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Recovery of Gold from Thiosulfate Solutions and Pulps with Anion- Exchange Resins

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Recovery of Gold from Thiosulfate Solutions and Pulps with Anion- Exchange Resins View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Research Repository Recovery of Gold from Thiosulfate Solutions and Pulps with Anion- Exchange Resins This Thesis is Presented for the Degree of Doctor of Philosophy in Extractive Metallurgy From Murdoch University, Western Australia Glen Peter O'Malley 2002 I declare that this thesis is an account of my own research and contains work that has not previously been submitted for a degree at any other educational institution. Glen O'Malley March, 2002 i ACKNOWLEDGEMENTS A special thanks goes to Professor Mike Nicol for his guidance and support throughout the PhD. Thanks also go to Rob Dunne (Newcrest Mining) and Dr. Steven La Brooy (Gold Resource and Development Macraes Ltd) for their support and feedback as the SPIRT sponsors for this PhD. I am grateful for the financial support of my two Australian Research Council SPIRT sponsors, Newcrest Mining and GRD Macraes. Also for the financial support of the sponsors of AMIRA Project P420A Module 3 which include Anglogold Australasia, Alcoa World Alumina Australia, Carpentaria Gold, Goldfields, Newcrest Mining, Normandy Mining, Placer Dome, Rio Tinto Research & Technology Development, WMC Resources and Worsley Alumina. The author is also grateful to Dr. Gamini Senanayake, Dr. Kathryn Hindmarsh, Dr. Peter Lye and Karen Barbetti for their suggestions and help in preparing the initial stages of the thesis. Special thanks go to Dr. Nimal Perera, Dr. Peter Lye and Dr. Hongguang Zhang for their suggestions during the final stages of the thesis. Thanks also go to J. Avilla (ResinTech Inc.), I. Needs and S. Stewert (Rohm and Haas) for providing the resin samples and G. Wardell-Johnson (Boddington Gold Mine) and G. Kelly (Kandowna Belle Gold Mine) for the ore samples. Lastly I would like to thank the A.J. Parker Cooperative Research Centre for Hydrometallurgy for the courses and seminars conducted as part of the PhD student development program. ii ABSTRACT With growing environmental and occupational safety concerns over the use of cyanide in gold processing, more acceptable alternatives are receiving increased interest. The most promising of the possible alternatives is thiosulfate. However, as activated carbon is not an effective substrate for the adsorption of the gold thiosulfate complex, the thiosulfate process lacks a proven in-pulp method for recovering dissolved gold. Anion exchange resins offer a possible route for in-pulp recovery. This thesis describes work aimed at evaluating the effectiveness of commercially available anion exchange resins for the recovery of gold from thiosulfate leach liquors and pulps. It was found that Strong-base resins are superior at accommodating the gold thiosulfate complex compared to Weak-base resins, which means Strong-base resins have a greater capacity to compete with other anions in leach solutions. Strong-base resins were therefore the preferred choice of resin for recovery of gold from thiosulfate leach solutions and pulps. Work with a selected commercial Strong-base resin showed that competing polythionates (particularly tri- and tetrathionate) lower the maximum possible loading of gold but that gold is selectively recovered over other base-metal anions in typical leach solutions. From kinetic experiments, it was found that competing polythionates did not affect the initial rate of loading of gold but displaced the loaded gold at long times. Thus it would be important to minimise the contact time of the resin with the pulp. Equilibrium loading isotherms of gold in the presence of competing anions could be analysed by treating the ion exchange reaction as a simple chemical reaction. However, a stoichiometry and equilibrium quotient which does not follow that normally used for anion exchange, was required to describe the experimental data. A single value for the equilibrium constant also cannot be used to describe the data over the range of concentrations for a given competing anion. The order of selectivity of the anions for the anion exchange resin could be explained by the difference in structure and the charge of each anion. iii The rate of loading of gold is controlled by mass transport in the aqueous phase in the presence of weakly competing anions such as sulfate and thiosulfate. An attempt was made to describe the more complex loading curves obtained in the presence of stronger competing anions such as sulfite, trithionate and tetrathionate in which it was found that the loading of gold increased to a maximum before declining to a lower equilibrium value. The difference in the rate of loading between the macroporous and gel anion exchange resins was explained by the difference in the location of their functional groups. Operation of a small-scale resin-in-pulp plant showed that gold could be recovered from a leach pulp to yield loadings of gold of up to 6000 mg L-1 and loadings of copper below 100 mg L-1. Under ideal conditions, the gold concentration in the barren pulp could contain less than 0.01 mg L-1. Throughout the trial it was shown that loaded copper would be displaced by gold which would result in the loading of copper falling from 2000 mg L-1 in the last stage to lower than 100 mg L-1 on the resin in the first stage. It was observed that some of the dissolved gold precipitated or adsorbed on the solids during leaching. Some of this adsorbed gold was found to be recovered by the anion exchange resins that would have reported to the tails if a solid/liquid separation method was employed. Gold was efficiently eluted with a nitrate solution and the two-step elution process using aerated ammonia followed by nitrate effectively stripped all the copper and gold from the resin. This process was found not to materially affect the equilibrium gold concentration on the resin after eight cycles, thus allowing the resin to be recycled without the need for regeneration. Electrochemical studies showed that the gold thiosulfate complex was reduced on stainless steel from a nitrate solution. Conventional electrowinning could therefore be used to recover the gold from the eluant. A copy of the thesis and the appendices are provided on CD. iv TABLE OF CONTENTS Page DECLARATION i ACKNOWLEDGEMENTS ii ABSTRACT iii TABLE OF CONTENTS v LIST OF TABLES xiii LIST OF FIGURES xvi LIST OF APPENDICES xxvi ABREVIATIONS xxvii CHAPTER 1 REVIEW OF THE LEACHING OF GOLD USING THIOSULFATE 1 1.1 INTRODUCTION 1 1.2 THE LEACHING OF GOLD WITH THIOSULFATE 2 1.2.1 History 2 1.2.2 Limitation and Advantages of Leaching of Gold with Thiosulfate 3 1.2.3 Condition Employed in Thiosulfate Leaching with Thiosulfate 4 1.3 THE CHEMISTRY OF THIOSULFATE 8 1.3.1 Oxidation State of Sulfur 8 1.3.2 Stability of Thiosulfate 10 1.3.3 Metal Complexation with Thiosulfate 12 1.3.4 Generation and Stabilization of Thiosulfate 13 1.3.5 Determination of Thiosulfate 14 1.3.6 Corrosion Properties 15 v 1.4 THERMODYNAMICS OF THE LEACHING OF GOLD AND SILVER BY THIOSULFATE 16 1.4.1 Stability of Gold and Silver Complexes 16 1.4.2 Stability of Copper Complexes 18 1.4.3 Stability of Sulfur Species 19 1.4.4 Alternative Stability Diagram for Gold 20 1.5 FACTORS INFLUENCING THE RATE OF DISSOLUTION OF GOLD AND SILVER 22 1.5.1 Effect of Thiosulfate Concentration 22 1.5.2 Effect of Ammonia Concentration 23 1.5.3 Effect of Copper Concentration 24 1.5.4 Effect of Temperature 25 1.5.5 Effect of pH 25 1.5.6 Effect of the Partial Pressure of Oxygen 26 1.5.7 Effect of Sulfite and Sulfate 26 1.5.8 Effect of Leach Time 27 1.5.9 Effect of Pulp Density 27 1.5.10 Effect of Pre-Oxidation 28 1.6 ELECTOCHEMICAL STUDIES ON THE MECHANISM OF GOLD DISSOLUTION IN THIOSULFATE SOLUTION 29 1.7 CONCLUSION 33 vi CHAPTER 2 REVIEW OF THE RECOVERY OF GOLD FROM THIOSULFATE LEACH SOLUTIONS AND PULPS 34 2.1 INTRODUCTION 34 2.2 REDUCTION OF THE GOLD THIOSULFATE COMPLEX 35 2.2.1 Cementation of Gold on Copper, Iron, Zinc or Aluminium 35 2.2.2 Chemical Reduction 37 2.2.3 Electrowinning 39 2.3 CHEMICAL PRECIPITATION 41 2.4 SOLVENT EXTRACTION 42 2.5 ACTIVATED CARBON 44 2.6 ADSORPTION ON ANION EXCHANGE RESINS 46 2.6.1 History 46 2.6.2 Structure and Synthesis of Anion Exchange Resins 47 2.6.3 Strong-Base and Weak-Base Anion Exchange Resins 50 2.6.4 Physical Properties of Anion Exchange Resins 52 2.6.5 Adsorption Equilibria and Loading Capacity 52 2.6.6 Equilibrium Gold Loading Models 54 2.6.7 Kinetic Studies and Models for Gold Loading 55 2.6.8 Selectivity of Anion Exchange Resins 61 2.6.8.1 Solution Chemistry 61 2.6.8.2 Properties of Anions 62 2.6.8.3 Structure of the Resin 69 2.6.9 Application of Resins to Recover the Gold Thiosulfate Complex 76 2.6.9.1 Strong-Base Resins 76 2.6.9.2 Weak-Base Resins 76 vii 2.6.10 Summary of Published Work on Recovering Gold from Thiosulfate Solutions and Pulps 78 2.6.11 Elution of Metal Complexes from Anion Exchange Resins 81 2.6.11.1 Strong-Base resins 81 2.6.11.2 Weak-Base resins 83 2.6.12 Characteristics of a Resin for the Recovery of Gold Thiosulfate from Pulps 84 2.7 FURTHER DEVELOPMENT 86 CHAPTER 3 MATERIALS AND METHODS 87 3.1 MATERIALS, REAGENTS, PROCEDURES AND APPARATUS 87 3.2 PROCEDURES FOR THE PREPARATION, CHARACTERISATION AND ANALYSIS OF THE RESINS 90 3.2.1 Preparation of Resins 90 3.2.2 Particle Size Distribution 90 3.2.3 Resin Density 91 3.2.4 Theoretical Exchange Capacity 91 3.3 SYNTHESIS OF TRITHIONATE AND TETRATHIONATE 93 3.3.1 Synthesis of Tetrathionate 93 3.3.2 Synthesis of Trithionate 93 3.4 DETERMINATION OF METAL CONCENTRATION IN SOLUTION BY ATOMIC ADSORPTION SPECTROPHOTOMETER (AAS) 95 3.4.1 Stability
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