JAWAHARLAL NEHRU TECHNOLOGICAL UNIVERSITY HYDERABAD

Non Ferrous Extractive Metallurgy

III Year B.Tech.II Sem

MODULE –II
Ms. Sindhu B
Assistant Professor C
Dpmt of Metallurgical
Engineering
JNTUHCEH
COPPER EXTRACTION
UNIT-1
 COPPER:
 Principal Ore and Minerals;
 Matte smelting – Blast furnace, Reverberatory, Electric furnace, Flash;
 Converting;
 Continuous production of blister Copper;
 Fire refining;
 Electrolytic refining;
 Hydro-Metallurgical copper extraction;
 Leaching processes,
 Recovery of copper from leach solutions;
 Electro-winning.
PROCESSING OF COPPER ORES

Mining

Transporting

Primary Crushing Froth Floatation

Heap Leaching

Thickening
Oxide Ore: Sulfide Ore:
Solvent Extraction
Hydrometallurgy Pyrometallurgy
Smelting

Electrowinning
Electrolysis
Final Product:
99.99% pure copper
cathode
The primary crusher reduces the size of the ore from
boulder to golf ball-sized rocks
(For example, Cyprus
Tohono Mine)
 Oxide ores are
generally
processed using
hydrometallurgy
 Mining
considerations:
 Oxide ore is usually
lower- grade
(contains less copper)
 Oxide ore is often
more abundant near
 Uses aqueous (water-based)
solutions to extract and purify
copper from copper oxide ores,
usually in three steps:
 Heap leaching
 Solvent extraction
 Electrowinning
 Uses percolating
chemical solutions
to leach out metals
from the ore
 Commonly used for
low- grade ore
 Process consists of:
 Crushed ore is piled into a heap on a slope
(impenetrable layer)
 Leaching reagent (dilute sulfuric acid) is sprayed
and trickles though heap to dissolve copper
from the ore
 Pregnant leach solution and copper sulfate is
In dump leaching or heap leaching the low grade ore is accumulated in the
form of a heap and dilute acid is passed through it
After percolation the lead solution is either treated with scrap Iron to recover
cement copper or it is subjected to solvent extraction to extract copper
Later subjected to electrowinning
To accelerated the leaching rate Thiobacillus ferroxidants bacteria can be
employed
In the case of an oxidized copper ore leaching is carried out in leaching tanks
employing a spent copper electrowinning electrolyte that contents 100 gram
per liter H2SO4
The resultant leach liquor contains 50 gram per liter copper and it is used for
electrowinning of copper
 Two immiscible (un-mixing) liquids are
stirred and allowed to separate, causing
the copper to move from one liquid to
the other
 Pregnant leach solution is mixed with a
solvent
 Copper moves from the leach solution into
the solvent
 Liquids separate
based on solubility
▪ Copper remains in solvent
 Electrical current passes through an inert
anode (positive electrode) and through
the copper solution from the previous
step, which acts as an electrolyte
 Positively-charged
copper ions (called
cations) come out
of solution and
are plated onto a
cathode (negative
electrode) asElectrowinning, Inspiration Consolidated Copper Co., Globe AZ. By
Keyes, Cornelius M. 1972.
(For example, Mission
Mine)
Extraction of Cu in Pyrometallurgical Process:
 Atomic Number: 29 Atomic Weight: 63.54 amu
 Density: 8.94 gm/cm3
 Melting Point: 10830 C
 Boiling Point: 25950 C

Common Minerals of Cu:

Extraction of Cu from Sulphide Ores:

The steps involved in extraction of Cu by conventional routes as

concentration, roasting, smelting, converting and refining at the left side of
the flow sheet and newer route at the right side of the flow sheet.

(i) Conventional Route:-

Concentration:
A naturally occurring Cu sulphide contains 0.5-2 % of Cu. To recover
this, first we go for crushing and grinding to liberate sulphide grains from
the gangue.
The avg particle size of average ore after grinding is 40 µm sizes.
Pyrometallurgical Extraction of Cu from Sulphide Ores

Then go for froth floatation, where addition of CaO and

Xanthate as collecter(controls pH), where we separate Cu
sulphide from a mixture of Cu Sulphide, Lead Sulphide and
Zinc Sulphide. The Cu Sulphide conc. contains 15-35% Cu,
15-35% Fe, 25-35% S, 3-15% gangue.

Roasting: The purpose of roasting to partially

oxidized the iron sulphide present in Cu Sulphide
which from slag in next i.e. smelting. Here the
concentrate contains high iron sulphide and low Cu
Sulphide content (<25%).
  In conventional plant, roasting carried out in multiple hearth roaster with gradually downward
movement of feed having gradual increase in temperature of each hearth by fuel firing as 5500 C. Where as
in newer route, roasting carried out in fluidized bed roaster at about 5500C. The product is SO2 gas which
finally used for manufacturing for H2SO4 .
 The principal reactions takes place in roasted calcine contains Cu Sulphides of and Fe oxides of Fe

and mixed sulphates of Fe and Cu given as

 Reaction 2.1: 2𝐶𝑢𝐹𝑒𝑆2 + 6.5𝑂2 → 2𝐶𝑢𝑂 + 𝐹𝑒2𝑂3 + 4𝑆𝑂2
 Reaction 2.2: 𝐶𝑢𝐹𝑒𝑆2 + 4𝑂2 → 𝐶𝑢𝑆𝑂4 + 𝐹𝑒𝑆𝑂4
 Reaction 2.3: 2𝐶𝑢𝐹𝑒𝑆2 + 𝑂2 → 𝐶𝑢2𝑆 + 2𝐹𝑒𝑆 + 3𝑆𝑂2
 Reaction 2.4: 2𝐶𝑢𝐹𝑒𝑆2 + 4.5𝑂2 → 2𝐶𝑢2𝑆 + 𝐹𝑒2𝑂3 + 3𝑆𝑂2
 Reaction 2.5: 2𝐶𝑢𝐹𝑒𝑆2 + 7.5𝑂2 → 𝐶𝑢𝑂. 𝐶𝑢𝑆𝑂4 + 2𝐹𝑒𝑆𝑂4 + 𝑆𝑂2
 Reaction 2.6: 3𝐶𝑢𝐹𝑒𝑆2 + 9.5𝑂2 → 3𝐶𝑢𝑂 + 𝐹𝑒3𝑂4 + 6𝑆𝑂2
 Reaction 2.7: 6𝐶𝑢𝐹𝑒𝑆2 + 13𝑂2 → 2𝐶𝑢2𝑆 + 2𝐹𝑒3𝑂4 + 9𝑆𝑂2
 Multiple Hearth Roaster

The roasted calcine is transferred to smelting furnace for the further recovery of copper
Fluidized Bed Roaster
Smelting:
Smelting process separates the metal sulphides in an ore, concentrate
or calcine from the gangue 0by charging the furnace with suitable charge
along with flux at about 1250 C.
During smelting two separate layers are formed, as slag and matte
layer having specific gravity 2.8-3.8 gm/cm3(slag) and 5.0-5.5 gm/cm3
respectively (Matte)
The gangue and iron oxides present in the concentrate/calcine is to be
smelted combine with each other during smelting to form iron silicate slag.
 If iron oxide insufficient the lime is added as flux to form an iron
0
calcium silicate slag. The melting point of slag approximately 11500
C and
for fluid slag with a low Cu content, the temperature at about 1250 C.
Exchange reaction takes place between oxides and sulphides of Cu
and FeS present in furnace charge.
2𝐶𝑢𝑂 + 4𝐹𝑒𝑆 → 2𝐶𝑢2𝑆 + 4𝐹𝑒𝑂 + 𝑆𝑂2
2𝐶𝑢𝑆𝑂4 + 2𝐹𝑒𝑆 → 𝐶𝑢2𝑆 + 2𝐹𝑒𝑂 + 3𝑆𝑂2

𝐶𝑢2𝑂 + 𝐹𝑒𝑆 → 𝐶𝑢2𝑆 + 𝐹𝑒𝑂

  These reactions occur because O2 has a greater affinity for Fe than Cu in Ellingham diagram. The unoxidised iron

sulphide reduces the higher oxides of iron to ferrous oxide as

10𝐹𝑒2𝑂3 + 𝐹𝑒𝑆 → 7𝐹𝑒3𝑂4 + 𝑆𝑂2

3𝐹𝑒3𝑂4 + 𝐹𝑒𝑆 → 10𝐹𝑒𝑂 + 𝑆𝑂2

The resultant ferrous oxide(FeO) and magnetite (Fe3O4)react with flux (silica or lime) to
form a slag

 The object is to produce a matte contains 35-45% Cu, 20-22% S, 25-35% Fe. Smelting not only minimize the
loss of Cu to slag, but also provides a matte with a sufficient quantity of iron sulphide for use in the next stage as
converting.
 Smelting conventional route occur in reverberatory furnace and electric furnace, where in newer route flash

smelting and continuous smelting takes place. The conventional route, electric furnace because a large volume of
combustion gas generation avoided and facilities both recovery of so2 and cleaning of furnace gases.
Reverberatory Furnace
Converting:
The purpose of converting is to remove Fe, S, and other impurities from matte. Generally side blown
converter used.
The capacity of converter is 100-200 tons, 4m diameter and 9 m in length. Lined with a layer of
Chrome-magnesite refractory about 40 cm thick. Oxidizing atmosphere inside the converter by supply of O2
enriched air through the tuyere of 5 c.m. with 40 tuyers in number. The total volume of gas is 600 m3/min.
The product is blister Cu and slag.
So, the Cu converting have 2 stages namely slagging stage and blister formation stage.
 Converter Operation Operating Principles of Side blown
Converter
 (i) Slaging Stage: The iron sulphide present in matte is oxidized and oxide is slaged out by addition of siliceous
flux. The reactions are
2𝐹𝑒𝑆 + 3𝑂2 → 2𝐹𝑒𝑂 + 2𝑆𝑂2
2𝐹𝑒𝑂 + 𝑆𝑖𝑂2 → 2𝐹𝑒𝑂. 𝑆𝑖𝑂2

 Slagging is carried out in 3 stages :

 Adding freshly obtain matte(from furnace) in the converter
 Blowing off air.
 Slag gets skimmed off by tilting the cylindrical converter

The slag contains 2-9% Cu, 40-50% Fe, 20-30% SiO2 , and 1-5% (CaO+MgO).
Conventionally, Cu is recovered from the slag produced in converter by transferring the slag in molten state to a
smelting furnace(Rev/ Arc/Flash), where in case of newer process, metallic values of the slag recovered by employing
either an electric furnace with provision for cleaning the slag or by slow cooling of slag followed by grinding and
floatation.
  (ii) Blister Formation Stage: After slagging is completed, the converter

contains Cu2S known as white metal because of its appearance. In blister Cu

formation stage, Cu2S is oxidized to form Cu by combination of reaction.
2𝐶𝑢2𝑆 + 3𝑂2 → 2𝐶𝑢2𝑂 + 2𝑆𝑂2
𝐶𝑢2𝑆 + 2𝐶𝑢2𝑂 → 6𝐶𝑢 + 𝑆𝑂2
The overall reaction is

3𝐶𝑢2𝑆 + 3𝑂2 → 6𝐶𝑢 + 3𝑆𝑂2

 When white metal (Cu2S) is oxidized the quantity of S
content in bath decrease about 19.5% and hence, the bath
split into two layers as
 Top sulphide layer of less dense.
 Bottom Cu layer of more dense contain about 1.2%
S.
As oxidation continues the volume of sulphide layer
(liquid b) decrease and Cu layer (liquid c) increase. The
relative volume of two phases determined by Lever rule.
The blister Cu contents 0.02-0.05% S along with 0.2-0.5%
dissolved O2 .
Refining:
 The purpose of refining to get Cu extraction is twofold as
 First, to obtain metal in pure form.
 Second, to recover precious metals containing in blister Cu produced.

(i) Fire Refining: The purpose is to remove S from liquid blister Cu as SO2 by
oxidation with air and eliminates O2 by introducing hydrocarbons. In this case, the
refining is done in reverberatory furnace of 400 ton of capacity contains blister Cu
get oxidized to recover Cu removing the impurities such as S, Fe, Se, Zn by
converting its corresponding oxides and then skimmed off. But some Cu also in the
form of oxides.

 To prevent Cu loss poling with green branches used to reduce Cu2O using
hydrocarbon or some other reducing gases. In this case, the purity of Cu obtained
99.97%.
Fire refining is also done in rotary type refining furnace, where blister Cu directly
treated by blowing air.
 (ii)Electrolytic Refining:
The purpose is to further refined the fire-refined Cu by electrolysis. The
electrolysis done in a electrolytic refining tank made of concrete or wood
of 3-5 m deep and utilization minimum space with maximum cathode and
anode area. The electrolyte
0
is CuSO4, H2SO4, some glue and alcohol at
temperature 50-60 C.

Cu transferred from crude anode to pure cathode. Impurities in blister Cu

such as Fe, Co, Ni, Se, Te etc. go into the solution and precious metals get
collected below anode known as anode slime
 (ii) Newer Process for production of Cu
FLASH SMELTING

 Process: Enriched preheated air or pure O2 used to increase combustion rate and autogeneous
smelting. The gases coming out rich of SO2 due to high combustion rate and used for H2 SO4
manufacturing.
 Process is autogeneous provide exothermic heat. Air used as oxidant to preheated. The
composition of concentrate used in flash smelting has Chalcopyrite (CuFeS2) 66%, Pyrite (FeS2) 24%,
gangue (SiO2) 10%. Whereas the Cu matte contains 70% Cu, 8% Fe, 22% S, slag contains Fe 40% at

Main reactions of flash smelting of Cu concentrate are mentioned below 𝐶𝑢𝐹𝑒𝑆2 +

furnacetemperature 13000 C.
0.5𝑂2 → 0.5𝐶𝑢2𝑆 + 𝐹𝑒𝑆 + 0.5𝑆𝑂2

𝐶𝑢𝐹𝑒𝑆4 + 0.5𝑂2 → 2.5𝐶𝑢2𝑆 + 𝐹𝑒𝑆 + 0.5𝑂2

Flash Smelting
𝐶𝑢𝑆 + 0.5𝑂2 → 0.5𝐶𝑢2𝑆 + 0.5𝑆𝑂2

𝐹𝑒𝑆2 + 𝑂2 → 𝐹𝑒𝑆 + 𝑆𝑂2

𝐹𝑒𝑆 + 1.5𝑂2 → 𝐹𝑒𝑂 + 𝑆𝑂2

𝐹𝑒𝑂 + 0.16𝑂2 → 0.33𝐹𝑒3𝑂4

𝐹𝑒𝑂 + 0.5𝑆𝑖𝑂2 → 0.5𝐹𝑒2𝑆𝑖𝑂4

𝐶𝑢2𝑆 + 1.5𝑂2 → 𝐶𝑢2𝑂 + 𝑆𝑂2

Continuous Smelting:
It encompass smelting and converting in a single vessel i.e. Cu concentrate charged at one end and Cu metal withdrawn continuously at the other end.
Mainly three are three processes, given below
 (a) WORCRA. (b) Noranda. (c) Mitsubishi.

WOCRA PROCESS:
This name divided as the first 3 alphabets stands for the developers and last 3 alphabets for the place.
Features:
 Counter current movement of gas and concentrate. So, continuous production of blister Cu.
 Directly blister Cu i.e. metal instead of matte form.
 Combine smelting and converting.
 The heat required for reaction directly obtained as the reaction is exothermic.
 Counter movement cause continuous production of H2 SO4 due to continuous extraction of gas.
 Cu% continuously obtains from slag by means of cleaning operation.
Process:
 The process combines 3 different operations in a single furnace as
 Continuously smelting
 Continuously converting
 Continuously slag cleaning by conditioning and settling
Efficiency:
It increases by means of counter current movement increase the reaction surface area in the smelting and converting zone. Hence, effective removal of impurity
occur i.e. mainly Fe due to counter movement of slag and matte. As a result, Cu gets reverted back to matte and obtain.
Advantage:
 Continuous process
 Capital cost low
 Concentrate passes large surface area. Hence accelerate the reaction.
 Disadvantage:
 Not durable
 Operating cost is high

Vertical Sectional Diagram of Straight form of

WORCRA reactor
 NORANDA PROCESS:
Principle: In this process, high grade Cu matte directly forms from the sulphide by means of air blown
through the tuyeres to oxidize. The Cu or matte collected at the tap hole where the
slag collected at the other tap hole at the slag end.

In this process, the slag contains high% Cu compare to WORCRA process. Mainly 3 layers present
in the product as
 Cu – First layer.
 Matte – Second layer.
 Slag – Third layer.
Condition:
 If given air is more than the stoichiometric amount of air required for oxidation, then matte level
decreases and Cu level increases.
 If insufficient air required for stoichiometric amount then unoxidised iron and S tends to
combine with Cu to form matte. So matte level increases and Cu level decreases.
 If air supply is equal to the stoichiometric amount then both matte and Cu level get increases.

Schematic diagram of Noranda Process

Mitsubishi Process:
Principle: There are three furnaces such as smelting, slag cleaning
and converting furnace are connected in a cascade manner. The
product of one furnace goes to next furnace for next operation by
means of gravity force.
Process:
First, in smelting furnace (wet concentrate + flux + air + O2 )
is smelted to produced matte of 60-65% Cu and rest is slag.
Secondly, both matte and slag goes into slag cleaning
furnace where slag get discarded and matte goes to next furnace
operation.
Thirdly, in converting furnace matte oxidized to blister Cu by
blow of O2 enriched air and limestone add as slag. So slag discarded
as lime ferrite. Blister Cu produced of low % S and hence, obstruct
the transfer of Cu to lime ferrite slag.
Mitsubishi Continuous Smelting Process
GATE NOTES
Froth Floatation
This method is used for the concentration of sulphide ores. This method is based on the
preferential wetting of ore particles by oil and that of gangue by water .. As a result. the ore
particles become light and rise to the top in the form of froth while the gangue particles
become heavy and settle down. Thus. adsorption is involved in this method.
The froth can be stabilised by the addition of stabilisers (aniline or cresols).
Activator They activate the floating property of one of the component of the ore I and help in
the separation of different minerals present in the same ore (CuSO4 is used as activator.

Depressants These are used to prevent certain types of particles from forming the froth with
air bubbled, e.g., NaCN can be used as a depressant in the separation of ZnS and PbS ores.
KCN is an another depressant.
Collectors It increases the non-wettability of ore particles by water, e.g., pine oils, xanthates
and fatty acids.
Copper Applications:

 Electrical Industry (due to high electrical conductivity) – manufacture of generators, motors, switchboards,
communication equipment, wires for transmission of sound and electricity
 Chemical Industry (due to resistant to corrosion and high thermal conductivity) – chemical plants, copper
tanks and utensils for food industries, milk processing and refining industries good quality copper is used for
manufacture of copper compounds like copper sulphate, copper cyanide, copper oxide etc. Copper powder has
been used extensively in powder metallurgy
 • Alloys of Copper – Forms very useful alloys with metallic zinc and metallic tin, which is go under the
common names of Brasses and Bronzes respectively