.2 <0.2
Si 0.49 1.47 1.12
Co 15 17.4 16.8
Ni 8.15 8.39 8.96
Raffinate pH before and 10.55 9.87 9.91
after SX
Cu from the loaded organics was stripped using a spent electrolyte solution (30 g/L Cu, 180
g/L H2SO4) at different O:A ratios (10:1 to 1:2) at 40 °C for 10 minutes. Table 7.13 gives the
strip recovery of Cu from loaded Mextral organic at various O:A ratios. About 99.4 % Cu was
stripped from loaded Mextral 54-100 at an O:A ratio of 10:1 while 81 % Cu was obtained
from Mextral 84H at the same O:A ratio. At a 1:1 O:A stripping ratio, the spent electrolyte
proxy solution could strip 99.99 % copper from the loaded Mextral 54-100 extractant while
it could only remove 89.45 % of the copper from the loaded Mextral 84H extractant.
Table 7.13 Stripping of copper from loaded Mextral 54-100 and Mextral 84H ( Cu loaded from
chalcopyrite leachate) using a proxy spent electrolyte solution (30g/L Cu, 180g/L H2SO4) at various
organic to aqueous ratios: 40 ° C, 10 mins.
Org/Aq ratio Cu stripped from loaded Mextral 54- Cu stripped from Mextral loaded
100, % 84H, %
10:1 99.37 81.43
4:1 99.93 85.38
2:1 99.98 89.15
1:1 99.99 89.45
1:2 99.99 90.69
The fate of impurity elements during copper stripping from the loaded organics was
investigated at an O:A ratio of 2:1. On stripping from loaded Mextral 54-100, the
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concentrations of Cu, Zn, Co and Ni in the rich aqueous phase were 35.0 g/L, 101 mg/L, 1.45
mg/L, and 1.15 mg/L respectively. For Mextral 84H, the concentrations of Cu, Zn, Co and Ni
were 34.4 g/L, 2.86 mg/L, 1.31 mg/L, and 2.01 mg/L respectively. Therefore the
concentration increase of copper in the aqueous electrolyte strip solution, from the 30 g/L
baseline, was the order of 4.4 g/L (from Mextral 54-100 strip) to 5.0 g/L (from Mextral 84H
strip).
The main objective of the extraction and stripping evaluation from actual leachates is to
provide a measure of the deportment of typical impurity elements. The two leachates were
chosen as examples of leachates derived from a copper oxide and a copper sulfide mineral
source..
7.5 Solvent Extraction of Copper from a

Copper-Gold leachate
The concurrent dissolution of copper and gold from their ores as noted in Chapter 6 makes
it paramount to investigate the fate of Au-glycinate during the solvent extraction of copper
from the leachate. The feed solution for this investigation was obtained by leaching 500 g
copper-gold ore C (mineralogy of the ore was reported in Section 6.3.1) in a 1 L glass reactor
for 96 hours under the following conditions: 100 % passing 75 µm, 60 °C, 0.5 M Gly and 0.05
L/min oxygen at an initial solution pH of 11.85 . The leachate at pH 10.32 contained 784 mg/L
Cu and 0.241 mg/L Au. Copper extraction by 10 % Mextral 54-100 and 5% Mextral 84H at an
A:O ratio of 2:1 was carried out and the results are shown in Table 7.14. Copper extraction
was 80.2 % and 99.8 % for Mextral 54-100 and Mextral 84H, respectively. Although the results
indicate that gold concentration in solution after copper extraction with Mextral 54-100 and
Mextral 84H, respectively, reduced by 1.7 and 2.1 %. The values are within an accepted
analytical error range. It can thus be concluded that the Au ions/Au-glycinate complex is not
picked up by either extractant. It has been reported by Eksteen and Oraby (2015a) that gold
from alkaline glycine solutions can be loaded onto activated carbon. Hence, a flowsheet can
be proposed in which Cu-Au ores are leached in alkaline glycine solutions, Cu can be
recovered by solvent extraction and then Au by activated carbon. Au recovery from alkaline
glycine solutions has already been studied by Oraby and Jacques, 2015. They found out that,
Au could be adsorbed onto carbon at a rate of 13.2 KgAu/tcarbon.
185
Table 7.14 Copper extraction from Cu-Au ore C leachate using Mextral 54-100 and Mextral 84H:
A:O 2:1, pH 10.32, 25 °C
Extractant Cu extraction, % Au extraction, %

10 % Mextral 54-100 80.22 1.66
5 % Mextral 84H 99.79 2.07
7.6 Qualitative Comparison of Cost Drivers of

the Alkaline Glycine Leach-SX and
Conventional Sulfuric Acid Leach-SX
Processes for Copper Ores.
The production capacity of installed conventional sulfuric acid based Leach-SX-EW as of 2001
was 2.8 million tonnes of copper accounting for about 20% of primary copper production
(Kordosky, 2002). Generally, several variables account for the operating costs of copper acid
leaching processing plants, and the cost of acid consumption forms a significant portion of
the operating cost. This is especially significant for treating carbonaceous ores whereby 1 ton
of carbonate mineral requires about a ton of sulfuric acid (International Atomic Energy
Agency, 2001). With alkaline glycine leach system having been proven to selectively leach
copper over carbonates and other impurity elements (Eksteen et al., 2016; Oraby & Eksteen,
2014; Tanda et al., 2017), lower operating costs due to low reagent inventory could be
realised. In addition, almost all of the glycine can be recovered and recycled to the leach
circuit, especially when CCD do not follow agitated leaching in which water (containing
glycine) is lost with solids.
Remote users of sulfuric acid incur high logistical and transportation costs due to safety
concerns. The capital cost of a site sulfur burning sulfuric acid plant could be very high as
well. With glycine being environmental friendly and supplied in a granular form,
transportation costs are low as safety concerns are insignificant.
Crud formation causes loss of reagent with entrainment (Rydberg et al., 2005). Crud is
common to most acidic solvent extraction operations and hampers the interaction of organic
and aqueous solutions. Crud is made up of organics, aqueous, air and solid particles. The
presence of cations such as Fe, Si, Ca, Mg and Al with sufficient agitation can produce stable
cruds (Aminian & Bazin, 1999; Rydberg et al., 2005). Major components of crud from a copper
186
SX plant in China were found to be SiO2, Al2O3, Fe2O3, CaO, MgO and MnO (Chengyan, 2005).
The nature of solvent extraction feed has been shown to influence crud formation during SX
(Mukutuma et al., 2008). Alkaline glycine leaching could significantly reduce crud formation
during SX by preventing the dissolution of crud forming metals and particles that would
otherwise be dissolved in sulfuric acid medium. As a comparison, whereas acidic heap leach
systems (of oxide ores) often lead to contaminant levels of Fe, Mn, Si, Al, Ca and Mg between
0.5 and 18 g/L in heap leach pregnant leach solutions (Zarate & Torres, 2016) in Chilean heap
leach operations, the alkaline nature (at 9<pH<12) of the glycine leach suppresses the
dissolution of these elements to below 20 ppm (Tanda et al. 2017; Oraby and Eksteen, 2014),
whilst Cu tenors of between 1 and 5 g/L can be achieved, giving a selectivity of around
between 100:1 to 1000:1 relative to the concentration of lithophile elements in solution.
In most SX operations from sulfuric acid leach, extraction occurs in two stages (Davenport et
al., 2002b) but the results in this research indicate that a 1-stage SX is probably sufficient for
glycine L/SX.
Capital costs related to construction material for glycine L/SX could be relatively lower as
compared to H2SO4 L/SX due to the less corrosive nature of alkaline glycine solution. In
sulfuric acid heap leach for example, HDPE is used as pads and 316 stainless steel used for
the construction of most mixer-settler equipment (Davenport et al., 2002b). However, in the
alkaline glycine leach process, painted mild steel can be easily used, similar to cyanide leahing
operations. In addition, the use of low cost portland cement binders/agglomeration agents
can be considered in the heap leach without the risk of dissolution.
Given that the alkaline glycine system has been shown to be able to dissolve copper oxide
minerals (Tanda et al., 2017) and native copper and copper sulfides including chalcopyrite
(Oraby and Eksteen, 2014, Oraby et al., 2016), it provides for a highly versatile leach system
across the geometallurgical spectrum of typical copper deposits, whilst minimising lithophile
element dissolution (e.g. Fe, Cr, Mn, Al, Mg, Ca and Si), thereby giving a significantly cleaner
pregnant leach solutions feeding into the solvent extraction circuit.
An important similarity between glycine L-SX of copper and that of conventional acid L-SX is
that copper can be stripped by a spent electrowinning electrolyte from both systems. Thus
the glycine system can replace a conventional acid leaching system without any change in
plant equipment.
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7.7 Copper Precipitation from a Synthetic
Copper Glycinate Solution
The feed solution used to study the effect of Cu:S molar ratio and pH was obtained from the
dissolution of CuSO4·5H2O in an aqueous alkaline glycine solution to obtain a copper
concentration of 2 g/L and a Gly:Cu ratio of 3:1. Sodium hydrogen sulfide, which is commonly
used in the industry (Lewis, 2010) was used as a precipitant. Precipitation experiments were
performed in a magnetically stirred open beaker and at room temperature (22-25 °C) by
adding a stoichiometric mass of NaHS powder into the copper glycinate solution. Copper
concentration in solution before and after precipitation was measured using AAS to
determine the extent of precipitation.
7.7.1 Effect of Copper to Sulfide Ratio (Cu:S)

The effect of Cu:S molar ratio was studied by varying the molar ratio of Cu2+ to S2- ions. Results
in Table 7.15 show that copper precipitation increases as the Cu:S ratio increases. At Cu:S
ratio of 1:1.2, 98.8 % of copper was precipitated in less than 10 minutes. This higher S:Cu
ratio needed for 98.8 % precipitation as opposed to the theoretically expected 1:1 could be
attributed to waters of hydration of NaSH (hydroscopic) that could be up to 20 % (O'Brien,
2012) which increases the mass of NaSH needed. This explains why a 1:1.2 gave the best
results. However, it is noted that 100 % copper precipitation is not desired since low
concentrations of Cu2+ ions in the recycle solution will act as oxidising agents in the leaching
of copper from its ore.
Table 7.15 Effect of Cu:S ratio on copper precipitation from alkaline glycine solution
Cu:S ratio 1:0.5 1:0.8 1:0.9 1:1 1:1.2
Cu precipitated, % 58.83 74.46 85.61 94.27 98.84
7.7.2 Effect of pH
The effect of solution pH on copper precipitation was studied by varying the solution pH from
8 to 11. Results in Table 7.16 indicate that the extent of copper precipitation from an alkaline
glycine solution is not influenced by the pH values considered.
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Table 7.16 Effect of pH on copper precipitation from alkaline glycine solution: Cu:S 1:1.
pH 8 9 10 11
Cu precipitated, % 93.76 92.99 93.81 94.27
7.7.3 Precipitate Analysis

To determine the type of precipitate produced from NaSH precipitation, the precipitate was
dried and analysed by XRD. Figure 7.4 indicates that 100 % of the precipitate is covellite (CuS).
This result is further confirmed by the information given in Section 5.2 that only Cu2+ ions are
involved in the formation of the stable copper glycinate complex in alkaline solutions.
Figure 7.4 XRD pattern of precipitate produced from NaSH precipitation of copper glycinate
solution
After precipitation and separation, a portion of the precipitate was immediately analysed by
laser diffraction (Malvern) to determine the particle size distribution. The distribution pattern
in Figure 7.5 illustrates that P80 of the precipitate is 66.96 µm. The significant diameter of the
particles account for the observed good settling and filtering properties of the precipitate.
189
10 100
9
8 80
% by Volume Passing size

% by Volume in interval 7
6 60
5
4 40
3
2 20
1
0 0
0.01 0.1 1 10 100 1000 10000
Size (µm)
Figure 7.5 Particle size distribution of copper precipitate (CuS) from a copper glycinate solution
7.8 Copper Precipitation from a Malachite Ore

Leachate
The leachate obtained from the leaching of a malachite specimen with mineralogy as
reported in Section 4.31 was used for the copper precipitation test. Sulfide was introduced
into the solution by adding a weighed powder of NaSH in order to obtained a predetermined
Cu:S molar ratio. Supernatant analysis by AAS noted that 81.37 % copper was precipitated
at Cu:S molar ratio of 1:1. At a Cu:S molar ratio of 1:1.1, 98.98 % of Cu was precipitated from
solution.
7.9 Copper Precipitation from Chalcopyrite B

Leachate
The leachate from chalcopyrite B (same leachate as in 7.4) was precipitated with NaHS at a
Cu:S molar ratio of 1:1 at pH 8, 11 and 12. After 5 minutes of precipitation, 93.5 % copper
was precipitated at all pHs considered. The Cu:S molar ratio was varied from 1:1 to 1:1.1 at
pH 11. At the Cu: S molar ratio of 1:1.1, 99.5 % copper was precipitated. During the leaching
of chalcopyrite B (muti-metal specimen), associated metals such as zinc were concurrently
leached into solution with copper. Table 7.17 tracks the concentration of copper and various
metals leached into solution and their fate after sulfide precipitation with NaHS at a Cu:S
molar ratio of 1:1. Copper precipitation was at 93.3 % Cu while those for Zn, Ca, Co and Ni
were 10.5, 6.3, 13.9 and 3.3 %, respectively. The calculated percentage precipitation for the
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rest of the major metals was negative, indicating that those metals were not precipitated
under the studied conditions.
Table 7.17 Precipitation of copper and accompanying metals from a complex multi-element
chalcopyrite specimen
Metals Cu Zn Fe Mg As Ca Si Co Ni
Metal concentration before 2287.6 699.2 3.5 1.7 1.8 5.5 0.5 14.9 8.2
precipitation, mg/L
Metal concentration after 153 626 4.5 2.14 1.6 5.2 0.8 12.9 7.9
precipitation, mg/L
7.10 Copper Precipitation from a Copper-Gold

Ore leachate
The Cu-Au solution used in this precipitation is the same as that used in Section 7.5. The
leachate copper concentration is 784 mg/L and that of gold is 0.241 mg/L. Copper was
precipitated at a Cu:S molar ratio of 1:1 and 1:1.1. The results in Table 7.18 show that 87.44
% Cu was precipitated at the Cu:S ratio of 1:1 while 97.32 % was precipitated at a Cu:S ratio
of 1:1.1. On analysing gold concentration in solution after precipitation, a gold loss of 16.18
and 24.07 % was noted at Cu:S ratio of 1:1 and 1:1.1, respectively. Although gold-sulphide
compounds have not been reported to form naturally, stable Au-S compounds ( Au2S, AuS3)
have been synthesized (Faltens & Shirley, 1970). These gold sulfides are black, finely divided
amorphous material that are sparingly soluble in water. Thus, the loss of gold during the
sulfide precipitation of copper could be attributed to the formation of gold sulfide
compounds. This may also be attributed to the metallic reduction of gold cause by the
reducing environment of sulfide ions or to the adsorption of gold onto the copper sulfide
precipitate. The nature of the gold deportment to the CuS precipitate has not yet been
determined. From a commercial perspective, gold precipitation along with copper is not lost
as the gold could be recovered during the smelting of the covellite precipitate.
Table 7.18 Copper precipitation from a Cu-Au ore leachate using NaSH: 25 °C, 10 mins, 50 rpm.
Cu:S ratio 1:1 1:1.1

Cu precipitated, % 87.14 97.32
Au precipitated, % 16.18 24.07
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7.11 Summary
The major objective of this paper was to investigate and evaluate the possibilty of copper
recovery from alkaline glycine solutions. Solvent extraction and sulfide precipitation from
both synthetic solutions and leachate from leaching natural ores were conducted. This
section therefore summarizes the results obtained from the solvent extraction and
precipitation experiments.
The extraction of copper from alkaline glycine solutions was investigated using Mextral 84H
and Mextral 54-100 extractants using kerosene as a diluent and results show that copper can
be efficiently recovered from the alkaline glycinate media and stripped using acidic solutions
similar to conventional spent electrolyte from copper electrowinning tank houses.
Copper extraction rates are fast as equilibrium is established in less than two minutes with
both extractants. A temperature range of 20–40 °C has no influence on the percentage
copper extracted by either extractants. Increasing the aqueous solution pH has no effect on
the ability of Mextral 84H to recover copper while a slight improvement from 97.3 to 99.7 %
copper extracted was noted for Mextral 54-100. Higher glycine to copper ratio 16:1 reduces
the copper extracted by Mextral 54-100 from 97.86 to 93.02 % meanwhile no changes are
noted in the case of Mextral 84H. Mextral 54-100 has superior loading capacities to Mextral
84H. With an aqueous solution containing 2 g/L copper, 5 % Mextral 84H extracts 99.90 %
copper while 10 % Mextral 54-100 was needed to extracted 95.87 % copper at an A:O ratio
of 2:1. In contrast to the cyanide and ammonia complexes of copper, which are solubilised
as the complete complex, the glycine lixiviant was not solubilised by any of the organic
extractants. All the glycine/glycinate reported to the aqueous raffinate, making recycling and
reuse of glycine on the leaching circuit feasible. Using a make-up spent electrolyte solution
containing 30 g/L Cu and 180 g/L sulfuric acid at 40°C, complete copper stripping was realised
from Mextral 54-100 at an A:O ratio of 10:1 while just 79.95 % was stripped from Mextral
84H under the same conditions.
In order to validate the results obtained from the copper extraction of synthetic solutions,
copper extraction from leached ore samples was performed. Copper extractions at O:A of 1:1
from malachite leachate were 99 % for both extractants while no impurity elements were
extracted. Copper extraction from a dirty chalcopyrite leachate at O:A ratio of 1:1 resulted in
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91.0 % and 86.6% Cu extracted by 10 % Mextral 54-100 and 5 % Mextral 84H, respectively,
while the concentration of most impurity elements in the aqueous raffinates increased. The
extractants show the ability to extract Cu from alkaline glycinate solutions over impurity
elements except zinc under the conditions used in this work. Solvent extraction on the PLS
of a Cu-Au ore containing 784 mg/L Cu and 0.241 mg/L Au at pH 10.3 revealed that up to 80.2
and 99.8 % Cu was extracted by Mextral 54-100 and Mextral 84H, respectively, while the gold
is rejected into solution. According to Eksteen & Oraby, (2015a), the rejected gold could then
be recovered with activated carbon.
One of the particular benefits of this system is the ability of performing the extraction under
alkaline conditions and the stripping using conventional spent electrolyte from conventional
copper electrowinning tank houses.
Precipitation of copper from the synthetic copper-glycinate solution at pH 11 resulted in 98.8

% precipitation in less than 10 minutes. It was observed that a pH range of 8-12 has no
influence on copper precipitation as approximately 94.0 % was precipitated at all pHs.
Precipitate analysis by XRD showed that 100 % of the product is covellite while Mavern laser
particle analyser showed that P80 of the precipitate was 66.96 µm. Copper precipitation from
a malachite leachate at a Cu:S molar ratio of 1.1.1 resulted in a 98.8 % copper precipitation.
During the precipitation of copper from a dirty multi-metallic chalcopyrite B specimen, it was
observed that at 93.3 % Cu precipitation, Zn, Ni and Co were co-precipitated but to a much
lesser extent (<10 %)
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Chapter 8 Conclusions
This chapter summarizes the major findings that have been discussed in the previous
chapters. In section, a retrospective of the research conducted is provided. The next section
outlines achievements and enumerates conclusions drawn from the results of the different
sections covered in this thesis. Some criticism of the research methodology that could have
improved the interpretation of the results is also given. Another section in this chapter
proposes possible flowsheets for different types of copper ores and copper-gold ores. The
final section then provides some recommendations for further investigations considered
worthy towards this research.
8.1 Retrospective and Discussions

The principal objective of this research was to investigate the application of glycine as a
lixiviant for low grade copper–gold ores. Processing of copper-gold by the traditional
cyanidation method as discussed in Chapter 1 possess challenges to metallurgists at all unit
stages of the process. Cyanidation efficiency is limited by the presesence cyanide soluble
copper by causing high cyanide demands. Copper found in the cyanide leached solution
interferes with the gold recovery process (carbon absorption). Copper forms WAD cyanide
that is not easily degradable by sunlight as compared to cyanide and thus makes the process
more environmentally un-friendly. Thus, there is the need to search for a new approach that
economically extracts and recovers copper and gold from copper-gold resources in an
environmentally benign manner.
Gold is generally found in association with primary copper ores. Porphyry copper deposits
are an important source of copper-gold ores as they are obtainable in many parts of the
world. More than 60 % of 2110 million tons of discovered copper reserves are made up of
porphyry deposits. However, porphyry deposits have significant mineralogical variations that
require extensive understanding in order to choose a suitable processing technique. Most of
these porphyry ore bodies containing copper-gold ores bear very low metal values that must
be processed via economical methods such as heap or dump leaching. Traditional cyanide
approaches not only have limitations at the level of reagent consumption and proccessing
steps, but their applications are highly restricted or banned for use on heaps or dumps due
to environmental concerns. An investigation into the use of cyanide alternatives is vital for
the extraction of valuable metals from low grade copper-gold ores.
194
Glycine has been presented as a potential alternative to cyanide not only due to it being
environmentally benign but also as a result of it being able to form stable complexes with
copper and gold. In alkaline environments, glycine can selectively leach copper and gold over
gangue metals such as iron, manganese, aluminium, calcium, magnesium and silicon. Glycine
can also be cheaply produced on an industrial scale.
8.2 Enumerated Conclusions

This section details the specific conclusions that have been drawn based on experimental
results. Leaching experiments were conducted with copper mineral specimens and copper-
gold ore samples with different copper and gold grades. The focus was also on the leaching
mechanisms and kinetics of copper leaching from its major minerals and the recovery of
copper metals from their PLSs.
Leaching experiments in this project were focused on leaching of mineral samples and ores
under different conditions and not much attention was given to the thermodynamics and
electrochemical response of copper minerals and gold ores in the alkaline glycine solutions.
Information from such such studies are very helpful in the interpretation of results obtained
during the bulk mineral ore leaching.
8.2.1 Leaching of Copper Minerals

Investigations into the leaching behaviour of individual copper minerals in alkaline glycine
solutions, in order to evaluate the extent of copper dissolution from common copper
minerals, were conducted using a bottle roller at different glycine concentrations and at
different initial leach solution pHs. At a Gly: Cu molar ratio of 4:1, initial solution pH of 11 at
25 °C, azurite was the easiest mineral to leach with 93.0 % Cu extraction in 6 hours. This was
closely followed by malachite with 88.0 % Cu obtained in 24 hours. Cuprite and metallic
copper leach rather slower than malachite and a Cu extraction of 91.7 % for both was
achieved after 48 hours. Chalcocite leaches fast in the first 24 hours (40.0 % Cu) and then
begins to plateaus as just about 44.0 % Cu is dissolved in 48 hours. The dissolution of copper
from chrysocolla is very slow with only 19.7 % Cu leached in 48 hours. Chalcopyrite shows
the lowest Cu dissolution with 15.1 % Cu extracted in 96 hours.
However, during the leaching kinetic studies of malachite, chalcocite and chalcopyrite
conducted using a glass reactor whereby variables such as temperature, dissolved oxygen
195
concentration, particle size and stirring speed could be controlled, copper extraction rates
were significantly improved. Under the following conditions, 50 °C, [Gly] of 0.5 M, stirring
speed of 400 rpm, particle size of +53-75 µm, 99.2 % Cu was extracted from malachite in just
30 minutes of leaching. For chalcocite, at 25 °C, 0.5 M Gly, DO 8 ppm, stirring speed of 400
rpm, particle size of P80 18.9 µm, 78.2 % Cu was extracted in 48 hours. The leaching of minus
10 µm size fraction of chalcopyrite at 50 °C, DO of 15 ppm, stirring speed of 400 rpm, and a
glycine concentration of 0.5 M resulted in 90.1 % Cu extraction after 96 hours.
The extent to which the different copper minerals leach in the alkaline glycine solution is
similar their leaching behaviours in other alkaline solutions such as cyanide (Hedley &
Tabachnick, 1968) and ammonium thiosulfate (Molleman & Dreisinger, 2002). In these
solutions, the oxide minerals show high copper leaching rates and secondary sulfides leach
to a limited extent, while primary sulfides such as chalcopyrite leach slowest. In industrial
applications whereby the ore to be leached contains a multitude of minerals, leaching
conditions should be chosen in order to maximise the leaching of the primary sulfides.
8.2.2 Mechanisms and Kinetics of Leaching

Malachite, Chalcocite and Chalcopyrite
In order to determine if Cu (I) and/or Cu (II) ions form the copper glycinate complex during
leaching of the different copper minerals, copper speciation was determined using UV-Vis
and AAS. The UV-Vis spectrum from leachates of azurite, malachite, cuprite, metallic copper,
chrysocolla, chalcocite and chalcopyrite showed a peak at 630 nm which is characteristic of
the Cu2+ of CuSO4·5H2O (as standard) in alkaline glycine solution. Copper concentration in the
leachates determined by UV-Vis (cupric) and AAS (total copper) confirmed that all the copper
in the leachates occurs as Cu2+ ions which then form the stable copper glycinate complex.
The fate of sulfur during the leaching of copper mineral sulfides was investigated by
performing sulfur speciation on the leachate of chalcopyrite. It was shown that about 90 %
of sulfur in the sample was converted to sulfate in the alkaline glycine solution.
Chalcocite leaching occurs in two stages. The chalcocite is quickly converted to Cu-glycinate
complex and covellite in the first stage. The second stage then involves the slow leaching of
the formed covellite. The kinetics of chalcocite investigated using equations of the shrinking
core model indicated that chalcocite leaching is controlled by diffusion through the product
layer. The apparent activation energy was calculated to be 43.92 kJ/mol.
196
Copper leaching rate from a malachite mineral sample was established to be controlled by
diffusion through the product layer. The calculated activation energy was 48.26 kJ/mol.
The shrinking core model equations were also used to predict the rate controlling steps
during the leaching of chalcopyrite. Applying the constrained multi-linear regression analysis
using the least square technique, the contributions of the different rate controlling shrinking
core models towards the overall leaching reaction could be predicted. As a consequence of
the significant difference in the dissolution regime of +20-38 µm size fraction of chalcopyrite
to that of the <10 µm size fraction, rate controlling step determination was on both size
fractions. The copper dissolution rate from +20-38 µm chalcopyrite fraction is limited by a
mixed diffusion regime. Diffusion through the product layer and liquid film both contribute
to limiting the leaching process. However, diffusion through the product layer is quite
dominant and its model equation was used to calculate the apparent activation energy for
the process to be 36.25 kJ/mol. On the other hand, the leaching rate from the < 10 µm
chalcopyrite is also controlled by diffusion through the product layer with an apparent
activation energy of 29.62 kJ/mol.
The leaching kinetics and activation energies reported for the minerals above are for the
given experimental conditions since disparities in leaching kinetics can occur due to different
experimental conditions (Nicol et al., 2010).
8.2.3 Leaching of Copper- Gold Ores

Copper-gold ore samples (oxides and sulfides) were leached to investigate the effect of
process variables on the dissolution of copper and gold in alkaline glycine solutions.
Copper dissolution from the gold-copper oxide ore was generally independent of glycine
concentration, initial solution pH from 8-12, temperature, oxygen flow rate and galvanic
interactions as the overall copper extracted after 96 hours was about 75 %. Gold dissolution
from the oxide ores was improved at 60 °C with 32.2 % Au obtained against 0.5 % at 25 °C.
Galvanic interactions in alkaline glycine solutions markedly improve the dissolution of gold
as up to 60.4 % was extracted with 20 kg/t pyrite addition.
Copper and gold from the copper-gold sulfide ores are both influenced by glycine
concentration. Higher Gly:Cu ratios favour both copper and gold dissolution while pH 11 was
found to be the optimum pH for both copper and gold leaching. Copper and gold are
simultaneously leached from the copper-gold sulfide ores at room temperature. The leaching
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of gold at room temperature from the sulfide ores was attributed to galvanic interactions
between pyrite in the ore and gold. However, the dissolution rate of both were significantly
higher at 60 °C.
The influence of galvanic interactions on the leaching of gold from Cu-Au ores was quite a
significant observation. Finely ground pyrite could be added to gold-copper oxide ores to
improve the leaching rates of gold. However, the added pyrite should be controlled to avoid
reactions that may have a counter influence on the either copper or gold.
8.2.4 Recovery of Metals from Leach Solutions

The solvent extraction/stripping and sulfide precipitation methods investigated in this thesis
were focused on copper recovery only.
During the solvent extraction of copper from synthetic Cu-glycinate solution, 5 % Mextral
84H extracted 99.9 % Cu while 10 % Mextral 54-100 extracted 97.0 % Cu at an A:O ratio of
2:1. Glycine concentration in the raffinate was 100 %, indicating that the investigated
extractants selectively extract copper leaving behind the glycine solution that can be recycled
to the leach circuit. Spent electrolyte (30 g/L Cu, 180 g/L H2SO4) at 40 °C stripped 100 %
copper from the loaded Mextral 54-100 at an A:O ratio of 1:10 while only 79.8 % copper was
stripped from Mextral 84H under the same conditions.
Copper solvent extraction on pregnant leach solutions of natural mineral specimens showed
a similar trend to that observed with the synthetic solutions. Solvent extraction from a multi-
metallic component PLS such as that from chalcopyrite A showed the co-extraction of Cu, Zn,
Co and Ni. However, the impurities were extracted to a much lower extent as compared to
copper. These impurities were tracked during stripping and low concentrations were
detected in the stripping solution. Other metals such as Fe, Mg, Ca, Si, and As were rejected
by the extracts. Because gold from the copper-gold ores was also noted to be concurrently
leached with copper, solvent extraction of copper from the leachate revealed that gold was
not transferred by either extractant. Gold in solution could then be recovered by activated
carbon adsorption.
Sulfide precipitation of copper from a synthetic copper glycinate solution using NaHS
precipitated up to 99.0 % Cu in less than 10 minutes at a Cu:S ratio of 1:1. Filtration of the
precipitate was found to be easy given that the precipitate particle size had a P80 of 66 µm.
XRD analysis of the precipitate reported that it was 100 % covellite (CuS).
198
Copper precipitation from the multi-metallic PLS showed that about 93.0 % Cu precipitation
was achieved. Impurity metals such as Zn, Ni, As and Co were also precipitated by the NaHS
addition though to a lesser extent (< 10 %).
At a 1:1 Cu:S molar ratio, Cu precipitation by NaHS from a Cu-Au leachate was 87.1 %, while
the concentration of gold in solution reduced by 16.2 %. It is supposed that the gold losses
are as a result of Au sulphide formation or adsorption of reduced metallic gold on to CuS
precipitate. The gold can then be recovered as a by-product of CuS smelting.
It was experimentally confirmed in this chapter that during the recovery of copper from
leach solutions containing copper and gold by solvent extraction, gold is rejected in solution.
Recently, Eksteen and Oraby (2015a) reported that gold can be efficiently recovered from
alkaline leach solutions by adsorption onto activated carbon. This research therefore claims
that a process flowsheet for Cu-Au ores in which both metals are concurrently leached into
solution should incoporate the solvent extraction of copper and then gold recovery by
activated carbon. However, the scope of this current thesis did not include experiments in
which gold was directly absorbed onto the activated carbon after copper solvent extraction.
It needs to be confirmed that gold could be recovered from copper depleted solution by
activated carbon absorption with or without modification of the raffinate.
8.3 Proposed Process Flowsheets for

Different Copper or Copper and Gold
Ores
The results obtained in this research project can lead to the development of a conceptual
flowsheet for the industrial production of copper and gold depending on the type of ore
being processed. Different flowsheets have been proposed for different copper or gold-
copper types.
8.3.1 Large Deposit of Low Grade Gold-Copper

Ore
In the case of a typical large deposit containing low grade copper sulfide ore such as
chalcopyrite with gold mineralisation whereby the size of the deposit justifies the
construction of a L/ SX/EW plant, the process will consist of the following steps:
199
I. Crushing of mined ore (agglomerate if necessary) and stacking on a prepared heap
leaching pad
II. Reagent make-up by adding the required amount of pH modifier (NaOH or Ca(OH)2) and
glycine to the predetermined water volume (Equation 8.1)
NaOH(aq) + NH2CH2COOH(aq) → Na+(aq) + NH2CH2COO -(aq) + H2O(l) (8.1)
III. Leaching is conducted by spraying the leach solution on top of the heap. As the solution
percolates through the heap, copper leaching occurs as per Equation 8.2 while gold is
leached according to Equation 8.3:
CuFeS2 + 2NH2CH2COO- + 4.5O2 + 2OH- → Cu(NH2CH2COO)2(aq) + H2O

FeO(OH) + 2SO42-(aq) (8.2)
Au + 2NH2CH2COO- + 0.5O2 + H2O → Au(NH2CH2COO)2] +2OH- (8.3)
IV. The PLS collected at the bottom of the heap is clarified to remove any solids (which may
aid in crud formation during solvent extraction):
V. Copper recovery from solution (through solvent extraction) and glycinate regeneration:
copper is removed from solution using LIX Mextral 54-100 (or similar)
2RH(Org) + Cu(NH2CH2COO)2(aq) → R2Cu(Org) + 2NH2CH2COOH(aq) (8.4)
The loaded organic is stripped with a conventional electrowinning (EW) spent electrolyte
R2Cu(Org) + 2H+(aq) → 2RH(Org) + Cu2+(aq) with SO42- as spectator

(8.5)
ion;
Copper is recovered by electrowinning from the rich electrolyte with acid regeneration:
Cu2+(aq) + 2e -→ Cu (s) at cathode (8.6)
2H2O (l) → O2(g) + 4H+(aq) + 4e - at anode (8.7)
VI. pH re-establishment and precipitation of sulfite/sulfate species or dissolved silicates,

phosphates or aluminates by lime addition (only sulfate shown below as predominant
species);
200
2NH2CH2COO-(aq) + Ca(OH)2(aq) + SO42-(aq) → CaSO4⋅2H2O(s) +
2NH2CH2COO-(aq) (8.8)
VII. Gold recovery: after the solid/liquid separation of the precipitate, the solution is pumped
into columns containing activated carbon for gold adsorption. The barren solution is
reconstituted by adding lost glycine and adjusting to the required pH. The solution is solar
heated up to 60 °C which is optimum for leaching gold and copper sulfide.
The proposed high level flowsheet for a possible industrial process is given in Figure 8.1.
Figure 8.1 Process flow diagram for glycine based leaching of a low Au-Cu ore in an alkaline
environment (copper is recovered by solvent extraction and electrowinning while gold recovery is
by carbon-in-column)
8.3.2 Lean Deposit of High Grade Copper Oxide

Ore
In the case of a typical lean deposit containing high grade copper oxide ore such as malachite
(with no gold content), the ore is crushed, milled and atmospherically leached in an agitated
tank at room temperature. The capital expenditure needed for the construction of a solvent
extraction and an electrowinning plant for copper is not justified copper for such a small
201
deposit. Leached copper can be recovered from the PLS by precipitating with NaHS or NaS
or H2S. Results from such precipitation experiments revealed that 100 % of the precipitate is
covellite. The covellite can be easily transported and sold to smelters. Figure 8.2 illustrates
the steps for the possible industrial processing of such an ore.
Figure 8.2 Process flow diagram for glycine based leaching of a high grade lean copper oxide
deposit in an alkaline environment (copper is recovered by sulfide precipitation)
8.3.3 Copper Sulfide Flotation Concentrate with

Gold Mineralization
The major difference between the processing of the flotation concentrate and a large deposit
of low grade gold-copper ore is that the concentrate can undergo ultrafine grinding (P80 <10
µm) and then leached in an agitated tank under elevated temperature (60 °C) in an oxidising
environment. Leach slurry also has to be filtered and the filtrate forwarded to the SX-EW
stage for copper recovery. Gold recovery is through a carbon-in-column stage. A proposed
process flowsheet for possible industrial application is shown in Figure 8.3.
202
CuFeS2-Au Conc.
UFG CIC CIC CIC CIC
for for for for
Glycine Au Au Au Au
Make-up pH Adjust &
P80<10 µm Precipitate
Ca(OH)2
O2, 10 ppm SX Extraction

Leach
Organic
Organic
10<pH<12;
T = 60°C
Thicken/CCD
Thicken/CCD
SX Stripping
L
L Filter
Filter S
Electrowinning
S CaSO3 / CaSO4, calcium
silicates, carbonates
Leach Residue Copper Cathode
Figure 8.3 A process flow diagram for the glycine based leaching of copper sulfide ore and
concentrates (with a gold content) in an alkaline environment (with concentrate ultrafine grinding,
copper recovery by SX-EW and gold recovery by carbon-in-column included).
8.4 Recommendations for Further Research

The following topics have been identified as being worthy of further research:
• A more extensive study of the mechanism and leaching kinetics of gold, and the influence
of copper minerals during gold leaching in order to increase the gold leaching rate;
• Focus on optimising the leaching of sulfide minerals in the alkaline glycine solution;
• Detailed investigations on glycine degradation during high temperature leaching;
• Dedicated research into impurity deportment (from alkaline glycinate solutions) should
be performed to optimise the extraction and stripping conditions for a given leach
system;
203
• Characterise nature of Au deportment during sulfide precipitation as being either Au-S
compounds adsorbed gold or reduced gold and;
• Extensive column leaching experiments on a variety of copper-gold ores should be
carried out to determine optimum conditions that would enhance heap leaching of low
grade copper-gold ores.
204
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Appendices
Appendix A: XRD Patterns
Appendix A1 XRD pattern for azurite mineral specimen
Appendix A2 XRD pattern for malachite A mineral specimen
239
Appendix A3 XRD pattern for cuprite mineral specimen
Appendix A4 XRD pattern for Chrysocolla mineral specimen
Appendix A 5 XRD pattern for chalcocite A mineral specimen
240
Appendix A6 XRD pattern for chalcopyrite A mineral specimen
Appendix B: Instrumental Detection Limits

.
Appendix B1 Elemental detection limits of XRF: Extended Iron Ore Suite, Fused with 12:22 Lithium
Borate flux. LOI determined by RTGA. Detection limits in ppm
Fe (100) SiO2 (100) Al2O3 (100) MnO (10) TiO2 (10) CaO (100)
MgO (100) K2O (10) P (10) S (10) Na2O (100) Cu (10)
Sn (10) Sr (10) Zr (10) Ba (10) V (10) Cl (10)

LOI (0 01%)
Appendix B 2 Fused Bead Laser Ablation ICP-MS: ppb otherwise detection limits are ppm
Ag (0.1) As (0.2) Ba (0.5) Be (0.2) Bi (0.2) Cd (0.1)

Ce (0.02) Co (0.1) Cr (1) Cs (0.01) Cu (2) Dy (0.01)
Er (0.01) Eu (0.01) Ga (0.1) Gd (0.01) Ge (0.05) Hf (0.01)
Ho (0.01) In (0.05) La (0.01) Lu (0.01) Mn (1) Mo (0.2)
Nb (0.01) Nd (0.01) Ni (2) Pb (1) Pr (0.01) Rb (0.05)
Re (0.01) Sb (0.1) Sc (0.1) Se* (5) Sm (0.01) Sn (0.2)
Sr (0.1) Ta (0.01) Tb (0.01) Te (0.2) Th (0.01) Ti (1)
Tl (0.2) Tm (0.01) U (0.01) V (0.1) W (0.05) Y (0.02)
Yb (0.01) Zn (5) Zr (0.5)
*partially volatilized
241
Appendix B 3 Lead Collection Fire Assay – ICP-MS: Nominal 40g charge analysed. Silver used as
secondary collector, Au, Pt, Pd determined with ICP quantification. Nature of the sample and/or
lower sample weights may compromise detection limits. Detection limits in ppb.
Au (1) Pt (1) Pd (1)
Appendix C: Particle size Distribution

Appendix C 1 Particle size distribution ultrafine Chalcocite B
Dispersant: Ethanol RI/ABS: 2.74 / 1

0 ml
Additives: Calgon Analysis Model: General purpose
15 minutes in ultrasonic
Sonication: bath Result units: Volume
Vol. Weighted Mean

Concentration: 0.01 % vol D[4,3]: 13.761 µm d(0.1): 2.811 µm
Surface Weighted Mean
Obscuration: 12.25 % D[3,2]: 6.031 µm d(0.5): 8.395 µm
Weighted Specific Surface
Residual: 0.846 % Area: 0.995 m2/cc P80: 18.883 µm
10 100
9
8 80

% by Volume in interval
7
6 60
5
4 40
3
2 20
1
0 0
0.01 0.1 1 10 100 1000 10000
Size (µm)
Appendix C 2 Particle size distribution ultrafine Chalcopyrite B
Dispersant: Water RI/ABS: 2.74 / 1

10 ml
Additives: Calgon Analysis Model: General purpose
Sonication: 20 minutes in ultrasonic bath Result units: Volume
Concentration: 0.0039 % vol Vol. Weighted Mean D[4,3]: 5.272 µm d(0.1): 0.838 µm
Obscuration: 16.87 % Surface Weighted Mean D[3,2]: 1.848 µm d(0.5): 3.392 µm
2
Weighted Residual: 0.891 % Specific Surface Area: 3.25 m /cc P80: 8.56 µm
d(0.9): 12.67 µm
242
10 100
9
8 80

% by Volume in interval 7
6 60
5
4 40
3
2 20
1
0 0
0.01 0.1 1 10 100 1000 10000
Size (µm)
Appendix D: XPS Spectra
Appendix D1The XPS survey spectrum for unleached chalcopyrite B
243
Appendix D2 XPS survey spectrum for leached chalcopyrite B
Appendix E: Properties of Reagents

Appendix E1 Properties of Glycine (Chemicalland21, 2017)
PRODUCT IDENTIFICATION
CAS NO. 56-40-6
EINECS NO. 200-272-2
FORMULA H2NCH2COOH
MOL WT. 75.07
H.S. CODE 2922.49
TOXICITY Oral rat LD50 7930 mg/kg
SYNONYMS
Aminoacetic Acid; Glycocoll; Athenon; Gly; G salt; Iconyl; Monazol; glycosthene; p-
Hydroxyphenylaminoacetic Acid; Aminoethanoic Acid; p-Hydroxyanilinoacetic Acid; para-
Oxyphenyl Glycocoll; Sucre De Gelatine;
PHYSICAL AND CHEMICAL PROPERTIES
PHYSICAL STATE White crystals, Odorless

MELTING POINT 245 C (Decompose)
BOILING POINT
244
SPECIFIC GRAVITY 1.6
SOLUBILITY IN WATER 25g/100 ml
pH 5.97 (Isoelectric point)

VAPOR DENSITY
REFRACTIVE INDEX
AUTOIGNITION
NFPA RATINGS Health: 0 Flammability: 1 Reactivity: 0

FLASH POINT 145 C
STABILITY Stable under ordinary conditions

APPLICATIONS:
Flavor enhancers and maskers, pH buffers and stabilizers, an ingredient in pharmaceutical

products, food and personal care products and as a chemical intermediate.
SALES SPECIFICATION
TECHNICAL GRADE
APPEARANCE white to off-white crystalline powder
ASSAY (DRY BASIS) 98.5% min
LOSS ON DRYING 0.5% max
CHLORIDE 0.5% max
Fe 0.003% max
FEED GRADE
APPEARANCE white to off-white crystalline powder
CHLORIDE 0.5% max
HEAVY METALS 20ppm max
ARSENIC 3ppm max
FOOD GRADE
BIBLIOGRAPHY FCC IV
APPEARANCE white, odorless, crystalline powder
IDENTIFICATION passes test
CHLORIDE 0.002% max
SULPHATE 50ppm max
245
pH 5.5 - 7.0
RESIDUE ON IGNITION 0.05% max
As 3ppm max
Pb 5ppm max
USP/BP GRADE
BIBLIOGRAPHY USP 24 / BP 93
APPEARANCE white, odorless, crystalline powder
ASSAY (DRY BASIS) 99.0 -101.0%
IDENTIFICATION passes test
CHLORIDE 70ppm max
SULPHATE 65 ppm
pH 5.5 - 6.5
RESIDUE ON IGNITION 0.1% max
As 3ppm max
Pb 5ppm max
HYDROLYZABLE SUBSTANCES passes test
PYROGEN CONTENT meets the requirements
ALUMINUM meets the requirements
ORGANIC VOLATILES meets the requirements
TRANSPORTATION
PACKING 25kgs in Fiber Drum
HAZARD CLASS Not regulated
UN NO.
GENERAL PROPERTIES OF GLYCINE
Glycine is a white, crystalline amino acid; dissolve in water and. As also known as aminoacetic
acid, it is the simplest amino acid. It has acid group as well as amino group which both groups act
as a base. It is not optically active, i.e., it does not have d- and l-stereoisomers as two hydrogens
are bonded to the central carbon atom. It is nonessential amino acids for mammals; i.e., they can
synthesize it from amino acids serine and threonine and from other sources and do not require
dietary sources. It is commercially synthesis from ammonia. It is also prepared
from bromoethanoic acid by reaction with potassium phthalimide. It helps to improve glycogen
storage utilized in the synthesis of hemoglobin, collagen, and glutathione, and facilitates the
amelioration of high blood fat and uric acid levels.
Appendix E2 Appendix D1 Properties of Mextral 54-100
Item Index
Extractant Appearance Clear light yellow liquid, free from visible impurities
Maximum Copper Loading (g/1 Cu) 100
246
Viscosity(cP) ( @ (kinematic)) 10
Specific Gravity(250/ ) 0.95-0.98
Flash Point ( °C ) 90
Extraction Isotherm Point, Organic (g/1 Cu) 14
Extraction Isotherm Point, aqueous (g/1 Cu) 0.5
Stripping Isotherm Point ,Organic (g/1 Cu) 0.1
Stripping Isotherm Point, aqueous (g/1 Cu) 54
Extraction Kinetics, 30sec (%) 95
Strip Kinetics, 30sec (%) 95
1200r/min Extraction Phase Separation (s) 120
1200r/min Strip Phase Separation (s) 90
Extraction Cu/Fe Selectivity 2000
Copper Net Transfer (g/1 Cu) 14
Complex solubility (g/1 Cu) 40
Appendix E 3 Properties of Mextral 84H
Item Index
Extractant Appearance fluid amber liquid, free from visible
Maximum Copper Loading (g/1 Cu) 4.7
Viscosity( cP) at 25 "C 40
Specific Gravity(25 "C) 0.900.92
Flash Point ("C ) 70
Extraction Isotherm Point, Organic (g/1 Cu) 3.65
Extraction Isotherm Point ,aqueous (g/1 Cu) 3
Strip Isotherm Point ,Organic (g/1 Cu) 0.5
Strip Isotherm Point ,aqueous ( g/1 Cu) 38
Extraction Kinetics,30sec(%) 90
Strip Kinetics,30sec (%) 90
1200r/min Extraction Phase Separation (s) 60
1200r/min Strip Phase Separation (s) 80
Extraction Cu/Fe Selectivity 2000
Copper Net Transfer (g/1 Cu) 3
Complex solubility (g/1 Cu) 30
247
248
Appendix F Examples of Metal leaching Calculations
Appendix F1 Copper extraction calculations from chalcopyrite A: 25 °C, Gly:Cu 4:1, pH 11 and 100
rpm.
Measurements Removed from soln Calaculations

Time Sol vol Cumm Cu leach Cu extrn Soln Cu
(hours) Ore (g) (mL) sol ,L [C],g/L vol(mL) Cu (g) Cu (g) vessel (g) total(g) extrn,%
14.81
0 0
3 500 0.5 0.159 3 0.000 0.000 0.080 0.080 3.800
29 497 0.497 0.270 3 0.001 0.001 0.134 0.135 6.419
97 494 0.494 0.643 3 0.002 0.003 0.318 0.321 15.231
192 491 0.491 0.995 3 0.003 0.006 0.488 0.495 23.467
266 488 0.488 1.506 3 0.005 0.011 0.735 0.746 35.387
435 485 0.485 2.056 3 0.006 0.017 0.997 1.014 48.119
600 482 0.482 2.278 3 0.007 0.024 1.098 1.122 53.225
864 479 0.479 2.399 0.000 0.024 1.149 1.173 55.651
Total 0.024
Product Qty grade cu mass,g
Solids 10.833 8.63 0.9348879
Sol(L) 0.479 2.399 1.149121
Total Cu removed 0.02372415
cal'ted Cu in sample 2.10773305
Appendix F2 Copper and gold extraction calculations from Cu-Au ore C: [Gly] 0.5M, 60°C, O2 0.05
l/min, 50% w/v % solids, Stirring, 250 rpm.
Measurements Cu removed from soln AU removed from soln
Au Au
Solution leach extrn
Au (μg)
Time volume Cumm Cu Cu leach Cu extrn Soln Cu Cumm vessel total(μ Soln Au
(hours) Ore (g) (mL) sol ,L [Cu],g/L Au, ppm vol(mL) Cu (g) (g) vessel (g) total(g) extrn % Au (μg) (μg) g) extrn %
500
1 500 0.5 0.0629 0.0113 5 0.00031 0.00031 0.03145 0.03145 4.702 0.057 0.0565 5.65 5.65 2.374
3 495 0.495 0.12425 0.0314 5 0.00062 0.00094 0.06150 0.06182 9.243 0.157 0.21350 15.543 15.60 6.554
6 490 0.49 0.206575 0.0404 5 0.00103 0.00197 0.10122 0.10216 15.274 0.202 0.41550 19.796 20.01 8.407
24 485 0.485 0.347575 0.0729 5 0.00174 0.00371 0.16857 0.17054 25.498 0.365 0.78000 35.357 35.77 15.029
48 480 0.48 0.6039 0.122 5 0.00302 0.00673 0.28987 0.29358 43.893 0.61 1.39000 58.56 59.34 24.931
72 475 0.475 0.586975 0.209 5 0.00293 0.00966 0.27881 0.28554 42.691 1.045 2.43500 99.275 100.67 42.293
102 475 0.475 0.494 0.22 0.23465 0.24431 36.527 104.5 106.94 44.927
30 0.00935 2.435
Cu GOLD EXTRACTION CALCULATIONS
Product Quantity grade mass,g PRODUCT Quantity GOLD
Solids 518.11 0.082 0.42485 GRADE MASS DISTn.
Solution 0.475 0.494 0.23465 (ppm) (µg) (%)
Removed 0.009346 SOLIDS 518.1 0.253 131 55.07
Total 0.668847 SOLUTION 475.00 0.220 105 43.90
REMOVED 2.435 1.02
TOTAL 993.1 238 100.00
CALC'd HEAD 0.46
249
Appendix G SEM Images of Un-leached and Leached
Mineral Specimens
Appendix G 1 SEM Images of un-leached and leached chalcocite B
250
Appendix G 2 SEM Images of un-leached and leached chalcopyrite B
Appendix H Experimental Leaching Data

Appendix H 1 Azurite leaching data
Eh, % Cu
Leaching Conditions Time,hrs pH [Cu], g/l
mV extraction
Gly:Cu 2:1 1 12.02 -1 1.679 41.98
mass sample= 4.750g 3 12.07 14 2.385 59.63
Gly: Cu= 2:1=4.725 g 6 12.06 24 2.526 63.15
DI = 500m l 24 12.06 42 2.771 69.28
Starting pH 11.09 48 11.96 53 2.922 73.05
Gly:Cu 3:1 1 11.99 7 2.308 57.70
mass sample= 4.750g 3 12.04 29 2.939 73.48
Gly: Cu= 3:1= 7.088g 6 12.11 25 3.245 81.13
DI = 500m l 24 12.14 48 3.6 90.00
Starting pH 11.04 48 12.09 50 3.902 97.55
Gly:Cu 4:1 1 11.99 40 2.65 66.25
mass sample= 4.750g 3 12.1 20 3.521 88.03
Gly: Cu 4:1 9.450g 6 12.14 27 3.735 93.38
DI = 500m l 24 12.16 42 3.874 96.85
Starting pH 11.01 48 12.09 46 3.878 96.95
Gly:Cu 8:1 1 11.72 -10 3.65 91.25
mass sample= 4.750g 3 11.87 -5 3.939 98.48
251
Gly: Cu= 8:1 =18.900g 6 11.92 8 3.988 99.70
DI = 500m l 24 11.93 23 4 100.00
Starting pH 11.00 48 11.83 29 4 100.00
pH 10 1 10.15 24 3.107 77.68
mass sample= 4.750g 3 10.23 40 3.595 89.88
Gly: Cu= 4:1= 9.450g 6 10.25 46 3.617 90.43
DI = 500m l 24 10.27 57 2.506 62.65
Starting pH 10 48 10.27 62 2.475 61.88
Appendix H 2 Malachite A leaching data
% Cu
Leaching Conditions Time,hrs pH Eh, mV [Cu], g/l extrn
Gly:Cu 2:1 1 12.16 1 2.085 52.13
mass sample= 4.813g 3 12.14 21 2.192 54.80
Gly: Cu= 2:1=4.725 g 6 12.11 21 2.308 57.70
DI = 500m l 24 12.13 28 2.326 58.15
Starting pH 11.00 48 12.04 28 2.379 59.48
72 11.99 42 2.393 59.83
96 11.98 41 2.599 64.98
Gly:Cu 3:1 1 12.23 -3 2.881 72.03
mass sample= 4.813g 3 12.22 -14 3.178 79.45
Gly: Cu= 3:1= 7.088g 6 12.21 14 3.303 82.58
DI = 500m l 24 12.22 18 3.39 84.75
Starting pH 11.17 48 12.15 31 3.433 85.83
Gly:Cu 4:1 1 12.26 12 3.091 77.28
mass sample= 4.813g 3 12.32 12 3.255 81.38
Gly: Cu 4:1 9.450g 6 12.25 18 3.365 84.13
DI = 500m l 24 12.27 34 3.546 88.65
Starting pH 11.01 48 12.12 23 3.581 89.53
Gly:Cu 4:1 1 12.17 -15 3.483 87.08
mass sample= 4.813g 3 12.18 -14 3.518 87.95
Gly: Cu= 8:1 =18.900g 6 12.17 -3 3.626 90.65
DI = 500m l 24 12.07 15 3.692 92.30
Starting pH 11.07 48 11.63 22 3.715 92.88
pH 9.5 1 9.33 71 2.756 68.90
mass sample= 4.813g 3 9.28 68 2.705 67.63
Gly: Cu= 4:1= 9.450g 6 9.26 70 2.809 70.23
DI = 500m l 24 9.31 69 2.004 50.10
Starting pH 9.50 48 9.28 76 1.532 38.30
252
Appendix H 3 Cuprite leaching data
% Cu
Leaching Conditions Time,hrs pH Eh, mV [Cu], g/l
extraction
Gly:Cu 2:1 1 12.25 -80 1.15 28.75

mass sample= 4.750g 3 12.39 -47 1.74 43.50
Gly: Cu= 2:1=4.725 g 6 12.45 -39 1.755 43.88
DI = 500m l 24 12.55 -21 2.722 68.05
Starting pH 11.14 48 12.49 -10 2.833 70.83
72 12.33 -6 2.986 74.65
96 11.94 15 3.114 77.85
Gly:Cu 3:1 1 12.29 -93 1.198 29.95
mass sample= 4.750g 3 12.44 -63 1.647 41.18
Gly: Cu= 3:1= 7.088g 6 12.5 -52 2.232 55.80
DI = 500m l 24 12.6 -34 3.036 75.90
Starting pH 11.03 48 12.52 -26 3.409 85.23
Gly:Cu 4:1 1 12.31 -124 1.339 33.48
mass sample= 4.750g 3 12.46 65 2.058 51.45
Gly: Cu 4:1 9.450g 6 12.55 -55 2.452 61.30
DI = 500m l 24 12.64 -33 3.369 84.23
Starting pH 11.06 48 12.58 -25 3.732 93.30
Gly:Cu 8:1 1 12.28 -219 1.459 36.48
mass sample= 4.750g 3 12.49 -74 2.328 58.20
Gly: Cu= 8:1 =18.900g 6 12.58 -53 2.822 70.55
DI = 500m l 24 12.64 -28 3.425 85.63
Starting pH 11.09 48 12.36 -7 3.755 93.88
pH 9.0 1 8.97 -176 1.615 40.38
mass sample= 4.750g 3 8.99 77 2.441 61.02
Gly: Cu= 4:1= 9.450g 6 8.99 105 2.968 74.20
DI = 500m l 24 9.11 104 2.122 53.05
Starting pH 9 48 9.1 86 1.812 45.30
pH 10.0 1 10.31 -181 1.923 48.08
mass sample= 4.750g 3 10.78 -3 2.473 61.83
Gly: Cu= 4:1= 9.450g 6 11.19 -6 3.282 82.05
DI = 500m l 24 11.62 8 3.665 91.63
Starting pH 10 48 11.4 -5 3.888 97.20
253
Appendix H 4 Chrysocolla leaching data
Time, % Copper
Leaching conditions hrs pH Eh,mV [CU], g/L extrn
Gly:Cu 2:1 1 11.07 9 0.274 6.85
sample = 2g Cu = 8.097g 3 11.07 -1 0.346 8.65
DI= 500mL 6 11.12 -3 0.39 9.75
Gly:Cu 2:1 (4.725g) 24 11.13 17 0.472 11.80
Initial pH 11 48 11.17 14 0.475 11.88
Gly:Cu 2:1 1 11.01 6 0.388 9.70
sample = 2g Cu = 8.097g 3 11.02 -9 0.424 10.60
DI= 500mL 6 11.05 -14 0.437 10.93
Gly:Cu 3:1 (7.088g) 24 11.09 3 0.479 11.98
Initial pH 11 48 11.13 13 0.631 15.78
Gly:Cu 2:1 1 11.13 -10 63 7.88
sample = 2g Cu = 8.097g 3 11.17 -28 -10 12.18
DI= 500mL 6 11.16 13 -28 12.75
Gly:Cu 4:1 (9.450g) 24 11.17 -2 13 18.98
Initial pH 11 48 11.36 4 -2 19.13
pH 8 1 8.16 211 0.444 11.10
sample = 2g Cu = 8.097g 3 8.06 211 0.534 13.35
DI= 500mL 6 8.05 201 0.573 14.33
Gly:Cu 4:1 (9.450g) 24 8.02 130 0.762 19.05
Initial pH 8.01 48 8.14 107 1.075 26.88
pH9.5 1 9.48 119 0.561 14.03
sample = 2g Cu = 8.097g 3 9.47 117 0.651 16.28
DI= 500mL 6 9.47 114 0.671 16.78
Gly:Cu 4:1 (9.450g) 24 9.5 49 0.813 20.33
Initial pH 9.57 48 9.55 70 0.89 22.25
254
Appendix H 5 Chalcocite A leaching data
Eh, [Cu], % Cu
Leaching Conditions Time,hrs pH
mV g/L extraction
Gly:Cu 2:1 1 11.96 -121 0.537 13.43
sample = 2g Cu = 2.538g 3 11.74 -86 0.661 16.53
DI= 500mL 6 11.58 -62 0.801 20.03
Gly:Cu 2:1 (4.725g) 24 11.47 -52 1.05 26.25
0.5% peroxide= 8.33mL 48 11.13 -37 1.269 31.73
Initial pH 11
Gly:Cu 3:1 1 11.76 -111 0.68 17.00
sample = 2g Cu = 2.538g 3 11.6 -66 0.827 20.68
DI= 500mL 6 11.46 -67 0.951 23.78
Gly:Cu 3:1 (7.088g) 24 11.34 -49 1.316 32.90
0.5% peroxide= 8.33mL 48 11.1 -61 1.504 37.60
Initial pH 11
Gly:Cu 4:1 1 11.62 -117 0.773 19.33
sample = 2g Cu = 2.538g 3 11.58 -65 0.922 23.05
DI= 500mL 6 11.51 -55 1.069 26.73
Gly:Cu 4:1 (9.450g) 24 11.35 -43 1.538 38.45
0.5 % peroxide= 8.33mL 48 11.14 -47 1.663 41.58
Initial pH 11
Gly:Cu 8:1 1 11.52 -148 0.896 22.40
sample = 2g Cu = 2.538g 3 11.56 -94 1.082 27.05
DI= 500mL 6 11.57 -93 1.277 31.93
Gly:Cu 8:1 (18.900g) 24 11.39 -58 1.696 42.40
0.5% peroxide =8.33mL 48 11.17 -68 1.858 46.45
pH 11
pH 9 1 8.15 101 1.529 38.225
sample = 2g Cu = 2.538g 3 7.84 74 1.581 39.525
DI= 500mL 6 7.9 56 1.552 38.8
Gly:Cu 4:1 (9.450g) 24 8.24 37 1.544 38.6
0.5% peroxide =8.33mL 48 8.42 30 1.573 39.325
Initial pH 9.06
pH 10 1 9.84 -21 1.644 41.1
sample = 2g Cu = 2.538g 3 9.83 -29 1.601 40.025
DI= 500mL 6 9.8 -37 1.532 38.3
Gly:Cu 4:1 (9.450g) 24 9.8 -25 1.676 41.9
0.5% peroxide =8.33mL 48 9.78 -24 1.678 41.95
Initial pH 10.08
0% peroxide 1 11.19 -140 0.288 7.2
sample = 2g Cu = 2.538g 3 11.36 -134 0.532 13.3
DI= 500mL 6 11.61 -63 1.071 26.775
Gly:Cu 4:1 (9.450g) 24 12.32 -62 1.615 40.375
0% peroxide 48 12.27 -49 1.751 43.775
Initial pH 11
255
Eh, [Cu], % Cu
Leaching Conditions Time,hrs pH
mV g/L extraction
sample = 2g Cu = 2.538g 3 11.58 -65 0.922 23.05
DI= 500mL 6 11.51 -55 1.069 26.725
Gly:Cu 4:1 (9.450g) 24 11.35 -43 1.538 38.45
0.5 % peroxide= 8.33mL 48 11.14 -47 1.663 41.575
Initial pH 11
Appendix H 6 Chalcopyrite A leaching data
Time, % Copper
Leaching condition pH Eh,mV [Cu], g/L
hrs extraction
Gly:Cu 2:1 3 11.1 -49 0.037 1.679

Sample 14.81g= 2.19 g Cu 29 10.85 -54 0.104 4.750
DI=500mL 97 10.4 -22 0.319 14.535
Gly:Cu 2:1 192 10.02 -17 0.463 21.106
0.5% peroxide 266 9.49 11 0.621 28.279
pH 11.22 435 8.99 50 0.686 31.277
Calculated head= 2.068g 600 8.71 63 0.896 40.825
864 8.22 91 0.937 42.708
Gly:Cu 3:1 3 11.05 -42 0.040 1.829
Sample 14.81g= 2.19 g Cu 24 10.97 -82 0.095 4.355
DI=500mL 97 10.73 -50 0.256 11.779
Gly:Cu 3:1 (7.088g) 192 10.57 -18 0.473 21.737
0.5 % peroxide 266 10.29 -14 0.485 22.313
pH 11 435 9.73 4 0.708 32.555
864 9.14 57 0.996 45.814
Gly:Cu 4:1 3 11.14 -67 0.072 3.262
Sample 14.81g= 2.19 g Cu 29 10.98 -67 0.121 5.536
DI=500mL 97 10.7 -57 0.363 16.551
Gly:Cu 4:1 192 10.44 -34 0.587 26.734
0.5% peroxide 266 10.11 -13 0.836 38.115
pH 11.16 435 9.69 3 1.058 48.222
Calculated head= 2.195% 600 9.25 20 1.105 50.382
864 9.01 45 1.209 55.128
Gly:Cu 8:1 3 11.01 -68 0.108 4.834
Sample 14.81g= 2.19 g Cu 29 10.94 -81 0.213 9.498
DI=500mL 97 10.78 -58 0.410 18.299
Gly:Cu 8:1 192 10.6 -55 0.653 29.104
0.5% peroxide 266 10.32 -43 0.968 43.169
pH 11.00 435 10.16 -14 1.320 58.857
Calculated head= 2.242g 600 9.75 -5 1.491 66.480
256
Time, % Copper
Leaching condition pH Eh,mV [Cu], g/L
hrs extraction
864 9.35 14 1.599 71.291

pH 9 3 8.93 12 0.057 2.760
Sample 14.81g= 2.19 g Cu 29 8.89 2 0.080 3.888
DI=500mL 97 8.66 21 0.175 8.476
Gly:Cu 4:1 192 8.53 14 0.209 10.097
0.5% peroxide 266 8.39 24 0.271 13.068
pH 9.02 435 8.28 34 0.345 16.646
864 7.92 54 0.417 20.145
EXPT 9 3 9.99 -22 0.068 2.924
Sample 14.81g= 2.19 g Cu 29 9.93 -41 0.093 4.023
DI=500mL 97 9.81 -18 0.209 9.005
Gly:Cu 4:1 192 9.64 -22 0.351 15.134
0.5% peroxide 266 9.41 1 0.563 24.282
pH 10.08 435 9.15 22 0.834 35.965
864 8.87 47 1.029 44.370
No peroxide 3 10.99 -14 0.080 3.800
Sample 14.81g 29 10.86 -47 0.135 6.419
DI=500mL 97 10.65 -53 0.321 15.231
Gly:Cu 4:1 192 10.43 -35 0.495 23.467
0% peroxide 266 10.15 -23 0.746 35.387
pH 11.01 435 9.78 4 1.014 48.119
Calculated head= 2.108% 600 9.34 18 1.122 53.225
864 9.08 34 1.173 55.651
0.1 % peroxide 3 11.03 -58 0.045 2.027
Sample 14.81g= 2.19 g Cu 29 10.89 -49 0.114 5.108
DI=500mL 97 10.67 -51 0.307 13.708
Gly:Cu 4:1 192 10.45 -25 0.515 22.981
0.1% peroxide 266 10.15 -27 0.751 33.548
pH 11.05 435 9.79 -2 0.968 43.241
Calculated head= 2.260% 600 9.34 14 1.132 50.529
864 9.18 27 1.196 53.423
1 % peroxide 3 11.14 -67 0.072 3.262
Sample 14.81g= 2.19 g Cu 29 10.98 -67 0.121 5.536
DI=500mL 97 10.7 -57 0.363 16.551
Gly:Cu 4:1 192 10.44 -34 0.587 26.734
1% peroxide 266 10.11 -13 0.836 38.115
pH 11.16 435 9.69 3 1.058 48.222
Calculated head= 2.195% 600 9.25 20 1.105 50.382
864 9.14 45 1.209 55.128
257
Appendix H 7 Malachite B leaching data
Time, Eh, [Cu], Cu

leaching conditions pH
mins mV g/L extrn, %
% Cu in ore 56 5 9.98 144 0.1136 5.64
sample , g 1.799 15 10.07 124 0.2479 12.30
Di, mL 500 30 10.14 110 0.4156 20.63
Gly, M 0.1 60 10.26 96 0.7227 35.87
Temp, degrees 25 120 10.36 96 1.0911 54.15
Expected total copper in soln, g/L 2.015 180 10.45 80 1.3618 67.59
Stirring speed, RPM 350
Particle size, µm +53-75
% Cu in ore 56 5 10.39 91 0.2398 11.90
sample , g 1.799 15 10.46 89 0.5885 29.21
Di, mL 500 30 10.52 70 0.8511 42.24
Gly, M 0.2 60 10.62 70 1.3119 65.11
Temp, degrees 25 120 10.76 78 1.6690 82.83
% Cu in ore 56 5 10.06 -19 0.4488 22.27
sample , g 1.799 15 10.08 1 0.9048 44.91
Di, mL 500 30 10.13 22 1.3823 68.60
Gly, M 0.4 60 10.16 27 1.8040 89.53
Temp, degrees 25 120 10.18 172 1.9507 96.81
Expected total copper in soln, g/L 2.015 180 10.29 -27 2.0141 99.96
% Cu in ore 56 5 10.14 -18 0.5230 25.96
sample , g 1.799 15 10.15 -12 0.8907 44.21
Di, mL 500 30 10.14 -6 1.3451 66.76
Gly, M 0.8 60 10.17 5 1.7570 87.20
Temp, degrees 25 120 10.14 14 1.9777 98.15
% Cu in ore 56 5 10.01 N/A 0.6833 33.91
sample , g 1.799 15 10.02 42 1.3800 68.49
Di, mL 500 30 10.07 36 1.6271 80.75
Gly, M 0.4 60 10.16 34 1.9536 96.96
Temp, degrees 30 120 10.18 28 1.9874 98.64
% Cu in ore 56 5 10.01 58 0.9933 0.28
sample , g 1.799 15 10.08 28 1.6953 0.48
Di, mL 500 30 10.22 15 1.9500 0.56
Gly, M 0.4 60 10.29 14 1.9855 0.57
258
Temp, degrees 40 120 10.32 42 2.0141 0.58
% Cu in ore 56 5 10.04 15 1.6840 3.01
sample , g 1.799 15 10.15 9 1.9537 3.49
Di, mL 500 30 10.26 -1 1.9981 3.57
Gly, M 0.4 60 10.16 3 2.0070 3.58
Temp, degrees 50 120 10.31 9 2.0145 3.60
% Cu in ore 56 5 10.29 39 0.3321 16.48
sample , g 1.799 15 0.6782 33.66
Di, mL 500 30 10.3 33 1.0159 50.42
Gly, M 4 60 10.31 26 1.3783 68.41
Temp, degrees 25 120 10.4 36 1.7360 86.16
% Cu in ore 56 5 10.27 53 0.5591 0.16
sample , g 1.799 15 10.31 63 0.9775 0.28
Di, mL 500 30 10.25 -29 1.4339 0.41
Gly, M 0.4 60 10.32 5 1.8328 0.52
Temp, degrees 25 120 10.37 14 1.9509 0.56
Expected total copper in soln, g/L 2.015 180 10.21 -1 2.0146 0.58
% Cu in ore 56 5 10.15 32 0.4830 0.86
sample , g 1.799 15 10.2 15 1.1953 2.13
Di, mL 500 30 10.33 29 1.5339 2.74
Gly, M 0.4 60 10.43 8 1.8630 3.33
Temp, degrees 25 120 10.19 21 2.0106 3.59
% Cu in ore 56 5 10.1 -29 0.8025 39.83
sample , g 1.799 15 10.14 12 1.3425 66.63
Di, mL 500 30 10.17 27 1.7150 85.12
Gly, M 4 60 10.15 -17 1.9847 98.50
Temp, degrees 25 120 10.34 -22 1.9995 99.24
Expected total copper in soln, g/L 2.015 180 2.0148 100.00
% Cu in ore 56 5 10.04 -3 0.8590 42.63
sample , g 1.799 15 10.06 -4 1.3081 64.92
259
Di, mL 500 30 10.28 15 1.6837 83.56
Gly, M 0.4 60 10.32 11 1.9982 99.17
Temp, degrees 30 120 10.36 35 2.0146 99.99
% Cu in ore 56 5 10.31 58 0.3598 17.86
sample , g 1.799 15 10.37 35 0.6894 34.22
Di, mL 500 30 1043 41 1.1569 57.42
Gly, M 0.4 60 10.51 44 1.6686 82.81
Temp, degrees 50 120 10.52 40 1.9035 94.47
+75-
Particle size, µm 106
Appendix H 8 Chalcocite B leaching data
Cu
Time, Eh,
leaching conditions pH [Cu], g/L extrn,
hours mV
%
% Cu in ore 78.5 0.5 10.04 -121 0.084 4.20
sample , g 1.274 1 10.06 -122 0.1088 5.44
Di, mL 500 3 10.01 -113 0.163 8.15
Gly, M 0.1 6 10.06 -36 0.2979 14.89
Temp, degrees 25 24 10.49 -11 0.555 27.75
Expected total copper in soln,
g/L 2.000 48 10.4 -28 0.6304 31.52
DO, ppm 8
% Cu in ore 78.5 0.5 10.03 -188 0.151 7.55
sample , g 1.274 1 10.04 -114 0.1576 7.88
Di, mL 500 3 10.05 -82 0.2267 11.33
Gly, M 0.3 6 10.05 -57 0.3949 19.74
Temp, degrees 25 24 10.14 -73 0.6561 32.80
g/L 2.000 48 9.59 7 0.7434 37.17
DO, ppm 8
% Cu in ore 78.5 0.5 10.19 -227 0.1351 6.75
sample , g 1.274 1 10.15 -228 0.1461 7.30
Di, mL 500 3 10.18 -132 0.2542 12.71
Gly, M 0.5 6 10.27 -164 0.4826 24.13
Temp, degrees 25 24 10.21 -106 0.7996 39.98
260
g/L 2.000 48 10.21 -58 0.8667 43.33
DO, ppm 8
% Cu in ore 78.5 0.5 10.05 -55 0.1411 7.05
sample , g 1.274 1 10.09 -128 0.1485 7.42
Di, mL 500 3 10.04 -180 0.264 13.20
Gly, M 1 6 10.05 -40 0.5043 25.21
Temp, degrees 25 24 10.16 -77 0.7983 39.91
g/L 2.000 48 10.09 -72 0.8633 43.16
DO, ppm 8
% Cu in ore 78.5 0.5 10.25 -123 0.102 5.10
sample , g 1.274 1 10.2 -16 0.132 6.60
Di, mL 500 3 10.23 26 0.2 10.00
Gly, M 0.5 6 10.21 71 0.273 13.65
Temp, degrees 25 24 10.29 54 0.351 17.55
g/L 2.000 48 10.31 -75 0.477 23.85
% Cu in ore 78.5 0.5 10.23 -161 0.117 5.85
sample , g 1.274 1 10.23 -175 0.155 7.75
Di, mL 500 3 10.21 -148 0.312 15.60
Gly, M 0.5 6 10.2 -93 0.596 29.80
Temp, degrees 25 24 10.3 -74 0.959 47.95
g/L 2.000 48 10.4 -56 1.048 52.40
% Cu in ore 78.5 0.5 10.33 -155 0.118 5.90
sample , g 1.274 1 10.26 109 0.166 8.30
Di, mL 500 3 10.06 -87 0.299 14.95
Gly, M 0.5 6 10.03 -117 0.46 23.00
Temp, degrees 25 24 10.1 -41 0.818 40.90
g/L 2.000 48 10.08 -45 0.882 44.10
% Cu in ore 79.2 0.5 10.28 -86 0.1316 6.52
sample , g 1.274 1 10.28 -99 0.1808 8.96
Di, mL 500 3 10.24 -57 0.424 21.01
Gly, M 4 6 10.27 -97 0.5989 29.68
Temp, degrees 25 24 10.31 -81 0.7986 39.57
261
g/L 2.018016 48 10.42 -12 0.8735 43.29
% Cu in ore 78.6 0.5 10.31 -200 0.1119 5.59
sample , g 1.274 1 10.26 -153 0.1157 5.78
Di, mL 500 3 10.33 -46 0.2181 10.89
Gly, M 0.4 6 10.24 -113 0.3208 16.02
Temp, degrees 25 24 10.39 -66 0.5681 28.37
g/L 2.002728 48 10.47 -200 0.6356 31.74
% Cu in ore 77.6 0.5 10.12 -97 0.0467 2.36
sample , g 1.274 1 10.37 -107 0.0949 4.80
Di, mL 500 3 10.06 -75 0.1878 9.50
Gly, M 0.4 6 9.83 -168 0.2837 14.35
Temp, degrees 25 24 9.97 -55 0.5275 26.68
g/L 1.977248 48 9.97 -10 0.6235 31.53
% Cu in ore 77.6 0.5 10.7 -93 0.351975 17.80
sample , g 1.274 1 10.66 -81 0.533525 26.98
Di, mL 500 3 10.91 -61 0.847775 42.88
Gly, M 0.4 6 10.9 -50 0.96905 49.01
Temp, degrees 25 24 10.87 -37 1.331 67.32
g/L 1.977248 48 10.66 -9 1.54645 78.21
pH 10.5
P80
Particle size, µm 18.88
% Cu in ore 78.5 0.5 9.86 -151 0.167 8.35
sample , g 1.274 1 9.88 -73 0.209 10.45
Di, mL 500 3 9.82 -46 0.442 22.10
Gly, M 0.5 6 9.98 -68 0.635 31.75
Temp, degrees 35 24 10.06 -71 0.887 44.35
g/L 2.000 48 10.09 -68 0.946 47.30
DO, ppm 8
% Cu in ore 78.5 0.5 10.4 -161 0.237 11.85
sample , g 1.274 1 10.39 -152 0.241 12.05
Di, mL 500 3 10.27 -98 0.436 21.80
Gly, M 0.5 6 10.33 -75 0.642 32.10
Temp, degrees 45 24 10.38 -91 0.879 43.95
262
g/L 2.000 48 10.47 -82 1.047 52.35
DO, ppm 8
% Cu in ore 78.5 0.5 9.93 -183 0.222 11.10
sample , g 1.274 1 10.02 -132 0.278 13.90
Di, mL 500 3 10.06 -110 0.566 28.30
Gly, M 0.5 6 9.92 -91 0.759 37.95
Temp, degrees 55 24 10.36 -84 0.91 45.50
g/L 2.000 48 10.1 -64 1.1 55.00
DO, ppm 8
% Cu in ore 78.5 0.5 10.17 -65 0.2363 11.81
sample , g 1.274 1 10.11 -126 0.2578 12.89
Di, mL 500 3 10.02 -75 0.5067 25.33
Gly, M 0.5 6 10.08 -83 0.7652 38.26
Temp, degrees 25 24 10.12 -71 0.9831 49.15
g/L 2.000 48 10.22 -19 0.9968 49.84
DO, ppm 15
% Cu in ore 78.5 0.5 11.1 -136 0.307 15.35
sample , g 1.274 1 11.1 -152 0.487 24.35
Di, mL 500 3 11.24 -162 0.633 31.65
Gly, M 0.5 6 11.34 -152 0.744 37.20
Temp, degrees 25 24 11.48 -103 0.998 49.90
g/L 2.000 48 11.42 -86 1.081 54.05
DO, ppm 20
% Cu in ore 78.5 0.5 10.14 -152 0.287 14.35
sample , g 1.274 1 10.15 -119 0.36 18.00
Di, mL 500 3 10.17 -46 0.682 34.10
Gly, M 0.5 6 10.2 88 0.841 42.05
Temp, degrees 25 24 10.24 -6 0.893 44.65
g/L 2.000 48 10.26 -16 0.891 44.55
DO, ppm 25
263
Appendix H 9 Chalcopyrite B leaching data
Time, Eh,
leaching conditions pH [Cu], g/L Cu extrn, %
hours mV
Gly, M 0.1 1 11.04 -35 0.0073 0.35

sample mass, g 3.8 3 11.03 -36 0.0145 0.70
% Cu in sample 27.2 6 10.96 -60 0.0279 1.35
DI, L 0.5 24 10.51 -11 0.1182 5.72
PS, um 20-38 48 0 -3 0.2154 10.42
SS 400 72 10.03 0 0.3008 14.55
Temp, degrees Celsius 50 96 9.77 22 0.3592 17.37
[O2],ppm 15
expected Cu in sol, g/L 2.0672
Gly, M 0.3 1 11.6 -35 0.0116 0.56
sample mass, g 3.8 3 11.29 -36 0.0282 1.37
% Cu in sample 27.2 6 11.19 -60 0.0538 2.60
DI, L 0.5 24 10.81 -11 0.1469 7.10
PS, µm 20-38 48 10.37 -3 0.2277 11.01
SS 400 72 0 0 0.3958 19.15
[O2],ppm 15
Gly, M 0.5 1 11.3 -4 0.0121 0.59
sample mass, g 3.801 3 11.17 1 0.0133 0.64
% Cu in sample 27.2 6 11.06 -5 0.0410 1.98
10.66-
DI, L 0.5 24 11.03 -9 0.1350 6.53
PS, um 20-38 48 10.85 3 0.2698 13.05
SS 400 72 10.5 4 0.4478 21.65
[O2],ppm 15
Gly, M 1 1 11.01 -28 0.0198 0.96
sample mass, g 3.8 3 10.91 -15 0.0405 1.96
% Cu in sample 27.2 6 10.9 -12 0.0760 3.68
DI, L 0.5 24 10.85 -19 0.2018 9.76
PS, um 20-38 48 10.83 -29 0.3388 16.39
SS 400 72 10.8 -23 0.4795 23.20
Temp, degrees Celsius 50 96 10.43 -16 0.5888 28.48
[O2],ppm 15
Gly, M 0.5 1 10.6 -40 0.0219 1.06
sample mass, g 3.804 3 10.71 -39 0.0246 1.19
% Cu in sample 27.2 6 10.93 -7 0.0450 2.17
DI, L 0.5 24 10.91 -1 0.1797 8.68
PS, µm 20-38 48 10.87 8 0.3109 15.02
SS 200 72 10.8 10 0.4135 19.98
264
[O2],ppm 15
Gly, M 0.5 1 11.02 2 0.0176 0.85
sample mass, g 3.8 3 10.86 -6 0.0330 1.60
% Cu in sample 27.2 6 10.83 -8 0.0642 3.11
DI, L 0.5 24 10.73 -2 0.2614 12.64
PS, um 20-38 48 10.72 23 0.3977 19.24
SS 400 72 10.42 -7 0.5207 25.19
[O2],ppm 15
Gly, M 0.5 1 10.92 -53 0.0059 0.29
sample mass, g 3.8 3 10.8 -35 0.0285 1.41
% Cu in sample 26.6 6 10.78 -27 0.0588 2.91
DI, L 0.5 24 10.75 -20 0.2342 11.58
PS, um 20-38 72 10.42 -7 0.5631 27.85
SS 600 96 10.38 5 0.6643 32.86
Temp, degrees Celsius 50
[O2],ppm 15
Gly, M 0.5 1 11.05 -54 0.0259 1.25
sample mass, g 3.804 3 11.04 -43 0.0310 1.50
% Cu in sample 27.2 6 10.9 -41 0.0502 2.42
DI, L 0.5 24 10.79 -46 0.2006 9.69
PS, µm 20-38 48 10.52 -27 0.4494 21.72
SS 800 72 10.47 -7 0.6441 31.12
[O2],ppm 15
Gly, M 0.5 1 10.96 -27 0.26158 12.94
sample mass, g 3.8 3 10.81 -17 0.6245 30.89
% Cu in sample 26.6 6 10.6 -13 0.9468 46.83
DI, L 0.5 24 10.17 1 1.4825 73.33
PS, µm -10 48 10.29 8 1.66308 82.27
SS 400 72 10.1 21 1.729 85.53
[O2],ppm 15
Gly, M 0.5 1 11.02 2 0.01765 0.85
sample mass, g 3.8 3 10.86 -6 0.03299 1.60
% Cu in sample 27.2 6 10.83 -8 0.06419 3.11
DI, L 0.5 24 10.73 -2 0.26138 12.64
PS, um 20-38 48 10.72 23 0.39769 19.24
SS 400 72 10.42 -7 0.52071 25.19
[O2],ppm 15
265
Gly, M 0.5 1 10.92 -35 0.0092 0.44
sample mass, g 3.804 3 10.88 -33 0.01568 0.76
% Cu in sample 27.2 24 10.82 -35 0.13873 6.70
DI, L 0.5 48 10.62 -14 0.31208 15.08
PS, µm 53-75 72 10.49 7 0.49423 23.88
SS 400 96 10.31 -6 0.6263 30.27
[O2],ppm 15
Gly, M 0.5 1 10.94 -33 0.0123 0.61
sample mass, g 3.804 3 10.91 -44 0.01718 0.85
% Cu in sample 26.6 6 10.87 -44 0.03385 1.67
DI, L 0.5 24 10.78 -9 0.1926 9.52
PS, µm 75-106 48 10.58 -13 0.38913 19.23
SS 400 72 10.57 -9 0.52968 26.17
Temp, degrees Celsius 50 96 0.64968 32.10
[O2],ppm 15
Gly, M 0.5 1 10.96 -19 0.0105 0.51
sample mass, g 3.8 3 10.89 -12 0.023 1.11
% Cu in sample 27.2 6 10.85 -13 0.03775 1.83
DI, L 0.5 24 10.66 -14 0.17975 8.70
PS, um 20-38 48 10.55 -10 0.2925 14.15
SS 400 72 0 0 0.4785 23.15
[O2],ppm 8
Gly, M 0.5 1 10.99 4 0.01875 0.91
sample mass, g 3.8 3 10.93 -1 0.03675 1.78
% Cu in sample 27.2 6 10.8 4 0.06775 3.28
DI, L 0.5 24 10.7 -8 0.26075 12.61
PS, um 20-38 48 10.5 20 0.51225 24.78
SS 400 72 10.01 10 0.52575 25.43
Temp, degrees Celsius 50 96 10 40 0.55425 26.81
[O2],ppm 25
Gly, M 0.5 1 11.02 2 0.01765 0.853655
sample mass, g 3.8 3 10.86 -6 0.03299 1.595963
% Cu in sample 27.2 6 10.83 -8 0.06419 3.105324
DI, L 0.5 24 10.73 -2 0.26138 12.64399
PS, um 20-38 48 10.72 23 0.39769 19.23816
SS 400 72 10.42 -7 0.52071 25.189
[O2],ppm 15
266
Gly, M 0.5 1 11.15 -15 0.00928 0.448203
sample mass, g 3.804 3 11.1 -42 0.01563 0.755059
% Cu in sample 27.2 6 11.07 -19 0.02545 1.229839
DI, L 0.5 24 0 0 0.07753 3.746298
PS, µm 20-38 48 10.94 -33 0.1492 7.209903
SS 400 72 10.93 -36 0.21948 10.60585
[O2],ppm 15
Gly, M 0.5 1 10.96 -27 0.02018 0.997972
sample mass, g 3.8 3 10.81 -17 0.05195 2.569747
% Cu in sample 26.6 6 10.6 -13 0.093 4.600317
DI, L 0.5 24 10.17 1 0.273 13.50416
PS, um 20-38 72 10.1 21 0.6172 30.53027
SS 400 96 9.88 27 0.78958 39.05694
[O2],ppm 15
Gly, M 0.5 1 0 0 0.02198 1.061914
sample mass, g 3.804 3 10.35 -34 0.05403 2.61069
% Cu in sample 27.2 6 10.3 -31 0.09018 4.357594
9.95-
DI, L 0.5 24 10.63 -7 0.27148 13.11869
9.91-
PS, µm 20-38 48 11.19 -6 0.50875 24.58471
9.38-
SS 400 72 11.30 11 0.70325 33.98367
[O2],ppm 15
Gly, M 0.5 0.5 11.82 -51 0.03446 1.727433
sample mass, g 3.7 1 11.82 -70 0.06281 3.148579
% Cu in sample 26.2 3 11.69 -46 0.15728 7.884231
DI, L 0.5 6 11.58 -40 0.26838 13.45352
PS, um 10 24 11.32 -4 0.72016 36.10063
SS 500 48 11.13 30 0.99615 49.93563
[O2],ppm 8
Gly, M 0.5 0.5 11.71 -83 0.06887 3.452359
sample mass, g 3.8 1 11.7 -79 0.11753 5.891618
% Cu in sample 27.2 3 11.34 -53 0.28529 14.3012
DI, L 0.5 6 11.25 -39 0.4699 23.55544
PS, um 10 24 10.97 -6 1.059 53.08622
SS 500 48 10.77 -10 1.18408 59.35631
Gly, M 0.5 1 11.4 -55 0.17999 9.022652
267
sample mass, g 3.804 3 10.95 -43 0.40387 20.24545
% Cu in sample 27.2 6 10.64 -34 0.64885 32.52596
DI, L 0.5 24 10.34 -14 1.09768 55.02519
PS, µm 10 48 10.14 -3 1.27891 64.11001
SS 400
[O2],ppm 15
Gly, M 0.5 0.5 11.22 -78 0.15885 7.962933
sample mass, g 3.8 1 10.75 -73 0.25971 13.01891
% Cu in sample 26.6 3 10.54 -45 0.66144 33.15708
DI, L 0.5 6 0.95744 47.99516
PS, um 10 24 10.04 -16 1.4491 72.6414
SS 400 48 10.03 -9 1.51172 75.78045
[O2],ppm 15
268
Appendix H 10 Copper-Gold ore A leaching data
leaching Conditions Time,h pH Eh, % cu % Au

mV [Cu],g [Au], extrn extrn
/L mg/L (recal't (recal'ted
ed h'grade)
h'grade
Peroxide,% 0 6 11.2 -47 0.174 2.41
pH (NaoH) 11 24 11.1 -61 0.455 6.28
DI 500 mL 120 10.6 -24 2.01 27.57
Sample mass, g ( % Cu
3.56, Au 1.96ppm) 100 168 10.4 -34 2.538 0.275 37.37 50.34
Cu:Gly 1:2
Peroxide, % 0 6 11 -18 0.235 3.21
pH (NaoH) 11 24 11 -25 0.628 8.54
DI 500 mL 500 120 10.7 -42 2.505 33.87
Sample mass, g 100g
(% Cu 3.56, Au 100 168 10.6 -35 3.372 0.211 46.68 42.33
Cu:Gly 1:4
0% peroxide 0 6 11.1 72 0.309 4.12
pH (NaoH) 11 24 11.1 -86 0.874 11.60
DI 500 mL 500 120 10.8 -64 2.85 37.61
Sample mass, g (% Cu
3.56, Au 1.96ppm) 100 168 10.7 -58 3.787 0.244 50.44 40.54
Cu:Gly 1:8
Peroxide, % 0 6 10.1 -6 0.18 2.45
pH 10 24 10 -25 0.542 7.35
DI, mL 500 120 9.73 -22 1.762 23.77
Sample mass,g (% Cu
3.56, Au 1.96ppm) 100 168 9.55 -9 2.267 0.258 31.36 51.44
Cu:gly 1:4
Peroxide,% 0 6 11 -18 0.235 3.21
pH 11 24 11 -25 0.628 8.54
DI,mL 500 120 10.7 -42 2.505 33.87
Sample mass,g ( % Cu
3.56, Au 1.96ppm) 100 168 10.6 -35 3.372 0.211 46.68 42.33
Cu:gly 1:4
Peroxide, % 0 6 11 -52 0.243 3.22
pH 12 24 11 -61 0.614 8.10
DI mL 500 120 10.6 -42 2.468 32.34
Sample mass,g (% Cu
3.56, Au 1.96ppm) 100 168 10.5 -32 3.268 0.238 46.53 39.61
Cu:gly 1:4
Peroxide, % 1 6 12.1 -80 5.75
pH (NaoH) 24 11.8 -81 11.82
DI ,mL 500 120 10.9 -51 38.71
Sample mass, g (% Cu
3.56, Au 1.96ppm) 100 168 10.3 -26 45.93 4.17
Cu:gly 1:4
269
Appendix H 11 Copper-Gold ore B leaching data
Leaching conditions Time, pH Eh, [Cu], Cu [Au], Au

h mV g/L extrn, % mg/L Extrn,%
(from (from
re-caltd re-caltd
h'grade) h'grade)
3 10.51 63 0.019 1.63 0 0.00

sample, g (0.134 Cu
= 0.67g Cu in
sample) 500 6 10.47 44 0.025 2.21 0 0.00
DI, mL 500 24 10.54 52 0.047 4.11 0.002 0.43
glycine,M 0.1 96 10.22 15 0.106 9.14 0.005 1.07
pH 11.06 192 10.24 36 0.152 13.03 0.008 1.71
Bottl roll, rpm 100 361 9.56 86 0.211 17.96 0.019 4.03
528 941 135 0.246 20.85 0.026 5.45
3 10.88 -20 0.026 2.16 0.001 0.20
sample, g (0.134 Cu =
0.67g Cu in sample) 500 6 10.79 -22 0.035 2.98 0.002 0.40
DI, mL 500 24 10.9 -7 0.066 5.56 0.004 0.79
glycine,M 0.3 96 10.64 -32 0.169 14.02 0.011 2.16
pH 11.06 192 10.63 -12 0.273 22.48 0.024 4.66
Bottl roll, rpm 100 361 10.48 40 0.444 36.24 0.058 11.13
528 10.44 71 0.567 46.03 0.082 15.66
3 10.94 -29 0.031 2.63 0.002 0.47
0.67g Cu in sample) 500 6 10.85 -40 0.04 3.46 0.002 0.47
DI, mL 500 24 10.97 -44 0.077 6.58 0.004 0.93
glycine,M 0.5 96 10.8 -57 0.202 17.01 0.017 3.89
pH 11.06 192 10.75 -23 0.335 28.00 0.034 7.72
Bottl roll, rpm 100 361 10.63 8 0.526 43.60 0.103 23.09
528 10.58 49 0.675 55.64 0.169 37.63
3 10.94 -64 0.041 3.51 0.003 0.69
0.67g Cu in sample) 500 6 10.95 -65 0.057 4.91 0.004 0.93
DI, mL 500 24 11.08 -70 0.108 9.28 0.009 2.07
glycine,M 1 96 10.94 -87 0.261 22.12 0.028 6.33
pH 11.06 192 10.86 -45 0.41 34.49 0.06 13.44
Bottl roll, rpm 100 361 10.83 -14 0.66 55.03 0.183 40.47
528 10.85 -3 0.784 65.10 0.241 53.08
3 7.81 82 0.019 1.61 0 0.00
0.67g Cu in sample) 500 6 7.83 74 0.025 2.19 0 0.00
DI, mL 500 24 7.94 99 0.084 7.23 0.001 0.24
glycine,M 0.5 96 7.89 69 0.095 8.16 0.001 0.24
pH 8 192 8.1 92 0.132 11.26 0.003 0.71
Bottl roll, rpm 100 361 7.92 163 0.188 15.90 0.005 1.27
528 8.23 167 0.225 18.93 0.01 2.33
270
3 9.05 47 0.028 2.37 0 0.00
0.67g Cu in sample) 500 6 8.93 19 0.042 3.53 0 0.00
DI, mL 500 24 9.1 36 0.048 4.07 0 0.00
glycine,M 0.5 96 9.05 27 0.194 16.06 0.003 0.61
pH 9 192 9.06 47 0.288 23.70 0.005 1.01
Bottl roll, rpm 100 361 8.92 83 0.404 33.03 0.015 3.04
528 8.95 128 0.514 41.78 0.022 4.36
3 9.97 19 0.039 3.35 0.001 0.22
0.67g Cu in sample) 500 6 9.94 -3 0.055 4.80 0.002 0.43
DI, mL 500 24 10.03 -19 0.114 9.82 0.004 0.85
glycine,M 0.5 96 10.02 5 0.267 22.72 0.008 1.69
pH 10 192 9.97 7 0.359 30.39 0.014 2.93
Bottl roll, rpm 100 361 9.91 45 0.51 42.84 0.03 6.23
528 9.96 50 0.62 51.82 0.038 7.83
sample mass, g 500 1 10.02-11.11 -4 0.076 6.99 0.001 0.17
DI, mL 500 3 10.6 -25 0.146 13.43 0.01 1.64
glycine, M 0.5 6 10.62-11 -22 0.232 21.22 0.02 3.25
-
pH (lime) 11.22 24 9.87-10.5 149 0.364 33.05 0.021 3.41
Temp, degrees celsius 60 48 9.22-11 34 0.62 55.77 0.093 14.83
Oxygen flow, L/min 0.3 99.5 8.59 52 0.777 65.96 0.103 15.38
sample mass, g 500 1 10.81 50 0.031 2.68 0.007 2.20
DI, mL 500 3 10.71 51 0.051 4.33 0.01 3.01
glycine, M 0.5 6 10.73 46 0.077 6.52 0.01 3.04
pH (lime) 11.22 24 10.66 56 0.205 17.10 0.011 3.25
Temp, degrees celsius 25 48 10.73 34 0.323 26.79 0.012 3.49
Oxygen flow, L/min 0.3 72 10.66 39 0.408 33.71 0.015 4.53
Stirring speed, RPM 250 95.5 10.08 30 0.495 40.67 0.029 8.52
sample mass, g 500 1 10.07-11.03 -9 0.074 4.44 0.008 3.35
DI, mL 500 3 10.77 -20 0.149 7.20 0.014 5.63
glycine, M 0.5 6.6 10.19-11.07 -9 0.267 10.83 0.021 8.45
pH (lime) 11.22 24 9.71-11.14 11 0.5 28.42 0.037 14.40
Temp, degrees celsius 60 48 9.51-11.07 33 0.682 44.51 0.05 19.48
Oxygen flow, L/min 0.05 72 9.17-11.08 32 0.691 56.01 0.062 23.95
Stirring speed, RPM 250 96 9.4 45 0.716 43.70 0.101 24.91
sample mass, g 500 1 10.27 0.142 9.63 0.023 4.09
DI, mL 500 3 9.96-11.27 -3 0.23 15.56 0.04 7.08
glycine, M 0.5 6 10.88 -10 0.308 20.77 0.065 11.44
pH (lime) 11.22 24 9.82-11.20 46 0.641 42.70 0.109 19.03
Oxygen flow, L/min 0.05 72 9.00-11.38 43 0.841 55.71 0.154 26.69

pyrite, g 4
sample mass, g 500 1.5 10.32-11.68 5 0.101 8.88 0.016 1.83
271
DI, mL 500 3 10.39 0.138 12.10 0.023 3.08
glycine, M 0.5 6 10.48 -27 0.236 20.57 0.044 4.62
pH (lime) 11.22 24 9.96-11.53 37 0.482 41.49 0.085 7.88
Temp, degrees celsius 60 48 9.87-11.30 -6 0.652 55.90 0.134 10.67
Oxygen flow, L/min 0.05 72 9.96-11.20 34 0.7 59.84 0.158 13.11
Stirring speed, RPM 250 96 0.618 53.64 0.168 21.35
pyrite, g 2
No pyrite 1 10.73 -12 0.063 4.70 0.011 2.37
sample mass, g 500 3 10.75 -7 0.124 9.24 0.031 6.55
DI, mL 500 6 10.21-11.5 5 0.207 15.27 0.04 8.41
glycine, M 0.5 24 10.08-11.46 -5 0.348 25.50 0.073 15.03
pH (lime) 11.7 48 9.48-11.56 19 0.604 43.89 0.122 24.93
Oxygen flow, L/min 0.05 96 10.15 47 0.494 36.53 0.22 44.93
Appendix H 12 Copper- Gold ore C leaching data
Au
Cu extrn, %
Extrn,%
Time, Eh, [Cu], (from re- [Au],
leaching conditions pH (from
h mV g/L caltd mg/L
re-caltd
h'grade)
h'grade)
3 10.51 63 0.019 1.63 0 0.00
0.67g Cu in sample) 500 6 10.47 44 0.025 2.21 0 0.00
DI, mL 500 24 10.54 52 0.047 4.11 0.002 0.43
glycine,M 0.1 96 10.22 15 0.106 9.14 0.005 1.07
pH 11.06 192 10.24 36 0.152 13.03 0.008 1.71
Bottl roll, rpm 100 361 9.56 86 0.211 17.96 0.019 4.03
528 941 135 0.246 20.85 0.026 5.45
3 10.88 -20 0.026 2.16 0.001 0.20
0.67g Cu in sample) 500 6 10.79 -22 0.035 2.98 0.002 0.40
DI, mL 500 24 10.9 -7 0.066 5.56 0.004 0.79
glycine,M 0.3 96 10.64 -32 0.169 14.02 0.011 2.16
pH 11.06 192 10.63 -12 0.273 22.48 0.024 4.66
Bottl roll, rpm 100 361 10.48 40 0.444 36.24 0.058 11.13
528 10.44 71 0.567 46.03 0.082 15.66
3 10.94 -29 0.031 2.63 0.002 0.47
0.67g Cu in sample) 500 6 10.85 -40 0.04 3.46 0.002 0.47
DI, mL 500 24 10.97 -44 0.077 6.58 0.004 0.93
glycine,M 0.5 96 10.8 -57 0.202 17.01 0.017 3.89
pH 11.06 192 10.75 -23 0.335 28.00 0.034 7.72
Bottl roll, rpm 100 361 10.63 8 0.526 43.60 0.103 23.09
528 10.58 49 0.675 55.64 0.169 37.63
3 10.94 -64 0.041 3.51 0.003 0.69
272
0.67g Cu in sample) 500 6 10.95 -65 0.057 4.91 0.004 0.93
DI, mL 500 24 11.08 -70 0.108 9.28 0.009 2.07
glycine,M 1 96 10.94 -87 0.261 22.12 0.028 6.33
pH 11.06 192 10.86 -45 0.41 34.49 0.06 13.44
Bottl roll, rpm 100 361 10.83 -14 0.66 55.03 0.183 40.47
528 10.85 -3 0.784 65.10 0.241 53.08
3 7.81 82 0.019 1.61 0 0.00
0.67g Cu in sample) 500 6 7.83 74 0.025 2.19 0 0.00
DI, mL 500 24 7.94 99 0.084 7.23 0.001 0.24
glycine,M 0.5 96 7.89 69 0.095 8.16 0.001 0.24
pH 8 192 8.1 92 0.132 11.26 0.003 0.71
Bottl roll, rpm 100 361 7.92 163 0.188 15.90 0.005 1.27
528 8.23 167 0.225 18.93 0.01 2.33
3 9.05 47 0.028 2.37 0 0.00
0.67g Cu in sample) 500 6 8.93 19 0.042 3.53 0 0.00
DI, mL 500 24 9.1 36 0.048 4.07 0 0.00
glycine,M 0.5 96 9.05 27 0.194 16.06 0.003 0.61
pH 9 192 9.06 47 0.288 23.70 0.005 1.01
Bottl roll, rpm 100 361 8.92 83 0.404 33.03 0.015 3.04
528 8.95 128 0.514 41.78 0.022 4.36
3 9.97 19 0.039 3.35 0.001 0.22
0.67g Cu in sample) 500 6 9.94 -3 0.055 4.80 0.002 0.43
DI, mL 500 24 10.03 -19 0.114 9.82 0.004 0.85
glycine,M 0.5 96 10.02 5 0.267 22.72 0.008 1.69
pH 10 192 9.97 7 0.359 30.39 0.014 2.93
Bottl roll, rpm 100 361 9.91 45 0.51 42.84 0.03 6.23
528 9.96 50 0.62 51.82 0.038 7.83
10.02-
sample mass, g 500 1 11.11 -4 0.076 6.99 0.001 0.17
DI, mL 500 3 10.6 -25 0.146 13.43 0.01 1.64
glycine, M 0.5 6 10.62-11 -22 0.232 21.22 0.02 3.25
pH (lime) 11.22 24 9.87-10.5 -149 0.364 33.05 0.021 3.41
Temp, degrees celsius 60 48 9.22-11 34 0.62 55.77 0.093 14.83
Oxygen flow, L/min 0.3 99.5 8.59 52 0.777 65.96 0.103 15.38
sample mass, g 500 1 10.81 50 0.031 2.68 0.007 2.20
DI, mL 500 3 10.71 51 0.051 4.33 0.01 3.01
glycine, M 0.5 6 10.73 46 0.077 6.52 0.01 3.04
pH (lime) 11.22 24 10.66 56 0.205 17.10 0.011 3.25
Temp, degrees celsius 25 48 10.73 34 0.323 26.79 0.012 3.49
Oxygen flow, L/min 0.3 72 10.66 39 0.408 33.71 0.015 4.53
Stirring speed, RPM 250 95.5 10.08 30 0.495 40.67 0.029 8.52
10.07-
sample mass, g 500 1 11.03 -9 0.074 4.44 0.008 3.35
273
DI, mL 500 3 10.77 -20 0.149 7.20 0.014 5.63
10.19-
glycine, M 0.5 6.6 11.07 -9 0.267 10.83 0.021 8.45
pH (lime) 11.22 24 9.71-11.14 11 0.5 28.42 0.037 14.40
Oxygen flow, L/min 0.05 72 9.17-11.08 32 0.691 56.01 0.062 23.95
sample mass, g 500 1 10.27 0.142 9.63 0.023 4.09
DI, mL 500 3 9.96-11.27 -3 0.23 15.56 0.04 7.08
glycine, M 0.5 6 10.88 -10 0.308 20.77 0.065 11.44
pH (lime) 11.22 24 9.82-11.20 46 0.641 42.70 0.109 19.03
Oxygen flow, L/min 0.05 72 9.00-11.38 43 0.841 55.71 0.154 26.69

pyrite, g 4
10.32-
sample mass, g 500 1.5 11.68 5 0.101 8.88 0.016 1.83
DI, mL 500 3 10.39 0.138 12.10 0.023 3.08
glycine, M 0.5 6 10.48 -27 0.236 20.57 0.044 4.62
pH (lime) 11.22 24 9.96-11.53 37 0.482 41.49 0.085 7.88
Temp, degrees celsius 60 48 9.87-11.30 -6 0.652 55.90 0.134 10.67
Oxygen flow, L/min 0.05 72 9.96-11.20 34 0.7 59.84 0.158 13.11
Stirring speed, RPM 250 96 0.618 53.64 0.168 21.35
pyrite, g 2
No pyrite 1 10.73 -12 0.063 4.70 0.011 2.37
sample mass, g 500 3 10.75 -7 0.124 9.24 0.031 6.55
DI, mL 500 6 10.21-11.5 5 0.207 15.27 0.04 8.41
10.08-
glycine, M 0.5 24 11.46 -5 0.348 25.50 0.073 15.03
pH (lime) 11.7 48 9.48-11.56 19 0.604 43.89 0.122 24.93
Oxygen flow, L/min 0.05 96 10.15 47 0.494 36.53 0.22 44.93
274
Appendix H 13 Copper-Gold ore C column leaching data
Cu Au
Time, Eh [Cu], extrn [Au], extrn,
Leaching conditions days pH (mV) mg/L ,% mg/L %
Sample mass, g 5000 0.063 10.56 55 5 0.32
DI, L 3 0.15 11.05 45 7.3 0.46
[Cu] in ore, % 0.095 0.25 14.9 0.94
expected Cu in soln, g/L 1.5833 1 10.95-11.12 33 20.5 1.29
[Au] in ore, % 8E-05 3 11.2 55 26.17 1.65
expected Au in soln 0.0013 10 10.48-11.30 27 35.5 2.24
solution flow, ml/min 3.5 28 10.96 -32 42.25 2.67
[Gly], M 0.1 39 10.39 33 56.175 3.55
56 88.075 5.56
60 88.875 5.61
87 101 6.38 0.007 0.54
111 115 7.26 0.019 1.46
125 9.89-11.45 121 7.64 0.00
159 147.25 9.30 0.009 0.68
166 148 9.35 0.023 1.76
mass sample, g 5000 1 10.46 9 22.4 1.41 0.00
DI, L 3 4 10.42 65 24.95 1.58 0.00
[Cu] in ore, % 0.095 8 32.05 2.02 0.00
expected Cu in solution 1.5833 30 80 5.05 0.00
[Au] in ore, % 8E-05 36 94.375 5.96 0.004 0.31
expected Au in soln 0.0013 60 105 6.63 0.007 0.54
solution flow, ml/min 3.5 74 10.44-11.21 110.425 6.97
[Gly], M 0.5 103 152.125 9.61 5E-04 0.04
115 156 9.85 0.013 1.00
275
Appendix H 14 Copper-Gold D column leaching data
Time, Cu extrn, [Au], Au

Leaching conditions days pH [Cu], g/L % mg/L extrn, %
Total sample mass, g 2698.7 1 9.39 0.348 7.07
minus 2mm, g 1553.3 3 9.24 0.498 10.11
plus 2 mm, g 1145.4 7 8.99 0.912 18.52
Soln vol, L 2 14 8.87 1.3825 28.07
Soln pH 11.04 24 9.97 0.9741 39.56
slon flow rate, mL/min 14.4 40 1.15 46.70 0.022 5.03
% Cu in sample 0.365 49 9.5 1.32 53.60 0.033 7.55
expexted Cu in soln b4
19/04/16, g/L 4.92513
expexted Cu in soln, g/L 2.46256
on 19/04/2016, (14 days)
leaching solution was
diluted with 2L of same
composition
Au in ore , % 6.5E-05
[Au] in soln, g/L 0.00044
276
Appendix H 15 Example of copper and gold leaching rates from recalculated head grades- leaching Cu-Au ore C with 0.5 M [Gly]
Recordings Cu removed from soln AU removed from soln

Solution Au leach
Time volume Cumm Cu Cu leach Cu extrn Soln Cu Cumm vessel Au extrn Soln Au
(hours) Ore (g) (mL) sol ,L [Cu],g/L Au, ppm vol(mL) Cu (g) (g) vessel (g) total(g) extrn % Au (μg) Au (μg) (μg) total(μg) extrn %
500
0 500 0.5 0 0 0
3 490 0.49 0.0305 0.002 10 0.00031 0.00031 0.01495 0.01495 2.626 0.02000 0.02000 0.98000 0.98000 0.469
6 485 0.485 0.04 0.002 5 0.00020 0.00051 0.01940 0.01971 3.462 0.01000 0.03000 0.97000 0.99000 0.474
24 480 0.48 0.077 0.004 5 0.00039 0.00089 0.03696 0.03747 6.583 0.02000 0.05000 1.92000 1.95000 0.934
96 475 0.475 0.202 0.017 5 0.00101 0.00190 0.09595 0.09684 17.015 0.08500 0.13500 8.07500 8.12500 3.892
192 470 0.47 0.335 0.034 5 0.00168 0.00358 0.15745 0.15935 27.998 0.17000 0.30500 15.98000 16.11500 7.720
361 465 0.465 0.526 0.103 5 0.00263 0.00621 0.24459 0.24817 43.602 0.51500 0.82000 47.89500 48.20000 23.090
528 460 0.46 0.675 0.169 0.31050 0.31671 55.645 77.74000 78.56000 37.634
35 0.00621 0.82000
Cu GOLD EXTRACTION CALCULATIONS
Product Qty grade mass,g PRODUCT Quantity GOLD
Solids 495 0.051 0.25245 GRADE MASS DISTn.
Solution 0.46 0.675 0.3105 (ppm) (µg) (%)
Removed 0.006205 SOLIDS 495.0 0.263 130 62.37
Total 0.569155 SOLUTION 460.0 0.169 78 37.24
REMOVED 0.82 0.39
GRAVITY
TOTAL 955.0 209 100.00

CALC'd HEAD 0.42
277
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Glycine As A Lixiviant For The Leaching of Low Grade Copper Gold Ores Bennson Chemuta Tanda

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Glycine As A Lixiviant For The Leaching of Low Grade Copper Gold Ores Bennson Chemuta Tanda

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What is the thesis about?

What is the thesis about?

What minerals were investigated for copper leaching?

What minerals were investigated for copper leaching?

Western Australian School of Mines

GLYCINE AS A LIXIVIANT FOR THE LEACHING OF LOW

Bennson Chemuta Tanda

This thesis is presented for the Degree of

Author’s Declaration ....................................................................................................... i

List of Publications ......................................................................................................... ii

Table of Contents .......................................................................................................... vii

List of Figures… ............................................................................................................. xv

List of Tables… ............................................................................................................ xxiii

List of Abbreviations ................................................................................................. xxvii

Chapter 1 Introduction ............................................................................................ 1

1.1 Background to this study ........................................................................ 1

1.2 Objectives and significance of this study ................................................ 5

1.3 Scope of this study .................................................................................. 6

1.4 Thesis Overview ...................................................................................... 7

Chapter 2 Review of Literature ............................................................................... 9

2.1 Chapter Objective ................................................................................... 9

2.2 Copper-Gold Resources .......................................................................... 9

2.2.1 Mineralogical variation in porphyry copper-gold deposits .................. 11

2.3 Processing of Copper-Gold Ores ........................................................... 15

2.3.1 Copper-Gold Cyanidation Challenges ................................................... 15

2.3.2 Coping with Copper-Gold Cyanidation Challenges ............................... 19

2.4 Attributes of Good Lixiviants ................................................................ 21

2.4.1 Attributes of Copper and/or Gold Ore Lixiviants .................................. 23

2.5 Alkaline Ammoniacal Hydrometallurgy of Copper and Gold ................ 25

2.5.2 Metal Recovery from Ammoniacal PLS................................................. 36

2.5.3 Challenges of Ammonia Leaching ......................................................... 37

2.6 Glycine as Copper and Gold Lixiviant.................................................... 38

2.6.1 Structure, Physical and Chemical Properties ........................................ 38

2.6.2 Industrial Applications of Glycine ......................................................... 39

2.6.3 Glycine Production................................................................................ 39

2.6.4 Aqueous Chemistry of Glycine .............................................................. 40

2.6.5 Glycine Analysis .................................................................................... 45

2.7 Leaching Methods Applicable to Low Grade Ores................................ 46

2.7.1 Dump Leaching ..................................................................................... 48

2.7.2 Heap Leaching ....................................................................................... 49

2.7.3 Vat Leaching .......................................................................................... 50

2.8 Summary ............................................................................................... 52

Chapter 3 Materials and Methods......................................................................... 53

3.1 Chapter Objectives................................................................................ 53

3.2 Materials and Reagents ........................................................................ 53

3.3 Procedures ............................................................................................ 55

3.3.1 Mineral and Ore Specimens Preparation ............................................. 55

3.3.2 Leaching Behaviour of Copper Minerals ............................................... 56

3.3.3 Copper Speciation ................................................................................. 57

3.3.4 Leaching Kinetics Experiments ............................................................. 57

3.3.5 Leaching of Copper-Gold Ores .............................................................. 59

3.3.6 Column Leaching................................................................................... 59

3.3.7 Solvent Extraction ................................................................................. 61

3.4.1 X-Ray Diffraction (XRD) ......................................................................... 64

3.4.2 X-Ray Fluorescence (XRF)...................................................................... 65

3.4.3 TESCAN Integrated Mineral Analyser (TIMA) ....................................... 65

3.4.4 UV-Visible (UV-Vis) Spectrophotometry ............................................... 65

3.4.5 Particle Size Analysis (PSA) ................................................................... 66

3.4.6 Atomic Absorption Spectrometry (AAS) ............................................... 66