Gold Extraction (Cyanidation and Amalgamation) Chromium Hydrometallurgy Nickel and Cobalt Hydrometallurgy Aluminum Hydrometallurgy Copper Hydrometallurgy Zinc Hydrometallurgy Cadmium Hydrometallurgy Uranium Hydrometallurgy Titanium Zirconium Mercury Antimony Tin Indium Gallium Beryllium Vanadium Tungsten Niobium Tantalum Leaching followed by cementation or electrowinning Ores (carbonates, oxides, sulfates, roasted sulfides(=sulfate) Temperature must be controlled at 670OC If T is high, copper oxide will be formed If T is low, then soluble iron sulfate will be formed In-Situ – bacterial leaching, thiobacillus ferooxidans Percolation Leaching Agitation Leaching (3 hours) LIX (or KELEX) dissolved in carrier(=kerosene) Pregnant organic solution is stripped by sulfuric acid Cementation with scrap iron then cemented Cu (80%) is sent to pyro to slag off Fe Electrowinning (more practiced than cementation) Done at 950OC where S is lowered below 2%. Fe tends to form zinc ferrite which is difficult to dissolve by sulfuric acid Done in Pachuka tanks or Dorr tanks Ways: double leaching, single leaching, reverse leaching and continuous leaching More metals are more noble than Zn, more noble metals must be eliminated prior to electrodeposition of Zn. Remove Fe, As, Sb, Ge, Cu, Cd, Co, Ni Purified zinc sulfate is electrolysed with anode=Pb and cathode=Al. Cathode Zn is stripped off from Al plate. Cadmium is byproduct of the purification of zinc sulfate electrolyte Leaching of used dusts with sulfuric acid. Pregnant solution contains cadmium sulfate Removal of Cu with Zn dusts Removal of Cd with Zn dusts Fractional distillation Electrowinning
Cd-plated steel is better than galvanized steel
Major sources of Au and Ag – anode slimes from Cu and Pb electrolysis; Parkes Process (addition of Zn to Pb bullion to recover Au and Ag) Grinding in NaCN solution to -200 mesh Dissolution reaction (Elsner’s equation) – aeration is essential by oxygen, alkaline solution is needed to prevent dissolution of NaCN, add CaO. CCD (slime washing) Impurities (S, As, Sb consume NaCN, these elements are called cyanicides), add Pb- acetate Merrill-Crowe Process – the removal of dissolved oxygen by spraying solution from the top of a high tower (otherwise the precipitation of Au by Zn will be incomplete) Precipitation (cementation) of Au with Zn dusts, Pb-acetate promoted Au deposition Slag off impurities from cement gold by use of soda ash and silica. Obsolete, recovery is from 50-70% only Slurry flows through a slanted Ag-plated copper plate w/ thin Hg layer. Au and Ag are picked up by Hg layer. Later, scrape the amalgam by rubber brush. Squeeze amalgam in deer skin to eliminate free Hg. Heat amalgam in retort at 360OC to evaporate Hg from amalgam. Product is sponge Au (50-90% Au). Sponge Au contains impurities such as Ag and Cu to be further refined. Parting with sulfuric acid (totally obsolete) Moebius Process – electrolysis of Ag-Au alloy in nitric acid solution. All the Au ends in anode slime. Anode slime is melted and cast for Wohlwill process. Cathode Ag = 99.98% Wohlwill Process – electrolysis of crude Au in HCl solution. DC+AC used to prevent anodic passivation. Byproducts are platinum and iridium. 99.999% Au Miller Process – substitute for Wohlwill process. 99.95%Au Sulfidic ores(=concentrates) , Sherritt- Gordon Process Concentrate = 10% Ni, 0.5% Co, 2%, 38% Fe, 31% Si Conc is leached by pressurized ammonia gas in autoclave (7 atm, 80OC). Ni becomes soluble and then precipitated by pressurized hydrogen gas (28 atm, 180OC) Byproducts are ammonium sulfate, Co, Cu Oxidic ores=no beneficiation possible Ores (1.3%) are reduced by producer gas (CO) to metallic Ni in the ore. Leach Remove ammonia from leach soln by steam Precipitation of nickel carbonate Calcining at 9000C to nickel oxide NiO is saleable and can be used for Ni- electroplating Primary Production Process - refining Al from grinding and extracting from bauxite ore = Bayer process - using reduction processes for crystalline alumina = Hall-Heroult Process Secondary Production Process - pre-treatment of scraps such as cleaning and sorting - smelting, refining or alloying of auminum Refining bauxite (boehimite, gibbsite and diaspore) Red mud – slurry contaning sodium aluminate and mixed metal oxides removed in clarifiers, chemicals are recovered after washing. Seed – aluminatrihydrate to crystallize hydrated alumina Reduction of alumina to aluminum By electrolysis Alumina is dissolved in molten cryolite (sodium aluminum fluoride) to reduce melting pt and thus energy for Al production Molten Al is produced and deposited at bottom of electrolytic cell and siphoned to reverb furnace. Alloyed, fluxed and degassed to remove impurities. Al is casted U-235 is only 0.72% natural U, balance belongs to U-238 and U-230 +neutron Ores = 0.1–0.3%, Uranite, pitch blende Extraction stages = milling and refining Milling = from ore to yellow cake (80% uranite) Refining = up to reactor grade, elimination of impurities from yellow cake. Allowable limits for the elements having a larger cross section for thermal neutron are lower (cadmium, boron, indium etc.) Acid leach U6+easy to leach U4+ must be oxidized to U6+ Autoclave leaching at 14000C and 1.1 atm for sulfidic ores Alkali leach Ore grinding with 4% soda ash. Spigot containing 55% solids. Autoclave leaching at 110OC and 1.5 atm Separation of yellow cake from pregnant soln, leach soln contain anions Ion exchange then precipitation Solvent extraction then precipitation Yellow cake produced by IX and SX can be purified by: Dissolution of yellow cake in nitric acid followed by SX Calcination at 5000C From UO3 to UO2 at 7000C Hydrogen or ammonia gas can be used. UO2 is converted by HF to UO4 Derby process – (6000C), add Mg Fused salt electrolysis Uses SX Used DTPA, HEDTA or EDTA May also use IX but it is expensive due to use of chelating agents. Also purifying effect decreases with increasing purity. Fused salt electrolysis follows Purification by distillation, zone melting, melt extraction and filtration, degassing in a high vacuum Titanium Zirconium Mercury Antimony Tin Indium Gallium Beryllium Vanadium Tungsten Niobium Tantalum