Sources of Nickel

Sulphide ores: Pentlandite [(Ni, Fe)9S8 ]

Accompanied by :Pt, Os, Ir, Rh, Ru & Pa.
0.3-5.5 %Ni, 0.6-2.5% Cu & upto 0.2% Co.
With high Cu content, Termed as Cu-Ni.
Gangue consists of pyrrohotitte, magnetite &
silicates of Fe, Al & Mg.

Magnetic separation, collective flotation to reject

rock & float concentrate containing Ni & Cu.
Differential floatation to produce Ni & Cu
concentrate.
Differential floatation is omitted as subsequent
treatment to separate two metals.

Sources of Nickel (contd.)

Silicate (oxide) ores: Garnierite, complex
hydrated Ni-Mg silicate, Ni & Mg contents
vary (nNiSO3.m Mg SiO3.H2O).
Cu occurs in oxide ores.
Co occurs in oxide form with Mn minerals.
(Ni is 0.9-1.5 % and Co is upto 0.15%)

Controlled Slow Cooling

Matte (980C) transported to cooling trays.
Fire clay moulds 12 x 8 x 2 ft with 45 angled
(25 tons).
Covered with an insulated steel cover & left
for three days.
Matte cools below 480C.
Cover is removed & cooled for fourth day in
air (204C).
Matte removed.
Slow cooling permits phase separation &
promotes larger grain growth.

Controlled Slow Cooling (Contd.)

Down to 927C, Ni, Cu & S are completely

miscible.
Cools to 921C, Cu2S crystals begin to form.
Temperature drops still further, more Cu2S
crystallizes, leaving a liquid phase richer in Ni
as Cu is removed from it.
More Cu precipitates, more Cu2S grains get
enlarged.

Controlled Slow Cooling (Contd.)

700C, a Ni-Cu alloy begins to precipitate.
At 630C,Ni3S2 begins to solidify.
At the solidification temperature, solubility of Ni
in solid Cu2S is < 0.5% & solubility of Cu in
solid Ni3S2 (designated as Ni3S2) is 6%.
At 520C, Ni3S2 undergoes a structural
transformation to Ni3S2.
Cu2S & Ni-Cu alloy are much less soluble in
Ni3S2 than in Ni3S2.

Controlled Slow Cooling (Contd.)

At 370C, 0.5% Cu2S still remains in Ni3S2 phase.
Metallic Ni-Cu alloy formed amounts to 10% of
ingot & contains Au & Pt metals, 20% available
Cu in matte.
Ag, Se & Te concentrate in Cu2S.
At 204C ingot is broken & crushed.
Three phases tend to fracture along their grain
boundaries.
Separation of the three phases are accomplished

Controlled Slow Cooling (Contd.)

Cu2S phase anayses 73% Cu & 5%Ni.
Ni3S2 concentrate analyses 73% Ni & 0.6%Cu.
Cast into anodes for direct electro-winning/ fire
refined by an oxidising roast to convert Ni3S2 to
oxide, a reduction to convert oxide to metal.
Reduction is by hydrogen in fluid bed reactor/
reducing gas mixture of H2 & CO in a hearth roaster.

Hydrogen Reduction
Dead roast Ni3S2 concentrate to oxide in FB reactors
(1093C).
2Ni3S2 + 7O2 6NiO + 4SO2
S to 0.2% after a long retention time of up to 8
hrs. in the roaster.
Calcine given another stage of FB roasting to S to
0.01% by using O2 enriched air for fluidizing.
Resulting NiO is reduced with H2 in another FB
reactor to give a product < 0.005%S.

Hydrogen-Carbon Monoxide Reduction

Roasted NiO is reduced to metal with
hydrogen-rich CO gas in MH roaster
H + Ni O = Ni + H2O
Reducing gas, 51% H2 & 40% CO by passing
steam over hot coke & coal.
Reduction temperature of 427C is
maintained.

Electro refining
Impure metal is tapped from the furnace & cast into
moulds.
Anodes are 38 x 24 x 2 in, weigh 264kg.
Cu, Fe, Co & As in to solution anolyte.
Deposition of impurities are prevented by having
cell divided by pure Ni cathodes being suspended
inside boxes of porous cotton duck on wood frames.
Cathodes: purity of 99.93%.
C.D. :16amp/sq.ft.; C. E. : 95%;
Operating voltage:2.5 V; Temp. : 57C.

Electro-winning of Ni Matte Anodes (contd.)

Converter matte analyzing 75%Ni & 20%S cast in to
molds.
Slow cooling with the anodes held at 510C for
12hrs., Completes the phase transformation from
Ni3S2 to Ni3S2.
Anodes cooled to 204C over another 24hrs. & left
in air to cool down to ambient temperature.
Cell temperatures are high at 63C due to increased
cell voltage to 4V.

Electro-winning of Ni Matte Anodes

Cathodes are pure Ni sheets & anodes enclosed in
woven bags treated with neoprene after weaving.
Anode potential: 1.2 V cf. 0.2 V metal anodes.
Ni3S2 = Ni + 2S
Elemental S with precious metals & Se collects in
dynel bag surrounding anode.
Co, Cu, Fe & As dissolves in anolyte along with Ni.

Electro-winning of Ni Matte Anodes (contd.)

Cathodes (99.95%Ni) weighing 64 kg are removed
after 10 days.
Washed solids are melted (135C) to melt 97%
elemental S, filtered off leaving undissolved
sulphides & precious metals.
Current efficiency : 99.5%; C.D.: 20 asf cf. 16asf

Nickel Carbonyl Process

Monds Process.
Impure Ni metal is contacted with CO 38C-93C.
Metal reacts with gas to form volatile nickel
carbonyl, carried out of reaction chamber in the gas
stream:
Ni + CO = Ni (CO)4
Reaction is reversible, if the gas is passed through
Ni shots heated to 150-316C, carbonyl decompose
in to metallic Ni, deposits on the shots causing it to
grow.
Ni (CO)4 = Ni + CO

Nickel Carbonyl Process (contd.)

Low temperature & atmospheric pressure
used in the process take only Ni in to volatile
carbonyl phase.
Operation is highly selective & produces pure
product 99.95%Ni.