Hydrometallurgy

1. Hydrometallurgy MINE 292 Introduction to Mineral Processing Lecture 21 John A Meech

2. Hydrometallurgical Processing • Comminution(Grinding) • Leaching Metal (Quantity - %Recovery) • Removal of Metal from Pulp a. Solid/Liquid Separation - CCD thickeners - Staged-washing filtration b. Adsorption (Carbon-in-Pulp and/or Resin-in-Pulp) (CIP/RIP or CIL/RIL) - granular carbon or coarse resin beads

3. Hydrometallurgical Processing 4. Purification (Quality - g/L and removing other ions) - Clarification and Deaeration (vacuum) - Precipitation (Gold: Zn or Al dust) (Copper: H2S or scrap Fe or lime) (Uranium: yellow cake) (Zinc: lime) - Solvent Extraction (adsorption into organic liquid) - Ion Exchange (resin elution columns) - Elution (contact carbon or resin with an electrolyte)

4. Hydrometallurgical Processing 5. Electrowinning or Precipitation followed by Smelting

5. Hydrometallurgical Processing

6. Hydrometallurgical Processing Classifier

7. Hydrometallurgical Processing Feed Grade = 5 g Au/t Ore %Recovery during Grinding = 60% >>> solids content = 2.00 g/t %Recovery during Leaching = 35% >>> solids content = 0.25 g/t %Recovery during CCD = 0% %Recovery Total = 95% Underflow Densities = 50%solids Leach Density = 40% solids Classifier O/F Density = 40%solids Pregnant Solution Flowrate = 300% Barren Bleed Flowrate = 25% Gold in Barren Solution = 0.05 g/t Calculate the gold content of the Pregnant Solution and the U/F water from each thickener. What is the actual mill recovery? What difference would occur if fresh solution was added to Thickener E rather than Thickener B?

8. Metal Recovery by Dissolution • Primary extraction from ores • Used with ores that can't be treated physically • Secondary extraction from concentrates • Used with ores that can be beneficiated to a low-grade level

9. Metal Recovery by Dissolution • Applied to • Copper (both acid and alkali) CuO + H2SO4 → CuSO4 + H2O CuO + 2NH4OH + (NH4)2CO3 → Cu(NH3)4 CO3 + 3H2O • Zinc (acid) ZnO + H2SO4 → ZnSO4 + H2O • Nickel (acid and alkali) – Nickel Laterite Ores NiO + H2SO4 → NiSO4 + H2O NiO+ 4NH4OH + (NH4)2CO3 → Ni(NH3)6CO3 + 5H2O

10. Copper Leaching by Ammonium Carbonate azurite = Cu3(OH)2(CO3)2 63.5x3+17x2+60x2 = 55.3%Cu malachite = Cu2(OH)2CO3 63.5x2+17x2+60 = 57.5%Cu pseudomalachite = Cu5(PO4)2(OH)4 63.5x5+17x4+95x2 = 55.2%Cu tenorite = CuO 63.5+16 = 79.9%Cu chrysocolla = CuSiO3.2H2O 63.5+16x3+28+2x18 = 36.2%Cu cuprite = Cu2O 63.5x2+16 = 88.8%Cu Cu3(OH)2(CO3)2 + 5NH4OH + (NH4)2CO3 = 3Cu(NH3)4CO3 + 12H2O Cu2(OH)2CO3 + 6NH4OH + (NH4)2CO3 = 2Cu(NH3)4CO3 + 8H2O CuO + 2NH4OH + (NH4)2CO3 = Cu(NH3)4CO3 + 3H2O Cu2O + 4NH4OH + 2(NH4)2CO3 = Cu(NH3)4CO3 + 5H2O xCu5(PO4)2(OH)4+ yNH4OH + z(NH4)2CO3= aCu(NH3)4CO3+ bH3PO4+ cH2O

11. Ammonia Leaching of Malachite NH4Cl → NH4+ + Cl– (1) NH4+ + H2O → H3O+ + NH3 (2) CuCO3·Cu(OH)2 + 2H3O+ → Cu2+ + CO2 + 3H2O + Cu(OH)2 (3) Cu(OH)2 + 2H3O+ → Cu2+ + 2H2O (4) Overall Leaching Reaction CuCO3·Cu(OH)2 + 4 NH4Cl → 2Cu2+ + 4Cl– + CO2 +3H2O +4NH3(5) Formation of complex amine ions Cu2+ + 2NH3 → Cu(NH3)22+ (6) Cu(NH3)22+ + 2NH3 → Cu(NH3)42+ (7)

12. Zinc Roasting/Leaching/Electrowinning

13. Nickel Lateritic Ores • acid heap leaching method similar to copper • H2SO4 much higher than for copper (1,000 kg/t) • patented by BHP Billiton • being commercialized by • Cerro Matoso S.A. in Columbia • Vale in Brazil • European Nickel Plc in Turkey, Balkans, Philippines

14. Metal Recovery by Dissolution • Applied to • Aluminum (alkali) Al2O3 + 3H2O + 2NaOH → 2NaAl(OH)4 • Gold and Silver (cyanidation / alkali) • Uranium (acid and alkali)

15. Alumina Leaching

16. Aluminum Smelting • Fused Salt Electrolysis – Hall-Herault Process

17. Aluminum Smelting • Fused Salt Electrolysis – Hall-Herault Process

18. Uranium Acid Leaching • Oxidize tetravalent uranium ion (U4+) to hexa-valenturanyl ion (UO22+) using MnO2 or NaClO4 • About 5 kg/t of MnO2 or 1.5 kg/t of NaClO4 • UO22+ reacts with H2SO4 to form a uranyl sulfate complex anion, [UO2(SO4)3]4-.

19. Yellowcake • uranyl hydroxide • uranyl sulfate • sodium para-uranate • uranyl peroxide • various uranium oxides yellowcake typically contains 70% to 90% triuraniumoctoxide (U3O8) and other oxides • uranium dioxide (UO2) and • uranium trioxide (UO3)

20. Leaching Processes • Tank Leaching (Agitation) • Vat Leaching • Pressure Leaching (high temperature/pressure) • Biological Leaching (Bacteria) • Heap Leaching • In-situ Leaching (solution mining)

21. Lixiviants • Lixiviant is a liquid medium used to selectively extract a desired metal from a bulk material. It must achieve rapid and complete leaching. • The metal is recovered from the pregnant (or loaded) solution after leaching. The lixiviant in a solution may be acidic or basic in nature. - H2SO4 - NH4OH - HCl - NH4Cl or NH4CO3 - HNO3 - NaOH/KOH - HCN >> NaCN/KCN

22. Tank versus Vat Leaching • Tank leaching is differentiated from vat leaching as follows: Tank Leaching • Fine grind (almost full liberation) • Pulp flows from one tank to the next Vat Leaching • Coarse material placed in a stationary vessel • No agitation except for fluid movement

23. Tank versus Vat Leaching • Tanks are generally equipped with • agitators, • baffles, • gas nozzles, • Pachuca tanks do not use agitators • Tank equipment maintains solids in suspension and speeds-up leaching • Tank leaching continuous / Vat leaching batch

24. Tank versus Vat Leaching • Some novel vat leach processes are semi-continuous with the lixiviant being pumped through beds of solids in different stages • Retention (or residence) time for vat leaching is much longer than tank leaching to achieve the same recovery level

25. Important Efficiency Factors Retention time = total volume of tanks / slurry volumetric flow - normally measured in hours - gold: 24 to 72 hours - copper: 12 to 36 hours - sequence of tanks called a leach "train" - mineralization &feed grade changes may need higher retention times

26. Important Efficiency Factors Particle Size - material ground to size to expose desired mineral to the leaching agent (“liberation”), tank leach >>> size must be suspendableby an agitation vat leach >>> size must be most economically viable - high recovery achieved as liberation increases or kinetics faster is balanced against increased cost of grinding & processing the material. Pulp density - percent solids determines retention time - determines settling rate and viscosity - viscosity controls gas mass transfer and leaching rate

27. Important Efficiency Factors Pulp density - percent solids determines retention time - determines settling rate and viscosity - viscosity controls gas mass transfer and leaching rate

28. Important Efficiency Factors Numbers of tanks - Tank leach circuits typically designed with 4 tanks Dissolved gases - Gas is injected below the agitator or into the vat bottom to achieve the desired dissolved gas levels - Typically, oxygen or air, or, in some base metal plants, SO2 is used.

29. Important Efficiency Factors Reagents - Adding/maintaining appropriate lixiviant level is critical - Insufficient reagent reduces metal recovery - Excess reagent increases operating costs and may lead to lower recovery due to dissolution of other metals - recycling spent (barren) solution reduces need for fresh reagent, but deleterious compounds may build-up leadingto reduced kinetics

30. Pressure Leaching • Sulfide Leaching more complex than Oxide Leaching • Refractory nature of sulfide ores • Presence of competing metal reactions • Pressurized vessels (autoclaves) are used • For example, metallurgical recovery of zinc: 2ZnS + O2 + 2H2SO4 → 2ZnSO4 + 2H2O + 2S • Reaction proceeds at temperatures above B.P. of water (100 °C) • This creates water vapor under pressure inside the vessel. • Oxygen is injected under pressure • Total pressure in the autoclave over 0.6 MPa.

31. Sulfide Heap Leaching • Ni recovery much more complex than Cu • Requires stages to remove Fe and Mg • Process produces residue and precipitates from recovery plant (iron oxides/Mg-Ca sulfates) • Final product – Ni(OH)2precipitates (NHP) or mixed metal hydroxide precipitates (MHP) that are smelted conventionally

32. Bio-Leaching • Thiobacillus ferrooxidans used to control ratio of ferric to ferrous ions in solution (Tf acts as a catalyst) 4Fe2+(aq) + O2(g) + 4H3O+ → 4Fe3+(aq) + 4H2O • Ferric sulfate used to leach sulfide copper ores • Basic process is acceleration of ARD • Typical plant leach times for refractory gold ore is about 24 hours

33. Bio-Leaching

34. Bio-Leaching at Snow Lake, Manitoba • BacTech to use bio-leaching to deal with As and recover gold from an arsenic-bearing waste dump • Two products • Chemically-stable ferric arsenate precipitate • Gold-rich Residue Concentrate • 110 tpd of concentrate for 10 years • Annual production = 10,400 oz plus some Ag • CAPEX = $21,400,000 OPEX = $973/oz • Gold Recovery after toll-smelting = 88.6%

35. SX - Solvent Extraction • Pregnant (or loaded) leach solution is emulsified with a stripped organic liquid and then separated • Metal is exchanged from pregnant solution to organic • Resulting streams are loaded organic and raffinate(spent solution) • Loaded organic is emulsified with a spent electrolyte and then separated • Metal is exchanged from the organic to the electrolyte • Resulting streams are stripped organic and rich electrolyte

36. Solvent Extraction Mixer/Settler

37. Reason for 4 Stages of SX

38. Solvent Extraction and Heap Leaching

39. Ion Exchange Resins • AMn = synthetic ion-exchange resin (class A - 0.6–1.6 mm) • Phenyl tri-methyl ammonium functional groups • Macro-porous void structure • Similar to strong base anion exchange resins • Zeolite MPF (GB) • Amberlite IRA (USA) • Levatite MP-500 (FRG) • Deion PA (JPN)

40. Resin-In-Pulp Pachuca Tank

41. Resin-In-Pulp Pachuca Tanks

42. Resin-In-Pulp Pachuca Tanks

43. Kinetics of RIP for Uranium

44. Effect of pH on RIP for Uranium

45. RIP Recovery in each stage

46. In-situ Leaching •  In 2011, 45% of world uranium production was by ISL • Over 80% of uranium mining in the USand Kazakhstan • In US, ISL is seen to be most cost effective and environmentally acceptable method of mining • Some ISLsadd H2O2 as oxidant with H2SO4 as lixiviant • US ISL mines use an alkali leach due to presence of significant quantities of gypsum and limestone • Even a few percent of carbonate minerals means that alkali leach must be used although recovery does suffer

47. In-situ Leaching Average grades of sandstone-hosted deposits range between 0.05% to 0.40% U3O8.

48. In-situ Leaching

49. In-situ Leaching

50. In-situ Leaching • Acid consumption varies depending on operating philosophy and geological conditions • In Australia, it is only a fraction of that used in Kazakhstan • In Kazakh , about 40 kg acid per kg U (ranging from 20-80) • Beverley mine in Australia in 2007 used 7.7 kg/kg U.  • Power consumption is about 19 kWh/kg U (16 kWh/kg U3O8) in Australia and around 33 kWh/kg U in Kazakhstan • www.world-nuclear.org/info/Nuclear-Fuel-Cycle/Mining-of-Uranium/In-Situ-Leach-Mining-of-Uranium/#.UUihT1fQhLo