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Fe6+) AS an ALTERNATIVE METHOD FOR FERRATE IRON (Fe6+) AS AN ALTERNATIVE METHOD FOR THE DETOXIFICATION OF CYANIDE AND CYANIDE SPECIES IN GOLD CYANIDATION LEACH TAILS by James M. Lorengo A thesis submitted to the Faculty and the Board of Trustees of the Colorado School of Mines in partial fulfillment of the requirements for the degree of Masters of Science (Metallurgical and Materials Engineering). Golden, Colorado Date: __________ Signed: __________________________ ______ James M Lorengo Signed: ________________________________ Dr. Patrick Taylor, Thesis Advisor Golden, Colorado Date: __________ Signed: __________________________ Dr. Michael Kaufman, Department Head Metallurgical and Materials Engineering ABSTRACT The oxidative properties of ferrate (VI) iron were investigated in an attempt to determine its destruction efficiency on the cyanide ion, cyanide containing species, and the resulting derivatives of the oxidative process. The species included free cyanide and the complexes of copper, nickel, silver, and thiocyanate respectively. Additionally, in an effort to harness the ferrate breakdown product of ferric hydroxide, the removal of heavy metals was also investigated. The studies were conducted in Newmont facilities on controlled synthetic solutions as well as ―real world‖ tailings from Newmont owned properties. It was established that, irrespective of metal specie studied, cyanide detox by ferrate was achieved. iii TABLE OF CONTENTS ABSTRACT ........................................................................................................................ iii LIST OF FIGURES ............................................................................................................ vi LIST OF TABLES ............................................................................................................. viii ACKNOWLEGEMENTS ................................................................................................... ix DEDICATION .................................................................................................................... ix CHAPTER 1 INTRODUCTION ......................................................................................... 1 1.1 Background ................................................................................................................................... 1 1.2 Scope of Work and Objective ....................................................................................................... 4 CHAPTER 2 LITERATURE REVIEW ............................................................................... 6 2.1 Chemistry of Cyanidation ............................................................................................................. 6 2.1.1 Gold ....................................................................................................................................... 6 2.1.2 Silver ................................................................................................................................... 13 2.1.3 Copper ................................................................................................................................. 14 2.1.4 Nickel .................................................................................................................................. 15 2.1.5 Sulfur ................................................................................................................................... 16 2.2 Remediation of Cyanide Waste................................................................................................... 16 2.2.1 Caro’s Acid ......................................................................................................................... 18 2.2.2 SO2/AIR .............................................................................................................................. 20 2.3 Ferrate Production ....................................................................................................................... 22 2.4 Ferrate Chemistry ........................................................................................................................ 24 CHAPTER 3 EXPERIMENTAL METHODS ................................................................. 29 3.1 Materials ..................................................................................................................................... 29 3.2 Experimental Procedures ............................................................................................................ 30 3.3 Analytical Procedure for Cyanide in Solution ............................................................................ 31 3.4 Determination of the Potassium Ferrate Salt Purity .................................................................... 33 CHAPTER 4 FERRATE OXIDATION TESTING AND RESULTS ................................. 35 - 4.1 Free Cyanide [CN ] .................................................................................................................... 35 - 4.2 Thiocyanate as [SCN ] ................................................................................................................ 39 2- 4.3 Copper (1) Cyanide as [Cu(CN)3] ............................................................................................. 43 iv 2- 4.3.1. Copper Cyanide as [Cu(CN)3] as a Catalyst for Free Cyanide Oxidation ......................... 45 2 - 4.4 Silver Cyanide as [Ag(CN) ] ...................................................................................................... 47 2- 4.4.1 Copper Cyanide as [Cu(CN)3] as a Catalyst for Silver Cyanide Oxidation ...................... 48 2- 4.5 Nickel Cyanide as [Ni(CN)4] .................................................................................................... 48 4.6 Cyanide Leach Tails from Newmont’s Phoenix Operation ........................................................ 50 4.6.1 Cyanide Leach Tails Slurry Detox ...................................................................................... 50 CHAPTER 5 CONCLUSIONS ......................................................................................... 54 5.1 Results on Synthetic Solutions .................................................................................................... 54 5.2 Results on Phoenix Leach Tails .................................................................................................. 56 5.3 Economic Considerations ........................................................................................................... 56 5.4 Suggestions for Future Research ................................................................................................. 57 REFERENCES .................................................................................................................. 58 APPENDIX A .................................................................................................................... 61 EXPERIMENTAL DATA – GAS DIFFUSION AMPEROMETRY OF CNwad ................. 61 APPENDIX B ..................................................................................................................... 71 EXPERIMENTAL DATA – ION CHROMATOGRAPY .................................................. 71 APPENDIX C .................................................................................................................... 73 EXPERIMENTAL DATA – LEACH TAILS CHARACTERIZATION AND DETOX ..... 73 APPENDIX D .................................................................................................................... 75 OIA-METHOD 1677 .......................................................................................................... 75 v LIST OF FIGURES Figure 1.1 Phoenix Process Flow Sheet ......................................................................................................... 2 Figure 2.1 Speciation of Cyanide and Hydrogen Cyanide in Solution as a Function of pH ........................ 8 Figure 2.2 Pourbaix Diagram of CN-H2O System. ......................................................................................... 9 Figure 2.3 Gold-Cyanide Surface Chemistry Electrochemical Illustration ................................................. 10 Figure 2.4 Pourbaix Diagram of Au-CN-H2O System ................................................................................. 11 Figure 2.5 Pourbaix Diagram Overlap Figures 3 and 4 ............................................................................... 12 Figure 2.6 Pourbaix Diagram of Ag-CN-H2O System .................................................................................. 13 Figure 2.7 Pourbaix Diagram of Cu-CN-H2O System .................................................................................. 14 Figure 2.8 Pourbaix Diagram of Ni-CN-H2O System ................................................................................. 15 Figure 2.9 Schematic Illustration of the Reaction of Polythionates in Aqueous Solutions to form thiocyanate ................................................................................................................................................ 17 Figure 2.10 Caro’s Acid Reactor Plant ........................................................................................................ 18 Figure 2.11 Reactor Schematic for SO2/Air Cyanide Detoxification ........................................................... 21 Figure 2.12 Electrochemical Cell for Ferrate Synthesis .............................................................................
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