Extraction Metallurgy

Question 1

Extractive metallurgy is that branch of metallurgy that deals with ores as raw material and metals
as finished products. It is an ancient art that has been transformed into a modern science as a result
of developments in chemistry and chemical engineering.

a) Describe any 5 different types of combined mineral resources used in industrial

applications with their chemical compositions. [30 Marks]

Answering any five of above will get

b) In order to convert a metal oxide or sulfide to a purer metal, the ore must be reduced
physically, chemically or electrolytically. Discuss five major important steps involved
in the metallurgical process? [30 Marks]

Metallurgy is the science and technology of extracting metals from minerals.

There are five important steps:
1. Mining (getting the ore out of the ground)
2. Concentrating (preparing it for further treatment)
3. Reduction (to obtain the free metal in the zero oxidation state)
4. Refining (to obtain the pure metal); and
5. Mixing with other metals (to form an alloy)

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 c) Describe three major metallurgical extraction processes and describe how you are
going to select one or more of those methods for metal extraction. [40 Marks]

Pyro metallurgy
Pyro metallurgy is a process using high temperatures to obtain the free metal.
Several steps are employed:
Calcination is heating of ore to cause decomposition and elimination of a volatile product (CO2
or H2O):
e.g. PbCO3(s) → PbO(s) + CO2(g)
Roasting is heating which causes chemical reactions between the ore and the furnace
atmosphere:
2ZnS(s) + 3O2(g) → 2ZnO(s) + 2SO2(g)
2MoS2(s) + 7O2(g) → 2MoO3(s) + 4SO2(g)
Smelting is a melting process that causes materials to separate into two or more layers.
Slag consists mostly of molten silicates in addition to aluminates, phosphates, fluorides, and
other inorganic materials.
Refining is the process during which a crude, impure metal is converted into a pure metal

Hydrometallurgy
Hydrometallurgy is a method for obtaining metals from their ores. It is a technique within the
field of extractive metallurgy involving the use of aqueous chemistry for the recovery of metals
from ores, concentrates, and recycled or residual materials
e.g. Hydrometallurgy of Aluminum
Aluminum is the second most useful metal.
Bauxite is a mineral that contains Al as Al2O3.xH2O.
Major impurities are silicates (SiO2) and iron oxides (Fe2O3).
e.g. Aluminum Hydroxide manufacturing
Bayer process:
The crushed ore is digested in 30% NaOH (by mass) at 150 - 230C and high pressure (30 atm to
prevent boiling).
Al2O3 dissolves:
Al2O3.H2O(s) + 2H2O(l) + 2OH-(aq) → 2Al(OH)4-(aq)
The silicates and iron oxides do not dissolve and can be filtered from the solution. The aluminate
solution is separated by lowering the pH causing separation of the aluminum hydroxide. The
aluminate hydroxide is calcined to produce the aluminum oxide.

Electrometallurgy
Electrometallurgy is the reduction of metal by electrolytic process
Bauxite contains alumina (Al2O3 aluminium oxide) plus impurities such as iron oxide – it is
purified before use. Aluminum oxide has a very high melting point. Adding cryolite lowers the
melting point and saves energy. Unlike iron, aluminium cannot be extracted using carbon. Since
Aluminium is above carbon in the reactivity series. Reactive metals are extracted using electrolysis
Electrolysis is expensive - it requires a lot of energy…
- ore must be molten (have high melting points)
- electricity is needed for the electrolysis process

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Selecting one or more of above extraction process depend on type of the mineral, metal going to
extract, purity of the ore, environmental and regulatory issues , cost of production and availability
of the resources and infrastructure facilities.

Question 2

Sri Lankan iron ore deposits are geologically divided into three broad categories such as primary
iron ore (Magnetite deposits), secondary iron ore (Hydrated iron oxide ore deposits) and Seruwila
copper-magnetite iorn ore deposits. The most common ferrous and ferroalloy minerals found in
Sri Lanka are magnetite, hematite and iron oxides. These deposits are found as surface as well as
subsurface occurrences.

a) Suppose one foreign investor is interested to invest substantial capital to establish an iron
making industry in Sri Lanka considering available local iron ore deposits, briefly describe
the factors to be considered to identify the suitable location for establishing an iron making
industry in Sri Lanka? [40Marks]

Many important geographical factors involved in the location of individual industries are of
relative significance, e.g., availability of raw materials, power resources, water, labor, markets,
and the transport facilities.
But besides such purely geographical factors influencing industrial location, there are factors of
historical, human, political and economic nature which are now tending to surpass the force of
geographical advantages. Consequently, the factors influencing the location of industry can be
divided into two broad categories i.e.

(I) Geographical factors, and

(II) Non-geographical factors.

Geographical Factors:
Following are the important geographical factors influencing the location of iron making industry.

1. Raw Materials:
The significance of raw materials in manufacturing industry is so fundamental that it needs no
emphasizing. Indeed, the location of industrial enterprises is sometimes determined simply by
location of the raw materials. Modem industry is so complex that a wide range of raw materials is
necessary for its growth.

Further we should bear in mind that finished product of iron industry may well be the raw material
of another. For example, pig iron, produced by smelting industry, serves as the raw material for
steel making industry. Industries which use heavy and bulky raw materials in their primary stage
in large quantities are usually located near the supply of the raw materials.
Industries like iron which use very large quantities of coal, limestone and iron ore. Therefore Iron
making industry may therefore close to the sources of raw materials.

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 2. Power:
Regular supply of power is a pre-requisite for the localization of industries. Coal, mineral oil and
hydro-electricity are the three important conventional sources of power. Most of the industries
tend to concentrate at the source of power.
The iron and steel industry which mainly depends on large quantities of coking coal as source of
power are frequently tied to coal fields.

3. Labour:
Labour supply is important in two respects (a) workers in large numbers are often required; (b)
people with skill or technical expertise are needed for iron making industry.

4. Transport:
Transport by land or water is necessary for the assembly of raw materials and for the marketing of
the finished products. Transportation of bulk quantities are necessary for iron making industry
therefore access to railway systems also prior important.

5. Market:
The entire process of manufacturing is useless until the finished goods reach the market. Nearness
to market is essential for quick disposal of manufactured goods. It helps in reducing the transport
cost and enables the consumer to get things at cheaper rates.

6. Water:
Water is another important requirement for industries. Many industries are established near rivers,
canals and lakes, because of this reason. Iron and steel industry, textile industries and chemical
industries require large quantities of water, for their proper functioning.

7. Site:
Site requirements for industrial development are of considerable significance. Sites, generally,
should be flat and well served by adequate transport facilities. Large areas are required to build
factories. Now, there is a tendency to set up industries in rural areas because the cost of land has
shot up in urban centers.

8. Climate:
Climate plays an important role in the establishment of industries at a place. Harsh climate is not
much suitable for the establishment of industries. There can be no industrial development in
extremely hot, humid, dry or cold climate.

Non-Geographical Factors:

Now-a-days alternative raw materials are also being used because of modern scientific and
technological developments. Availability of electric power supply over wider areas and the
increasing mobility of labour have reduced the influence of geographical factors on the location of
industries.

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The non-geographical factors are those including economic, political, historical and social factors.
These factors influence our modern industries to a great extent. Following are some of the
important non- geographical factors influencing the location of industries.

1. Capital:
Iron making industry is capital-intensive and require huge investments.

2. Government Policies:
Government policies on industrial zonation, national development plan, environmental and other
regulatory measures and financial policies also need to consider.

3. Industrial Inertia:
Industries tend to develop at the place of their original establishment, though the original cause
may have disappeared. This phenomenon is referred to as inertia, sometimes as geographical
inertia and sometimes industrial inertia.

4. Efficient Organisation:
Efficient and enterprising organisation and management is essential for running modem industry
successfully. Bad management sometimes squanders away the capital and puts the industry in
financial trouble leading to industrial ruin. Bad management does not handle the labour force
efficiently and tactfully, resulting in labour unrest. It is detrimental to the interest of the industry.
Strikes and lock-outs lead to the closure of industries. Hence, there is an imperative need of
effective management and organisation to run the industries.

5. Banking Facilities:
Establishment of industries involves daily exchange of money which is possible through banking
facilities only. So the areas with better banking facilities are better suited to the establishment of
industries.

6. Insurance:
There is a constant fear of damage to machine and man in industries for which insurance facilities
are badly needed.

b) What are the basic raw materials and other infrastructure facilities required for iron making
industry in sri lanka? [20Marks]
Raw materials
Ion ores, Limestone and Coal
Infrastructure
Electricity, Land and building, Water, Telecommunication facilities, Transportation facilities
Distance to port and airport, Proper road network, Waste disposal facilities, Environmental and
other regulatory measures.

c) Briefly describe the present iron making process and draw a neat sketch of a typical iron
making blast furnace and name the important part and chemical reactions happening in the
different temperature zones. [40Marks]

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 Present Iron making process

Most important sources of iron ore are hematite Fe2O3 and

magnetite Fe3O4.
Reduction occurs in a blast furnace. The ore, limestone and
coke are added to the top of the blast furnace. Coke is coal that
has been heated to drive off the volatile components.

Coke reacts with oxygen to form CO (the reducing agent):

2C(s) + O2(g) → 2CO(g) H = -221 kJ
CO is also produced by the reaction of water vapor in the air
with C:
C(s) + H2O(g) → CO(g) + H2(g), H = +131 kJ
Since this reaction is endothermic, if the blast furnace gets too
hot, water vapor is added to cool it down without interrupting
the chemistry.
Also around 250C iron oxides are reduced by CO(g) and H2(g): Fe3O4(s) + 4CO(g) → 3Fe(s) +
4CO2(g), H = -15 kJ
Fe3O4(s) + 4H2(g) → 3Fe(s) + 4H2O(g), H = +150 kJ

Molten iron is produced lower down the furnace and removed at the bottom. If iron is going to be
made into steel it is poured directly into a basic oxygen furnace.

At around 250C limestone is calcinated (heated to decomposition and elimination of volatiles).

CaCO3(s) → CaO(s) + CO2(g)

This reacts with the silicates and other components of the

ore to form the slag.

Formation of Steel
Oxygen diluted with Ar is used as the oxidizing agent.
When oxygen emerges from the converter, then all the
impurities have been oxidized and the iron is poured into
a ladle.

Question 3

Aluminium is the third most abundant element in the Earth’s crust, but does not occur as a metal
naturally, but it’s compounds are present to a greater or lesser extent in almost all rocks. Bauxite
is the principal mineral resources for aluminum making.

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a) Alumina is used for the production of aluminium metal. Bayer has invented one
hydrometallurgical refining process to produce alumina from Bauxite for Aluminum
extraction. Briefly describe this refining process to produce high purity anhydrous alumina
for Aluminum extraction? [50 Marks]

Refining process to produce high purity anhydrous alumina for aluminum extraction
Bayer process
• Bayer process is the process of extracting aluminum oxide from bauxite.
• Bauxite is powdered prior to the process.
• As aluminum oxide is amphoteric, it dissolves in sodium hydroxide solution.
• Al(OH)3(s) + NaOH(aq) → NaAlO2(aq) + 2H2O(l)
• In chemistry, an amphoteric species is a molecule or ion that can react as an acid as well
as a base
• The aluminate solution is filtered leaving behind the impurities.
• Seeding with aluminum hydroxide then reverses the reaction.
• The pure recrystallized aluminum hydroxide is then heated to produce aluminum oxide
(alumina).
• 2Al(OH)3 → Al2O3(s) + 3H2O(l)

Use of cryolite
• To make the electrolysis happen, alumina has to be in aqueous state.
• Alumina has a very high melting point of 2045°C.
• Cryolite (sodium hexafluoroaluminate (III), Na3AlF6) melts at about 950°C and the
solution can dissolve alumina sufficiently well.
• Considerable energy is still required to heat cryolite and dissolve alumina, but it is much
more energy-efficient than melting the alumina itself.

b) Aluminium is placed above the Carbon in reactivity series and hence Aluminium cannot be
extracted by reduction of its oxide with Carbon. Hall-Heroult has invented electrolysis
process to extract Aluminium from its oxide. Briefly describe the Hall- Heroult Aluminium
Extraction Process? [50 Marks]

Hall-Heroult process
Hall-Heroult process is an electrolysis process that extracts aluminum out of alumina
(aluminum oxide).
Overall cell reaction is
Alumina + carbon = aluminum + carbon dioxide

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 • Aluminum oxide has a high melting point (2054°C) (EXPENSIVE)
• Aluminum oxide will dissolve in molten cryolite which melts at “only” 959°C (Bayer
process)
• The molten liquid is put into a large chamber, the walls of which are connected to the
negative side of a circuit (cathode). Large positive electrodes (anodes) made of graphite
are lowered into the mixture.
• Aluminum oxide is an ionic compound. The positive aluminum ions drift to the negative
electrode (cathode) and the negative oxygen ions to the positive electrodes (anodes).
• At the cathode the aluminum ions gain electrons and become aluminum atoms.
4Al 3+ + 12e- = 4Al
• At the anodes the oxygen ions lose electrons and become oxygen atoms.
6O2- = 3O2 + 12e-
• The oxygen immediately reacts with the hot graphite to form carbon dioxide. This means
the graphite electrodes have to be replaced occasionally as they wear away.
• Molten aluminum is tapped from the bottom of the chamber

Question 4

a) State and explain Faraday’s laws of electrolysis. What is Hydrogen over voltage? Discuss
the role of hydrogen voltage in the electrolysis from aqueous solution.
[Marks 20]

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Faraday's First Law of Electrolysis states that the chemical deposition due to flow of current
through an electrolyte is directly proportional to the quantity of electricity (coulombs) passed
through it. i.e. mass of chemical deposition,

Where, Z is a constant of proportionality and is known as electrochemical equivalent of the

substance.

If we put Q = 1 coulombs in the above equation, we will get Z = m which implies that
electrochemical equivalent of any substance is the amount of the substance deposited on passing
of 1 coulomb through its solution.

This constant of passing of electrochemical equivalent is generally expressed in terms of

milligram per coulomb or kilogram per coulomb.

Faraday's second law of electrolysis states that, when the same quantity of electricity is passed
through several electrolytes, the mass of the substances deposited are proportional to their
respective chemical equivalent or equivalent weight.

Chemical Equivalent or Equivalent Weight

The chemical equivalent or equivalent weight of a substance can be determined by Faraday’s

laws of electrolysis and it is defined as the weight of that subtenancy which will combine with or
displace unit weight of hydrogen. The chemical equivalent of hydrogen is, thus, unity.
Since valency of a substance is equal to the number of hydrogen atoms, which it can replace or
with which it can combine, the chemical equivalent of a substance, therefore may be defined as
the ratio of its atomic weight to its valency.

Hydrogen overvoltage
Hydrogen overvoltage is the potential difference that can be found between an electrode and a
reversible hydrogen electrode within a single solution. This is where hydrogen (H2) undergoes
formation from ions of hydrogen.
Overvoltage typically occurs when equilibrium within a reaction does not take place. This is the
case when more powerful currents pass across the boundaries of metals and electrolytes or when
other electrodes are acquired.

b) In an electrolysis cell, a current was passed for 10 hours through two cells connected in
series. The first cell contains a solution gold salt and the second cell contains copper
sulphate solution. 19.70 g of gold was deposited in the first cell. If the oxidation number
of gold is +3, find the amount of copper deposited on the cathode in the second cell. Also
calculate the magnitude of the current in ampere.

(Atomic weight of Au= 196.967, Atomic weight of Cu= 63.546) [Marks 40]

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We know that

(Mass of Au deposited)/(Mass of Cu deposited)=(Eq.mass of Au)/(Eq.Mass of Cu)

Eq. mass of Au = 197/3; Eq. mass of Cu 63.5/2

Mass of copper deposited = (Mass of Au deposited) x (Eq.Mass of Cu) / (Eq.mass of Au)

= 19.70 x 63.5/2 /( 197/3)
= 19.70x63.5/2x 3/197
= 19.70 × 63.5/2 x 3/197 g = 9.525 g
Let Z be the electrochemical equivalent of Cu.
E = Z × 96500
or Z =E/96500=63.5/(2×96500)
Applying W = Z × I × t
T = 10 hour = 10 × 3600 second
9.525 = 63.5/(2×96500) × I × 10 × 3600
or I = (9.525 × 2 × 96500)/(63.5 × 10 × 3600
= 1,838,325/2,286,000 = 0.80417 amp

c) 30 g of molten SnCl2 is electrolyzed for sometime using inert electrodes until 0.180g of Sn
is deposited at the Cathode. No substance is lost during electrolysis. Find the ratio of the
masses of SnCl2: SnCl4 after electrolysis

(Atomic weight of Sn = 118.71, Atomic weight of Cl = 35.453) [Marks 40]

Suppose the chemical reaction occurring during electrolysis is

2SnCl2 --> SnCl4 + Sn
2×189.62 g 260.552 g 118.71 g
118.71 g of Sn is deposited by the decomposition of 379.24 g of SnCl2
So, 0.180 g of SnCl2 of Sn is deposited by the decomposition of
379.24/118.71×0.180=0.575 g of SnCl2
Remaining amount of SnCl2 = (30-0.575) = 29.425 g
379.24 g of SnCl2 produce = 260.552g of SnCl4

So 0.575g of SnCl2 produce = 260.552/379.24×0.575=0.395 g of SnCl4

Thus, the ratio SnCl2: SnCl4 =29.425/0.395, i.e., 74.49: 1

Question 5

a) Any material can be described as a ‘refractory,’ if it can withstand the action of abrasive
or corrosive solids, liquids or gases at high temperatures. The various combinations of
operating conditions in which refractories are used, make it necessary to manufacture a
range of refractory materials with different properties. Refractory materials are made in
varying combinations and shapes depending on their applications. What are the general
requirements of a refractory material used in industrial applications?
[Marks 20]

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General requirement of a refractory material used in industrial applications.

Materials that

• Withstand high temperatures and sudden changes

• Withstand action of molten slag, glass, hot gases etc
• Withstand load at service conditions
• Withstand abrasive forces
• Conserve heat
• Have low coefficient of thermal expansion
• Will not contaminate the load

b) Themal conductivity is one of the properties of the refractories. Brieifly discibe the
factors affecting on thermal conductyivity. [Marks 20]

Factors affecting thermal conductivity

• Thermal conductivity depends on the chemical and mineralogical composition and silica
content of the refractory and on the application temperature.
• The conductivity usually changes with rising temperature.
• High thermal conductivity of a refractory is desirable when heat transfer though brickwork
is required, for example in recuperators, regenerators, muffles, etc.
• Low thermal conductivity is desirable for conservation of heat, as the refractory acts as an
insulator.
• Additional insulation conserves heat but at the same time increases the hot face temperature
and hence a better quality refractory is required. Because of this, the outside roofs of open-
hearth furnaces are normally not insulated, as this could cause the roof to collapse.
Lightweight refractories of low thermal conductivity find wider applications in low
temperature heat treatment furnaces, for example in batch type furnaces where the low heat
capacity of the refractory structure minimizes the heat stored during the intermittent
heating and cooling cycles. Insulating refractories have very low thermal conductivity.

c) Insulating materials greatly reduce the heat losses through walls. Insulation is achieved by
providing a layer of material with low heat conductivity between the internal hot surface
of a furnace and the external surface, thus keeping the temperature of the external surface
low. Describe the five categories of Insulating materials may be classified into the
following groups [Marks 20]

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Insulating materials may be classified into the following groups:
• Insulating bricks
• Insulating castables
• Ceramic fiber
• Calcium silicate
• Ceramic coating

d) A furnace’s efficiency increases when the percentage of heat that is transferred to the stock
or load inside the furnace increases. The efficiency of the furnace can be calculated in two
ways such as direct method and indirect method. Following information were collected
from the furnace room of an industry, determine the efficiency of the furnace from direct
method. [Marks 40]

m = Weight of the stock = 8000 kg

Cp= Mean specific heat of stock = 0.16 kCal/kg oC
t1 = Final temperature of stock = 1330 oC
t2 = Initial temperature of the stock = 30 oC
Calorific value of oil = 10000 kCal/kg
Fuel consumption = 368 kg/hr

Initially calculate the heat output.

The heat output = m x Cp x ΔT
= 8000 kg x 0.16 x (1330 – 30)
= 1664000 kCal

The efficiency is:

= (heat input / heat output) x 100
= [(1664000 / (368 x 10000)] x 100 = 45.21 percent

The approximate heat loss is 100% – 45.21% = 54.78%

= 55.0%*/

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