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 Hydrometallurgy in PASAR (Se Recovery)

 Copper Leaching Methods


 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