Extraction of Base Metals

(Copper, Nickel and Cobalt)

S. K. Sahu
Metal Extraction & Forming Division
National Metallurgical Laboratory, Jamshedpur
 Introduc
Copper – the most extensively used metal
32%
tion next only to steel & aluminium
35%

Its chemical, physical & aesthetic properties

3%
make it suitable for wide range of domestic,
8% 10% 7% 5%
Electrical (35%) Telecommunications (5%) industrial & technological applications
Power Transmission (7%) Automobile industry (10%)
Building construction (8%) Railway equipment (3%) Global demand for Cu – 18 million tons
Miscellaneous (32%) (Primary production - 88% & secondary
Copper Consumption production - 12%)
Cu demand is growing by an avg. of 4% per
year

Indian demand for Cu – 4.5 lakh tons i.e. ~ 3% of world copper market
Birla Copper, Sterlite Copper & Hindustan Copper Ltd. – three major
Cu producers in India
Indian production of refined copper : 6.5 lakh tons
India is emerging as a net exporter of refined copper
Over 90% of concentrate requirement is imported
 Nick
6% 10%
Cob 22%

el alt
9% 7%
8%

20% 65%
9% 22%
11%
11%
Stainless steel (65%) Batteries (22%) Superalloys (22%)
Other steel and non-ferrous alloys & suoper alloys (20%) Catalys ts (11%) Hardmetals (11%)
Electroplating (9%) Pigments (9%) Tyre adhesives/driers (8%)
Coins & nickel chemicals (6%) magnets (7%) others (10%)
Nickel Consum ption Coba lt C on su m p tion

Nickel is the most volatile owing to its

strong demand and tight supply
Global demand for nickel – 1.3 million
tons & consumption rate increasing @
3% a year
About 65% Ni is used in manufacture
of stainless steel
Due to lack of Ni reserves nickel
market in India is import dependent
India imports ~30,000 tons of nickel
Cobalt is least abundant element
compared to Cu & Ni
In terms of application, Co is
regarded as a specialty metal
Global demand for Co – 60,000 tons
It lacks any primary cobalt resources
India consumes ~ 700 tons Co for
application in the metallurgical &
chemical sector
World Copper Usage, 1900-2006 Copper Ore Grades mined in USA
Thousand metric tonnes
Year Ore Grade
Source: ICSG
(Mean Cu %)
1932 1.80

1939 1.23
1949 0.90

1960 0.73

1970 0.61

2000 0.48

Demand for refined copper increasing by an average of 4% per year

Due to continuous mining and processing, mineral grades of promary
resources are declining
However, newer & energy efficient processes are being developed to
recover metal from low grade ores & secondaries to meet the
requirement of the society
 Extraction of
Copper
Copper exists in nature mostly in the form of copper sulfide
Oxides or oxidised ores are found only in limited quantities
Some common minerals of copper are: Chalcopyrite (CuFeS2);
Covelite (CuS); Chalcocite (Cu2S), Cuprite (Cu2O); etc.
Chalcopyrite is most abundant copper bearing mineral (70%
of world Cu reserves)
Sulfide ore containing 0.5-2.0% Cu is considered satisfactory
for Cu extraction by pyrometallurgy
From poor grade ores, Cu extracted by hydrometallurgical
processes
Conventional Process for extraction of
Copper from sulfide concentrate

Possible to roast sulfide ore of copper

to oxide & then reduce it by carbon in
the blast furnace
Concentrate also contains iron sulfide
which form iron oxide
Cu2S does not oxidise until FeS is fully
oxidised yielding Fe2O3
Fe2O3 is difficult to remove by
slagging

Therefore, blast furnace smelting is not used for copper extraction

Cu extracted by matte smelting process without using any
reductant
 Ore (1-2% Cu)

Grinding

Flotation

Concentrate (15-35% Cu)

Conventional route Newer routes

Hearth/fluid
bed roasting Drying

Discard slag Reverberatory/ele

ctric furnace Flash smelting
(0.3-0.8% Cu) smelting
Continuous
Matte smelting
Matte (35-60% Cu)

Converting Slag Converting Slag for

cleaning &
discard
Blister copper (98.5%
Cu)
Anode slime for recovery
of precious metals Refining Bleed electrolyte

Cathode copper (99.99%

Cu)
Roast
ing Iron sulfide is partly converted to FeO for
subsequent removal by slagging

2CuFeS2 (s) + O 2 (g) → Cu 2S(s) + 2FeS(s) + SO 2 (g)

FeS + 3 2 O 2 (g) → FeO(s) + SO 2 (g)

Smel
tin
g

FeO removed by slagging with silica (SiO2)

at 1200-1300 OC in reverberatory furnace
Cu2S melt collected as matte
Converti
ng

FeS(l) + 3 2 O 2 (g) → FeO(l) + SO 2 (g) ΔH01200 = -5.1 x 105 kJ/kg mol

Cu 2 S(l) + 3 2 O 2 → Cu 2 O(l) + SO 2 (g) ΔG01200 = -2.3 x 105

Cu 2 S(l) + 2Cu 2 O(l) → 6Cu(l) + SO 2 (g) ΔG01200 = -0.5 x 105

Cu 2S(l) + O 2 (g) → 2Cu(l) + SO 2 (g) ΔG01200 = -0.2 x 105

ΔH01200 = -2.2 x 105 kJ/kg mol

FeO separated as slag

No external heat supply required – the reactions are exothermic
No reducing agent required for removal of oxygen from the
oxide
 Flash
smelting
Conventional smelting operation is a melting
Concentrate
process rather than oxidation process
Its offgas – dilute in SO2 & difficult to Flux Drying Air/O2
remove
Energy intensive process because heat not Flash smelting
generated during smelting
Matte

Slag for
Converting
cleaning &
discard
Blister copper

Refining
Controlled oxidation of Fe & S – offgas strong Copper cathode
enough in SO2 for efficient recovery as H2SO4
Evolution of large amount of heat – making the
process autogenous and energy efficient
 Outokumpu
process

Dry particulate feed and pre heated oxygen enriched air blown through the
concentrate burners down into the furnace
Produce matte containing 45-65% Cu under autogenous condition
depending on the quantity of fuel used & degree of oxygen enrichment
employed
A closed process – captures upto 99% sulfur rich gases to produce H2SO4
 INCO
process
Uses commercial oxygen (95-98% O2),
rather than oxygen enriched air
Oxygen blast & prticulate feed blown
horizontally into the furnace
No external fuel is used – all of the
energy comes from oxidation of Fe & S
The matte produced contains 45% Cu
Slag contains 05-06% Cu – discarded
Offgas containing 70-80% SO2 captured
to produce H2SO4
 Continuous
smelting
Copper concentrate

Slag for
Continuous
smelting cleaning & Combines
discard
smelting & converting
in a single furnace
Blister copper

Refining

Copper cathode
 WORCRA
process
Combines smelting, converting & slag
cleaning operations in separate but
interconnected zones
Directly produces metal, rather than
matte from a concentrate Concentrate
Oil or SiO2 Acid
coal Flux plant
In the converting zone,
countermovement of slag & matte takes Gas
place, that leads to effective removal of cleaner
impurities from the matte Heat exchanger

Conserves energy by utilizing heat

Air
evolved during smelting and converting in
the reactor itself
WORCRA Furnace
The Cu content of the slag is very low &
can be discarded
Slag
Blowers Copper
 Mitsubishi
process
 Smelting furnace, slag cleaning furnace
& converting furnace - connected in
cascade fashion
 Concentrate & oxygen enriched air
enter S-furnace through lances to
produce matte and low Cu slag
 In the C-furnace matte gets oxidised to
blister copper

Main features
All of the furnaces are stationary, driving mechanisms viz. furnace
tilting, tuyere punching, hood driving etc. are not required
Molten products are transferred from one furnace to the next furnace
under gravity
Molten products overflow continuously through the outlet hole of the
furnace eliminating need for tapping and slag skimmig operations
 IsaSmelt/Ausmelt
process
A high intensity smelting process producing matte from Cu-
concentrate & secondary materials
Uses an extremely efficient top-submerged lance & a simple
stationary refractory-lined furnace
Air, oxygen & fuel are fed through the lance into the molten
bath, creating a high turbulant environment that promotes
rapid reaction of raw materials
Depending upon the grade of raw materials, matte
containing upto 75% Cu can be produced

Advantages
Low capital cost due to simple furnace construction &
peripheral system arrangements
Flexibility to use various fuel types (coal, oil, gas)
Ability to produce high grade product from low grade
materials
Small furnace foot-print
 Energy
consumptio
The table compares the energy requirements for seven smelter types,
including the energy equivalents of the materials consumed by each
process. n
Energy requirements vary for the different pyrometallurgical
processes.
Flash furnaces make the most efficient use of the thermal energy
released during the oxidation of sulfides; they generate sufficient
heat to provide a large proportion of the thermal energy for heating
and melting the furnace charge.
Electric furnaces use electrical energy efficiently because of the low
heat loss through the effluent gas, they make limited use of the heat
produced during oxidation of the sulfide minerals, and their energy
costs are high because of the high price of electricity.
 Hydrometallurgical
extraction of Cu
Environmental aspects
Exploitation of complex Hydrometallurgical
& low grade ores extraction of Cu
Small isolated deposits

Simplified flow-chart
Leach-SX-EW Process
Ore or
mine waste Cu loaded
organic

Cu loaded Stripped Aq. solution

leach liquor organic of Cu Cu
Leaching Extraction Stripping EW cathode

Spent electrolyte
Solid waste

Acid
make up
Chalcopyrite is a very stable mineral, therefore it very
hard to leach Cu from chalcopyrite concentrate
However, under oxidising condition Cu can be leached
from chalcopyrite concentrate

Ferric chloride
2 leaching
CuFeS + 4FeCl → CuCl + 5FeCl + 2S
3 2 2
Produces elemental sulfur as a
by-product – eliminates setting
CuFeS2 + 3CuCl2 → 4CuCl + FeCl2 + 2S up of sulfuric acid plant

Electrolysi
s Half Cu is deposited cathodically
Cu+ + e → Cuo at cathode

Rest half Cu is oxidised to Cu2+ at anode

Cu+ - e → Cu2+ at anode

 Pressure sulfuric acid
leaching
Sulfide concentrates can be leached in
the acidic system under oxygen pressure
Sulphide concentrate

Pressure Acid
CuFeS2 + 2H2SO4 → CuSO4 + FeSO4 + 2S + 2H2O Leach

Iron ppt
Solution purification

FeSO4 +1/2H2SO4 + 1/4O2 →1/2Fe2(SO4)3 + 1/2H2O LIX 84 Leach liquor

1/2Fe2(SO4)3 + 3H2O → Fe(OH)3 + 3H2SO4 Cu Extraction

Cu Stripping CYANEX 272

Co Extraction
Cu Solution
Co Solution Ni Solution

CuSO4/Cu
CoSO4/Co NiSO4/Ni
 Extraction of
nickel & cobalt
The principal ore of nickel is pentlandite [(NiFe)9S8]
Cobalt does not have any primary ore
Cobalt is extracted as a by-product of Cu, Ni, Zn or
precious metals
 Process flow sheet for
extraction
Ore
of nickel
(1.3% Cu, 1.2% Ni)

Tailings
Grinding
(0.1% Cu,
Flotation Roasting Flux
0.2% Ni)

Bulk Cu-Ni Reverberatory

Concentrate furnace smelting
(6% Ni, 7% Cu)
Cu concentrate Pyrrhotite Matte (20% Ni, 7% Cu)
(30% Cu, 1% Ni) Copper cliff mill concentrate Slag
(0.9% Ni) Slag
Converting
Ni concentrate discard
(10% Ni, 2% Cu)
Matte (50% Ni, 25% Cu, 20%
S)

1
 1

Slow cooling Grinding Metallics to

Cu concentrate (70
Magnetic separation precious metals
% Cu, 5% Ni)
Flotation recovery (64% Ni,
16% Cu, 10% S)
Low Cu (0.8%) High Cu (3-4%)
Nickel sulfide Nickel sulfide

Fluid bed Fluid bed

roasting roasting

Nickel oxide Nickel oxide

(low copper) (high copper)

Reduction
Reduction Reduction smelting
Metallic nickel
(95% Ni) Carbonylation Electrolysis

Nickel pellets Nickel powder Electronickel

(99.95%) (99.93%) (99.93%)
Extraction of nickel & cobalt
from lateritic ore
Laterites are weathered, metal rich rocks (oxides) either in the form
of limonite or serpentine
Limonites are mainly iron oxide containing Ni & Co & minor
amount of magnesium silicate
Serpentine comprise nickel ferrous hydrated magnesium silicate
From such lateritic ores Ni & Co are extracted either by high-
pressure acid leaching or by ammonia leaching (Caron process)
Serpentines are not treated by high pressure acid leaching because
high magnesium content results in excessive acid consumption
 LIMONITE SERPENTINE
H2SO4

Pressure acid leaching CO Reduction CO2

NH3+(NH4)2CO3

Filtration Residue to waste Cooling

Air

Neutralisation Leaching

NH4HS
Residue to waste
Filtration Filtration & NH3 recovery
H2S

Precipitation Precipitation

Filtration Filtration CoS + NiS

CoS + NiS
Acid to waste Acid to waste
 Process for recovery of Ni & Co from scrap

H2SO4

India does not have any primary

resource for Ni & Co
Indian refiners depend on imported
feed materials
Type of materials imported to India
for recovery of Co & Ni are sludges,
scrap, metallic grinding dust, slags,
etc.
Process for recovery of Ni & Co from sludge
Process for recovery of Ni & Co from slag