CHAPTER-2

EXTRACTION OF NON-FERROUS METALS

2.1 Extraction of Cu in Pyrometallurgical Process:

2.1.1 Details about of Cu:

Atomic Number: 29

Atomic Weight: 63.54 amu

Density: 8.94 gm/cm3

Melting Point: 10830 C

Boiling Point: 25950 C

2.1.2 Common Minerals of Cu:

Copper Oxides Copper Sulphides

Name Chemical Formula Name Chemical Formula

Cuprite Cu 2 O Chalcosite Cu 2 S

Chrysocolla CuSiO 3 .2H 2 O Chalcopyrite CuFeS 2

Malachite CuCO 3 .Cu(OH) 2 Bornite Cu 5 FeS 4

Azurite 2CuCO 3 .Cu(OH) 2 Covellite CuS

2.1.3 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 drawn in fig 1.1
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 of average
40 µm sizes.

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Chapter 2 Extraction of Non-Ferrous Metals

Then go for froth floatation, where addition of CaO as PH controls and Xanthate as collecter,
where we separate Cu sulphide from a mixture of Cu Sulphide, Lead Sulphide and Zinc
Sulphide. The Cu Sulphide contains 15-35% Cu, 15-35% Fe, 25-35% S, 3-15% gangue.

Fig. 2.1: Pyrometallurgical Extraction of Cu from Sulphide Ores

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%).

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Chapter 2 Extraction of Non-Ferrous Metals

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 SO 2 gas which finally used for manufacturing for H 2 SO 4 .
The principal reactions takes place in roasted calcine contains Cu Sulphide and Fe
oxides of Fe and mixed sulphates of Fe and Cu given as
Reaction 2.1: 2𝐶𝑢𝐹𝑒𝑆2 + 6.5𝑂2 → 2𝐶𝑢𝑂 + 𝐹𝑒2 𝑂3 + 4𝑆𝑂2
Reaction 2.2: 𝐶𝑢𝐹𝑒𝑆2 + 4𝑂2 → 𝐶𝑢𝑆𝑂4 + 𝐹𝑒𝑆𝑂4
Reaction 2.3: 2𝐶𝑢𝐹𝑒𝑆2 + 𝑂2 → 𝐶𝑢2 𝑆 + 2𝐹𝑒𝑆 + 3𝑆𝑂2
Reaction 2.4: 2𝐶𝑢𝐹𝑒𝑆2 + 4.5𝑂2 → 2𝐶𝑢2 𝑆 + 𝐹𝑒2 𝑂3 + 3𝑆𝑂2
Reaction 2.5: 2𝐶𝑢𝐹𝑒𝑆2 + 7.5𝑂2 → 𝐶𝑢𝑂. 𝐶𝑢𝑆𝑂4 + 2𝐹𝑒𝑆𝑂4 + 𝑆𝑂2
Reaction 2.6: 3𝐶𝑢𝐹𝑒𝑆2 + 9.5𝑂2 → 3𝐶𝑢𝑂 + 𝐹𝑒3 𝑂4 + 6𝑆𝑂2
Reaction 2.7: 6𝐶𝑢𝐹𝑒𝑆2 + 13𝑂2 → 2𝐶𝑢2 𝑆 + 2𝐹𝑒3 𝑂4 + 9𝑆𝑂2

Fig. 2.2: Multiple Hearth Roaster

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Chapter 2 Extraction of Non-Ferrous Metals

Fig. 2.3: Fluidized Bed Roaster

Smelting:
It seeks to separate the metal sulphides in an ore concentrate or calcine from the
gangue by charging the furnace with suitable charge along with flux at about 12500C. During
smelting two separate layers are formed, as slag and matte layer having specific gravity 2.8-
3.8 gm/cm3 and 5.0-5.5 gm/cm3 respectively. If gangue and iron oxides present in the
concentrate/calcine to be smelted combine during smelting to form iron silicate slag. If iron
oxide insufficient the lime add as flux to form an iron calcium silicate slag. The melting point
of slag approximately 11500C and for fluid slag with a low Cu content, the temperature at
about 12500C.
Exchange reaction takes place between oxides and sulphides of Cu and FeS present in
furnace charge.
Reaction 2.8: 2𝐶𝑢𝑂 + 4𝐹𝑒𝑆 → 2𝐶𝑢2 𝑆 + 4𝐹𝑒𝑂 + 𝑆𝑂2
Reaction 2.9: 2𝐶𝑢𝑆𝑂4 + 2𝐹𝑒𝑆 → 𝐶𝑢2 𝑆 + 2𝐹𝑒𝑂 + 3𝑆𝑂2
Reaction 2.10: 𝐶𝑢2 𝑂 + 𝐹𝑒𝑆 → 𝐶𝑢2 𝑆 + 𝐹𝑒𝑂

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Chapter 2 Extraction of Non-Ferrous Metals

These reactions occur because O 2 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

Reaction 2.11: 10𝐹𝑒2 𝑂3 + 𝐹𝑒𝑆 → 7𝐹𝑒3 𝑂4 + 𝑆𝑂2

Reaction 2.12: 3𝐹𝑒3 𝑂4 + 𝐹𝑒𝑆 → 10𝐹𝑒𝑂 + 𝑆𝑂2
Smelting determine the extent of oxidation of FeS in charge to slag 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 so 2 and cleaning of furnace gases.
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 O 2 enriched air through the tuyere of 5 c.m. with 40 in number. The
total volume of gas is 600 m3/min. The product is blister Cu and slag. So, the Cu converting
namely slaging stage and blister formation stage.
(i) Slaging Stage: The iron sulphide present in matte is oxidized and oxide is slaged
out by addition of siliceous flux. The reactions are
Reaction 2.13: 2𝐹𝑒𝑆 + 3𝑂2 → 2𝐹𝑒𝑂 + 2𝑆𝑂2
Reaction 2.14: 2𝐹𝑒𝑂 + 𝑆𝑖𝑂2 → 2𝐹𝑒𝑂. 𝑆𝑖𝑂2
Mainly three process are done as
• Adding freshly obtain matte.
• Blowing of air.
• Slag gets skimmed off by tilting.

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Chapter 2 Extraction of Non-Ferrous Metals

The slag contains 2-9% Cu, 40-50% Fe, 20-30% SiO 2 , and 1-5% (CaO+MgO).
Conventionally, Cu is recovered from the slag produce in converter by transferring the slag in
molten state to a smelting furnace, 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.

Fig. 2.4: Converter Operation

(ii) Blister Formation Stage: After slagging converter contains Cu 2 S known as white
metal because of its appearance. In blister Cu formation stage, Cu 2 S is oxidized to form Cu
by combination of reaction.
Reaction 2.15: 2𝐶𝑢2 𝑆 + 3𝑂2 → 2𝐶𝑢2 𝑂 + 2𝑆𝑂2
Reaction 2.16: 𝐶𝑢2 𝑆 + 2𝐶𝑢2 𝑂 → 6𝐶𝑢 + 𝑆𝑂2
Reaction (Overall) 2.17: 3𝐶𝑢2 𝑆 + 3𝑂2 → 6𝐶𝑢 + 3𝑆𝑂2

Fig. 2.5: Operating Principles of Side blown Converter

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Chapter 2 Extraction of Non-Ferrous Metals

When white metal (Cu 2 S) is oxidized the 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 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 O 2 .
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 SO 2 by
oxidation with air and eliminates O 2 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 Cu 2 O 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 is CuSO 4 , H 2 SO 4 , some glue and alcohol at temperature 50-600 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.

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Chapter 2 Extraction of Non-Ferrous Metals

(ii) Newer Process:

Flash Smelting:

Fig. 2.6: Flash Smelting

Process: Enriched preheated air or pure O 2 used to increase combustion rate and
autogeneous smelting. The gases coming out rich of SO 2 due to high combustion rate and
used for H 2 SO 4 manufacturing.
Process is autogeneous provide exothermic heat. Air used as oxidant to preheated.
The composition of concentrate used in flash smelting has Chalcopyrite (CuFeS 2 ) 66%,
Pyrite (FeS 2 ) 24%, gangue (SiO 2 ) 10%. Whereas the Cu matte contains 70% Cu, 8% Fe, 22%
S, slag contains Fe 40% at furnace temperature 13000 C.
Main reactions of flash smelting of Cu concentrate are mentioned below
Reaction 2.18: 𝐶𝑢𝐹𝑒𝑆2 + 0.5𝑂2 → 0.5𝐶𝑢2 𝑆 + 𝐹𝑒𝑆 + 0.5𝑆𝑂2
Reaction 2.19: 𝐶𝑢𝐹𝑒𝑆4 + 0.5𝑂2 → 2.5𝐶𝑢2 𝑆 + 𝐹𝑒𝑆 + 0.5𝑂2
Reaction 2.20: 𝐶𝑢𝑆 + 0.5𝑂2 → 0.5𝐶𝑢2 𝑆 + 0.5𝑆𝑂2
Reaction 2.21: 𝐹𝑒𝑆2 + 𝑂2 → 𝐹𝑒𝑆 + 𝑆𝑂2
Reaction 2.22: 𝐹𝑒𝑆 + 1.5𝑂2 → 𝐹𝑒𝑂 + 𝑆𝑂2
Reaction 2.23: 𝐹𝑒𝑂 + 0.16𝑂2 → 0.33𝐹𝑒3 𝑂4
Reaction 2.24: 𝐹𝑒𝑂 + 0.5𝑆𝑖𝑂2 → 0.5𝐹𝑒2 𝑆𝑖𝑂4
Reaction 2.25: 𝐶𝑢2 𝑆 + 1.5𝑂2 → 𝐶𝑢2 𝑂 + 𝑆𝑂2

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Chapter 2 Extraction of Non-Ferrous Metals

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.
(a) WORCRA 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 H 2 SO 4 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.

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Chapter 2 Extraction of Non-Ferrous Metals

Disadvantage:
• Not durable
• Operating cost is high

Fig. 2.7: Vertical Sectional Diagram of Straight form of WORCRA reactor

(b) 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.

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Chapter 2 Extraction of Non-Ferrous Metals

Fig. 2.8: Schematic diagram of Noranda Process

(c) 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 + O 2 ) 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 O 2 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.

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Chapter 2 Extraction of Non-Ferrous Metals

Fig. 2.9: Mitsubishi Continuous Smelting Process

2.1.4 Area of Extraction:

• HCL (Hindustan Copper Ltd.)
• Khetri mines
• Kholihana mines
2.1.5 Uses:
• Conducting element
• Alloying addition

Question 2.1: What do you mean by Zone refining?

Answer:

Fig. 2.10: Zone Refining

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Chapter 2 Extraction of Non-Ferrous Metals

This refining technique applied only for ultra pure material i.e. low concentration of
impurity. If ‘A’ is solvent and ‘B’ is solute then addition of A with B caused increase in
melting point of B as due to bond formation as A-A, A-B, B-B.
When A at composition of ‘P’, it get melted and when it is at ‘Q’ get solidify, whereas
the same compositions for B at equilibrium condition is less than A.
The free energy difference is
𝑎
∆𝐺𝐵 (𝑠) − ∆𝐺𝐵 (𝑙) = 𝑅𝑇 ln � � = 𝑅𝑇 ln 𝐾0
𝑏
[Where K 0 = a/b= segregation coefficient
a= concentration of impurity in liquid
b=concentration of the liquid ]
It mainly applicable to semiconductor industry during coal refining of Ge and Si
2.2 Extraction of Zn by Pyrometallurgical Process:
2.2.1 Details about of Zn:

Atomic Number: 30

Atomic Weight: 65.38 amu

Density: 7.13 gm/cm3

Melting Point: 419.50 C

Boiling Point: 9100 C

2.2.2 Common Minerals of Zn:

Zinc Oxides Zinc Sulphides

Name Chemical Formula Name Chemical Formula

Zincite ZnO Sphalerite ZnS

Franklinite [ZnO(Fe, Mn) 2 O 3 ]

Willemite Zn 2 SiO 4

Smith Sonite ZnCO 3

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Chapter 2 Extraction of Non-Ferrous Metals

2.2.3 Extraction of Zn from Sulphide Ores:

Mainly five important processes are there in extraction of Zn. Given as follows
1. Horizontal Retort
2. Vertical Retort
3. Electrothermic
4. Electrolytic
5. Imperial Smelting
The first 3 processes are retort process. Horizontal retort made a major contribution to
Zn production. Electrolytic process gives high degree purity at about 99.95%. In this case Si
rectifiers incorporated in electrolytic cells to reduce power consumption and higher current
density achieve.
Recently imperial smelting process (ISP) used, in which ZnO get reduces by use of
molten lead to give Zn vapour which on condensation gives Zn.

Reaction 2.26: 𝑍𝑛𝑆 + 1.5𝑂2 → 𝑍𝑛𝑂 + 𝑆𝑂2

Reaction 2.27: 𝑍𝑛𝑂 + 𝐶𝑂 → 𝑍𝑛 + 𝐶𝑂2

Reaction 2.28: 𝐶 + 𝐶𝑂2 → 2𝐶𝑂

Flow sheet Explanation

The technique of smelting and converting not applicable for Zn extraction because
ZnS not melt even at 15000 C. Zn% 55 in concentrate treated under roasting, then it go for
sintering where roasted oxide ground and agglomerates then go under C reduction to give Zn
in vapour form. For volatisation hearth roaster used instead of other.
Initial stage roasting i.e. volatisation a hearth roaster employs. Then remaining PbS
removed during sintering rather than high temperature. In order to prevent distillation of Pb
present in Zn concentrate to obtain high grade Zn with low Pb in retort distillation.

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Chapter 2 Extraction of Non-Ferrous Metals

In most cases, fluid bed roaster allotted instead of hearth roaster because of following
advantages

• Autogeneous
• Good control over high through put of Zn calcine
• Generate SO 2 suitable for acid production

Fig. 2.11: Extraction of Zinc by Reduction of ZnO by Carbon

1. Horizontal Retort Reduction:

It is a 2m long, 0.25 m dia., 5-6 cm thick gas fired retort furnace made of clay used
instead of metal retort because most metals gives alloy when heated with Zn. Here, first loose
mixture of ZnO presence of coke breeze charged at 14000 C to volatize Zn which on
condensation gives Zn.

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Chapter 2 Extraction of Non-Ferrous Metals

2. Vertical Retort Reduction:

It is a 10 m height, 0.7 m dia., and 30 cm thick of capacity 7-10 tons Zn per clay made
of SiC because has high conductivity approximately 5 times compare to horizontal retort.
3. Electrothermic Reduction:
It occurs in a vertical retort 15 m high, internal dia. of 24 m about 100 tons Zn per
day. Electrodes of graphite introduce through SiC walls at two places near the bottom and at
a zone of 9 m from the bottom. The gas liberate due to the reduction of charge contains 40-
45% Zn, 45% CO, 5-8% H 2 , 5-10% N 2 . Avoid formation of blue oxide of Zinc (ZnO+Zn)
quick condensation takes place. Residue contains 3-4% Zn. Zn recovery over 95%.
Zn product obtained in foregoing retort is known as Spelter.

Three distinct layers as

• Bottom layer is molten lead contains some Zn of 1.5%.

• Top layer is Zn contains some lead of 0.8%.
• Intermediate layer of Zn and Fe (15-20)% called hard metal.

Zn layer further refined by fractional distillation because wide difference in boiling

point of Zn (9070 C), Cd (7800 C), and Pb (16200 C) facilities the separation of one metal
from the other.

4. Electrolytic Reduction:
In this case, when Zn immersed in their salt solutions, rapidly establish a reversible
potential. Since the activation over potential is low, the displacement behavior exhibits a
good correlation with the electrochemical series of standard potentials.
5. Imperial Smelting Process (ISP):
The process inside the furnace based on reaction i. e. reduction of ZnO by C in the imperial
blast furnace gives rise to Zn in vapour form which gets condensed by using molten lead.

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Chapter 2 Extraction of Non-Ferrous Metals

Fig. 2.12: Imperial Smelting Blast Furnace

Principle: The process is carried out by using counter current principle, where the blast and
preheated air given to the furnace through the tuyere and the preheated coke get charged from
the top.

• ISP furnace is of square cross section consists of water jacket brick lined shaft.
• Feed is given from the top of the furnace at positive pressure where we
introduced preheated coke and sinter through a double bell charging system.
• ISP consists of two condensers.

Function of Condenser: These are used mainly for two purposes as

• Cooling of furnace gases resulting due to condensation of Zn

• Dissolving condensed Zn in molten Pb

The smelting reactions takes place in ISP are

1
Reaction 2.29: 𝐶 + 𝑂2 → 𝐶𝑂
2

Reaction 2.30: 𝐶 + 𝑂2 → 𝐶𝑂2

Reaction 2.31: 𝐶 + 𝐶𝑂2 → 2𝐶𝑂
Reaction 2.32: 𝑍𝑛𝑂 + 𝐶𝑂 → 𝑍𝑛 + 𝐶𝑂2
Reaction 2.33: 𝑃𝑏𝑂 + 𝐶𝑂 → 𝑃𝑏 + 𝐶𝑂2

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Chapter 2 Extraction of Non-Ferrous Metals

Carbon does not reduce ZnO until 11200 C, since at this temperature Zn gets
vaporized. After reduction complete the molten slag and Pb are taken out from the furnace
hearth at the melting point of the slag. Hence, Zn gets collected. So the reaction (2.31) may
backward as due to the difference.
Lead Bullion (Rich 70-80% Pb):
It is the mixture of Pb and precious metal, where preheated coke 8000 C and sinter
21% Pb are charged from the top of ISP furnace. So at bottom collect precious metals such as
Au, Cu etc. and this liquid is known as Lead Bullion.
Advantages of ISP:
• Economical production of Zn.
• Efficiency overall high but Zn recovery expensive.
• Entire amount of Au, Sb etc. recover.
• Capacity large.
• Complete mixed charge of Zn and Pb simultaneously charged and
recovered.
• Operational cost is low.
• No additional C required.

Fig. 2.13: Zinc Recovery System

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Chapter 2 Extraction of Non-Ferrous Metals

Zn from Lead Slag by Slag Fuming Process:

The process initiated by Consolidated Mining Smelting Corporation (COMINCO) of
Trial, Canada.
Process:
The slag produce in lead bath or furnace are 15-18% Zn. Molten slag from lead blast
furnace together with cold slag from dump get transformed by ladle and charged to the
furnace. Then the treatment growing of molten slag by treated with mixture of pulverized fuel
and air through tuyere. Hence, Zn get volatized and slag get solidified by means of water
jacket in all sides of furnace except roof as roof is cover with fire bricks.
So, due to mixture of pulverized fuel and air through tuyere the reactions occur as

In bath,
Reaction 2.34: 2𝐶 + 32 𝑂2 → 𝐶𝑂 + 𝐶𝑂2
Reaction 2.35: 𝐶𝑂 + 𝑍𝑛𝑂 → 𝑍𝑛 + 𝐶𝑂2
Above bath,
Reaction 2.36: 𝑍𝑛 + 12 𝑂2 → 𝑍𝑛𝑂
1
Reaction 2.37: 𝐶𝑂 + 𝑂2 → 𝐶𝑂2
2

Fig. 2.14: Zinc Elimination during Slag Fuming

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Chapter 2 Extraction of Non-Ferrous Metals

The excess heat gets collected by boiler located in gas collection system and the
control of coal to air ratio determine the extent of heat released and maintained the bath
temperature at about 12000 C.
First, the elimination of Zn is slow but reaching 10000 C get accelerate so Zn% 2.5%.
Whereas Zn 1% in slag product contain 93-94% Zn. Fume leaves furnace at 11000 C by
combustion which effected by water cooling tower at 2000 C.
Then fume enters to big house where Zn collected and dispatched to Zn smelter on an
electrolytic plant.

2.2.4 Uses or Applications:

• Zn extensively used as a protective coating for steel (Galvanization).
o Restrict atmosphere corrosion by impervious basic ZnCO 3 layer.
o Zn is more electropositive.
• Fabrication of Cu-Zn alloys i. e. brasses.
• Spraying – Zn used as for spraying in comparison to other metal on that metal which
has low melting point.
• Rolled Zn: Usual method of cold working. Zn is rolled to sheet, plate, and strip.
Where, sheet plates are rolled from 98.5% Zn.
• Pigment: Zn in the form of its oxides used in manufactured of paints.
• Alloys: Mainly Cu-Zn alloy produce of 30-37% Zn which is much less plastic when
cold and worked about 5000 C which mainly used as die casting alloy.
2.2.5 Area of Extraction:
• Zawar Mines (Rajstan).
• HZL (Hindustan Zinc Ltd.).
• COMINCO-BINANI at Kerela.

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Chapter 2 Extraction of Non-Ferrous Metals

2.3 Extraction of Pb by Pyrometallurgical Process:

2.3.1 Details of Pb:
Atomic Number: 82
Atomic Weight: 207.21 amu
Density: 11.34 gm/cm3
Melting Point: 327.400 C
Boiling Point: 17370 C
2.3.2 Common Minerals of Pb:
Pb Oxides Pb Sulphides

Name Chemical Formula Name Chemical Formula

Cerrusite PbCO 3 Galena PbS

Anglesite PbSO 4

2.3.3 Extraction of Pb:

2.3.3.1 Production of Pb bullion:

Fig. 2.15: Flow Sheet of Production of Lead Bullion

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Chapter 2 Extraction of Non-Ferrous Metals

Complete Description of Flow Sheet (Extraction of Lead Bullion):

The concentrate roasted to oxides which get reduced by C at 8000 C above to fuse
PbS, which occur in Dwight-Lloyd sintering machine in which not only S eliminate but also
produce sinter with liquidize properties. In this S% reduce from 16-18% to 1-2%.
Now, up draught is more preferred compare to down draught because of
• Higher capacity
• Elimination of precipitate wind box Pb
• Production of high grade SO 2 gas
In, up draught air is admitted from perforated bottom gate. Heat liberated due to
roasting of Galena ore out of temperature below fusion temperature.
Reaction 2.38: 2𝑃𝑏𝑆 + 72 𝑂2 → 𝑃𝑏𝑂 + 𝑃𝑏𝑆𝑂4 + 𝑆𝑂2

Hence, free Pb gravitated to the wall of furnace, and was trapped out at working
temperature 10000 C. Thick crust allow to accumulate slowly down even stopped reaction by
the action of the air blast.

Fig. 2.16: Molten Blast Furnace

Older Blast Furnace Reduction: Furnace decrease in area from throat downward a
minimum being attend end at tuyere of area 4-5 m2. Blast pressure increases resulting in
volatization of lead. As increase volume of blast lead volatization decreases.
Siphon top: A device connects molten Pb in the crucible with a bowl shape which
keeps the level of Pb in the crucible constant by withdrawn from the top.

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Chapter 2 Extraction of Non-Ferrous Metals

Bosh: Purpose is to retard the descent of charge in front of tuyere as material melts
away.
Newer Blast Furnace Reduction: Furnace area increases from the throat to downward at the
end of tuyere in this case following advantages are occur

• Gases more evenly through charge

• Decreasing their velocity
• Decrease the amount of dust
• Here scrap used for reduction of unreduced PbO

PbO also helps in reducing PbS left unroasted in the sinter machine and hence,
combine with Silica (SiO 2 ) in charge to form 2FeO.SiO 2. Hence, lower the melting point of
slag and increase the fluidity of metal layer.
Reaction 2.39: 𝑃𝑏𝑆𝑖𝑂3 + 𝐹𝑒 → 𝐹𝑒𝑆𝑖𝑂3 + 𝑃𝑏
Finally helps to reducing the Pb as
Reaction 2.40: 𝑃𝑏𝑂 + 𝐹𝑒 → 𝐹𝑒𝑂 + 𝑃𝑏
Disadvantage of Newer Process:
• A thick mushy layer form in between matte and slag which interfering into the
separation
• A wide variation in temperature as 2000 C at top to 12000 C at tuyere

In blast furnace reduction produce 4 distinct layers on the basis of their specific
gravity as

• First layer – Slag Layer – Specific gravity 3.6

• Second layer – Matte Layer – Specific gravity 5.2
• Third layer – Speiss Layer – Specific gravity 6
• Forth layer – Lead Bullion/Base Bullion

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Chapter 2 Extraction of Non-Ferrous Metals

Question 2.2: What is Speiss?

Answer: When Unvolatized As reacts with Fe and C to form Speiss

OR

A molten phase consists primarily Fe, As which is commonly encountered in lead

smelting operation.

Mainly Speiss closely relate in the presence of As and Fe in the blast furnace.

Reaction 2.41: 𝐴𝑠2 𝑂3 + 8𝐹𝑒𝑂 + 11𝐶 = 2𝐹𝑒4 𝐴𝑠 + 11𝐶𝑂

Speiss have high content of Cu which get recovered by treated it in converter to get
Cu in blister form. Finally, the Pb bullion or base bullion get from the blast furnace which on
refining produce pure lead.

2.3.3.2 Refining of Pb Bullion to extract Pb:

Liquation: Refining technique for removing impurities from metal based on the factor such
as difference in melting point of alloy components. So as a number of layers formed on the
basis of their difference in density.

Fig. 2.17: Lead Zinc Phase Diagram

The crude Zn containing of 5% Pb refined in a reverberatory furnace by slowly
cooling of molten matte.

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Chapter 2 Extraction of Non-Ferrous Metals

Fig. 2.18: Refining of Lead Bullion

Drossing: It is the combine process of liquation and oxidation in reverbaratory furnace at
around temperature 3500 C at which many metals oxidized and skimmed off subsequently
increase to (500-550)0 C. At that temperature Cu get eliminates using S in the form of Cu 2 S
and at last softener slag (Sb, Sn, As, Te, Se) are removed.

Question 2.3: What do you mean by softening and why it is required?

Answer: Drossed bullion containing 1-1.5% of impurities as Sn, As and Sb treated in a

softening furnace in oxidized condition. It required for refining of soft malleable Pb and
hence, increases corrosion resistance. As presence of impurities Sn, As, Sb causes hardened
of alloy. So softening required.

Desilverising of Pb (PARKE’S Process):

The process of desilverising of Pb by Zn addition followed by cooling for Ag
recovery is known as desilverising of Pb or PARKE’s process.
In this process, Zn is added in molten Pb because of high affinity of Zn for Ag and Au
than Pb. Then two liquid layers such as

• Liquid Zn at the upper layer having Zn% of 0.6

• Liquid Pb at the bottom layer having Pb% of 1.5

As Zn layer (first layer) has higher melting point. So, solidify first.

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Chapter 2 Extraction of Non-Ferrous Metals

Question 2.4: What is Cupellation?

Answer: Melting Ag containing Pb in reverbaratory furnace by exposing it to a blast in a

layer. So as Pb or other metals get oxidized and slag off except Ag as it has no attraction
towards O 2 . Hence Ag remains behind i. e. get separated in the hearth.

Dezincing:

Fig. 2.19: Dezincing Process

As Cl 2 reacting with Zn to give ZnCl 2 in an enclosed chamber cause left of Pb and
falling on bath looks grayish scum surface (layer of bubble formation) which gets skimmed
off.
At the end point, all Zn chlorinated and white crystal of PbCl 2 appeared on surface.
Vacuum dezincing desilverised lead pump to kette i. e. bath enclosed by steel ball shaped
with a stirrer and vacuum pump attached. As temperature rose to 5400 C vacuum distillation
carried out in reduction of Zn content from 0.6 to 0.002% in lead.
Debismuthizing:
The base bullion consist high Bi% which getseparated by addition of Ca and Mg to
forms an insoluble intermetallic compound of Bi.
2.3.3.3 Refining of Lead bullion to get Pb using electrolytic reefing:
In the electrolytic cell, the pure Pb obtained by taking base or Pb bullion at anode
where, electrolyte consists of a solution of PbSiF 6 (Lead Flouro Silicate) in H 2 SiF 6
(Hydrogen Silicic acid). In this case, H 2 SiF 6 get acted on white Pb. So, granulated Pb
obtained to give PbSiF 6 in the next step.

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Chapter 2 Extraction of Non-Ferrous Metals

2.3.4 Use of Pb:

• Manufacture of battery, cable, pigment, flexible sheet and pipe. Basic Pb

carbonate such as 2PbCO 3 .Pb (OH) 2 used in Pb pigment form on basis of
grade point. Also, litharge (PbO) used in reverbaratory furnace for oxidation
for pigmented varnish and glass production.
• Red Lead (Pb 3 O 4 ): Higher oxide of Pb made by heating Litharge under
control condition about 4500 C and same use as Litharge.
• Lead Chromate: Normal yellow chromate made by the precipitate from the
solution of Lead acitate and nitride to which Sodium Bicarbonate will be
added.

2.3.5 Area of Extraction:

• HZL – Major production of Pb in Bihar (Tundoo)
• Visakhapatnam (Andhra Pradesh) – 15,000 tonne/year
Question 2.5: Discuss the important mechanical properties of Lead (Pb).
Answer: Important mechanical properties of Lead (Pb) are
• Heaviest metal
• Most malleable, easy to shaping and working
• Low melting point

2.4 Extraction of Ni by Pyrometallurgical Process:

2.4.1 Details about of Ni:
Atomic Number: 28

Atomic Weight: 58.69 amu

Density: 8.98 gm/cm3

Melting Point: 14520 C

Boiling Point: 29000 C

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Chapter 2 Extraction of Non-Ferrous Metals

2.4.2 Common Minerals of Ni:

Pentalandite – [(NiFe) 9 S 8 ]

Violarate – [Ni 2 FeS 4 ]

2.4.3 Extraction of Ni from Sulphide Ore:

2.4.3.1 Explanation of Flow Sheet:
Initial Treatment: The ore is a mixed Cu-Ni ore with nearly equal amount of Cu and Ni.
The ore undergoes into grinding and froth floatation to produce a bulk concentrate which sent
to copper cliff mill for separation of Cu concentrate, Ni concentrate and Pyrrohotite
concentrate with iron sulphide with about 0.8% Ni.
Then the Cu concentrate subjected to O 2 flash smelting for Cu extraction. From
Pyrrohotite after roasting iron oxide form and Ni separated by leaching. The Ni concentrate
with about 10% Ni, 2% Cu, 40% Fe, and 30% S goes for extraction of Ni in next stage.
Roasting: In conventional process, the concentrate partially roasted to oxidize the iron
sulphide either multiple hearth roaster or fluidized bed roaster. But fluidized bed roaster is
more preferable because of
• High output and rich SO 2 gas stream generates
• Process is Autogeneous
• Temperature range (550-600)0 C about 40% S oxidized
Smelting: The roasted calcine contains desired amount of siliceous flux is smelted in a
reverberatory furnace to produce a matte containing Cu, Ni as 20%, 7% respectively where
the slag discarded contains gangue and oxidized iron. There is also converter slag of both Ni
and Cu converters are returned to the reverberatory furnace.
Converting: Furnace matte is converted to Ni enriched matte with 50% Ni, 25% Cu, 0.7%
Fe, and 21.5% S at 11500 C in Pierce-Smith converter. The slag discarded contains 2% Ni,
1.5% Cu, 40% Fe, and 25% SiO 2 return to reverberatory furnace for recovery of Ni and Cu.
Slow Cooling: Converter matte subjected to slow cooling process from melting point to 4000
C for 3 days to form three layers precipitate out as
• First layer, Cu 2 S precipitate and grows
• Second layer, metallic Cu-Ni alloy at 7000 C
• Third layer, solid Ni 3 S 2 phase precipitate at 5750 C

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Chapter 2 Extraction of Non-Ferrous Metals

Fig. 2.20: Nickel Extraction (INCO Process)

45
Chapter 2 Extraction of Non-Ferrous Metals

Question 2.5: Why slow cooling required after converting process?

Answer: Slow cooling required obtaining necessary grain growth, which then go for
subsequent processing of sulphides to recover it in the froth floatation.
Magnetic Separation and Floating: Diphenyl guanidiene used as collector as well as frother
rather than Xanthate. In floatation, Ni-Cu alloy contains 95% precious metals is undergo for
magnetic separation for recovery of it. Cu 2 S produced by floatation contains 70% Cu, 5% Ni,
20% S. Ni sulphide recovered as a low Cu-Ni sulphide with 74% Ni, 0.8% Fe, 0.8% Cu, and
22% S. High Cu-Ni sulphide with 72% Ni, (3-4) % Cu, 0.8% Fe, and 21% S at a temperature
(1100-1250)0 C roasting produce granular nickel oxide.
Final Treatment:
• Low Cu-Ni oxide is marketed directly as Nickel oxide or reduced to metal.
• High Cu-Ni oxide sends for refining by carbonyl process and other half by
electrolytic refining.

2.4.3.2 Refining Process:

1. Carbonyl Process for Refining Ni:
(i) Mond’s Process:
In 1889, this refining process of Ni recovered by Carl Langer and Ludwig
Mond. In this process, at temperature (40-90)0 C metallic Ni combine with CO to give
gaseous nickel carbonyl [Ni(CO) 4 ]. At higher temperature (150-300)0 C Ni(CO) 4
decomposes to give Ni and CO gas. The reactions are
𝑎𝑡 500 𝐶
Reaction 2.42: 𝑁𝑖 + 4𝐶𝑂 �⎯⎯⎯⎯� 𝑁𝑖(𝐶𝑂)4
𝑎𝑡 2300 𝐶
Reaction 2.43: 𝑁𝑖(𝐶𝑂)4 �⎯⎯⎯⎯� 𝑁𝑖 + 4𝐶𝑂

Other forms of Carbonyls are volatile carbonyl [Fe(CO) 5 ], Co carbonyl in

tetracarbonyl [Co 2 (CO) 8 ] tricarbonyl [Co 4 (CO) 12 ] form. Cu and other major elements are not
form carbonyls.

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Chapter 2 Extraction of Non-Ferrous Metals

(ii) INCO Process:

INCO Atmospheric Carbonylation Process:

The oxide first reduces to active Ni in the presence of H 2 at about 4000 C. Then active
Ni undergoes for carbonylation at 500 C to form Ni(CO) 4 then at 2300 C goes for
decomposed to Ni either in pellets about 1 cm dia or powder form about 3.5 µm size.

INCO Pressure Carbonylation Process:

The carbonylation reaction has 4 to 1 volume change permits at about 1800 C and 70
atm pressure carbonyls of Ni, Fe, and Co formed. From which Ni(CO) 4 recovered by
fractiona distillation and converted to metallic Ni in pellet decomposer or a powder
decomposer.
2. Electrolytic Refining of Ni:

Fig. 2.21: Electrolytic Refining of Ni

The Ni oxide reduce by coke in fuel fired furnace or electric furnace, and then cast
into Ni metal anode. These anodes are electrolytically refined in a bath contains 60 gm/lit
Ni+2, 95 gm/lit SO 4 2-, 35 gm/lit Na+, 55 gm/lit Cl-, 16 gm/lit H 3 BO 3 . This electrolysis carried
out at 600 C. Cu remove by cementation with active Ni powder, Fe and other impurities
remove by aeration of electrolyte, Co remove by Cobaltic Hydroxide for further Chlorine
oxidation. Electrolyzed Ni analyzes about 99.93% Ni.

47
Chapter 2 Extraction of Non-Ferrous Metals

But in INCO process, electro refining Ni sulphide to metallic Ni to produce anode

contains 76% Ni, 0.5% Co, 2.6% Cu, and 20% S. The process is same as the above one, only
difference is that the anode enclosed in a bag to collect anode slime contains 95% S and is
processed to recover elemental Sulpher and precious metals. The electronickel contains
99.95% Ni.
2.4.4 Uses of Ni:
• Important alloying elements used in chemical processing, space research and
nuclear reactor.
• Ni-Cu alloys known as Mnel metals are used in chemical oil industry and
electric industry.
• Ni, Cu, and Zn alloys are known as German silver. It is used for manufacture
of ribbons, bands, and wires for various applications.

2.4.5 Area of Extraction:

Canada, INCO-80% production

2.5 Extraction of Magnesium by Pyrometallurgical Process:

2.5.1 Details about of Mg:
Atomic Number: 12
Atomic Weight: 24 amu
Density: 1.738 gm/cm3
Melting Point: 6500 C
Boiling Point: 11070 C
2.5.2 Common Minerals of Mg:
Dolomite – (MgCO 3 .CaCO 3 )
Magnesite – MgCO 3
MgCl 2 and MgSO 4 present in sea water.
Brucite – Mg (OH) 2
Carnallite – MgCl 2 .KCl.6H 2 O
Olivine – Mg 2 SiO 4
Sarpentine – Mg 3 Si 2 O 7

48