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Course Objectives
Kwame Nkrumah University of
Science & Technology, Kumasi, Ghana

MSE 353 PYROMETALLURGY • Understand the fundamental concepts of pyrometallurgy

• Understand the concepts of materials and energy balance and its
application to industrial units

• Provide methodologies for producing metals (iron oxide to steel,

bauxite to aluminium and chalcopyrite to copper)

• Understand the physico-chemical reactions in pyrometallurgical

extraction of metals from ores
Ing. Anthony Andrews (PhD)
Department of Materials Engineering
• Select appropriate process routes for the refining of metals
Faculty of Mechanical and Chemical Engineering
College of Engineering [Link]

Website: [Link] 2

Course Outcomes Prerequisite

• Use Ellingham diagram in the extraction of metals • Knowledge of thermodynamics of materials (phase diagrams,
Gibbs free energy, physical chemistry)
• Gain general knowledge of the various methods available for the
production iron, copper and aluminium • Principles of material and energy balance across process units

• Design a system, component, or process to meet the desired needs

• Understand principles underlying processing-structure-properties-

performance

[Link] [Link]

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Forms of Assessment Course Outline

• Introduction
• Drying and Calcination, Roasting
Quizzes 5
• Principles of pyrometallurgy; reduction of metal oxides (use of
Assignments 10 Ellingham diagram)
Mid-Sem Exam 15
• Beneficiation of iron ores
Final Exam 70
– Blast furnace iron making, alternative iron-making processes,
Total 100 slag-metal reactions, steel making processes, refining
processes
• Pyrometallurgy of nonferrous metals
– Alumimium, Copper

[Link] [Link]

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Recommended Books Recovery of metals from ores

• Steel: processing, structure and performance: Kraus
• Ore: deposit that contains enough metal that we can
• Physical metallurgy of steels: Leslie extract economically.
– Most metals are found in minerals.
• Mechanical metallurgy: Dieter
– Most important ores are oxide, sulfide and carbonates.
• Fundamental of physical metallurgy: Verhoeven – Why?

• Introduction to the thermodynamics of materials: Gaskel

• Reducing agent converts the oxide to metal
• The chemistry of gold extraction, Ellis Horwood: Marsden, J.
and House, I.
• In pyrometallurgy, thermal energy is one of the important
• The extractive metallurgy of gold, Chapman and Hall,
London: Yannopoulos, J.C. inputs

[Link] [Link]

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Principal mineral sources of some common metals

Occurrence and Distribution of Metals
• Metallurgy is the science and technology of extracting
metals from minerals.

• Five important steps are involved:

o Mining (getting the ore out of the ground)
o Concentrating (preparing it for further treatment)
o Reduction (to obtain the free metal in the zero oxidation
state)
o Refining (to obtain the pure metal)
o Mixing with other metals (to form an alloy).

[Link]

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Principles of Pyrometallurgy Pyrometallurgy

• Pyrometallurgy: branch of extractive metallurgy
Pyrometallurgy: using high temperatures to obtain the free
• It involves the thermal treatment of minerals/ores resulting in
metal.
physical and chemical transformations in the materials to enable
recovery of valuable metals.
Four major steps are employed, all requiring high amount
• Pyrometallurgy requires energy input of thermal energy:

• Sources of energy include fossil fuel combustion, exothermic 1. Calcination is heating of ore to cause decomposition
reactions, electrical heat.
and elimination of a volatile product (CO2 or H2O):
• Elements that can be extracted by pyrometallurgical processes
include the oxides of less reactive elements like Fe, Cu, Zn, Cr, PbCO3(s)  PbO(s) + CO2(g)
Sn, Mn.
[Link] [Link]

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Pyrometallurgy Pyrometallurgy

2. Roasting: heating which causes chemical reactions 3. Smelting: melting process which separates chemical
between the ore (solid) and the furnace atmosphere reaction products into 2 or more layers.
(gas). • Slag consists mostly of molten silicates in addition to
• That is solid-gas reactions at elevated temperatures aluminates, phosphates, fluorides, and other inorganic
materials.

4. Refining: the treatment of crude metal product to

2ZnS(s) + 3O2(g)  2ZnO(s) + 2SO2(g)
improve its purity
2MoS2(s) + 7O2(g)  2MoO3(s) + 4SO2(g)

[Link] [Link]

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Principles of Calcination Principles of Calcination

• Calcination: a thermal treatment process and applied to ores and • Calcination is more endothermic than drying.
other solid materials for the following reasons:
1. thermal decomposition • Calcination involves the removal of:
2. phase transition • free water
3. to remove volatile fractions such as CO2 and H2O
• adsorbed water
• loosely bound water and
• Material is heated below the melting point in rotary kiln or
• strongly bound water
fluidized bed reactor.
• The last two are chemical in nature and represent phase
• Rate of calcination is governed by the supply of necessary heat of
transformations.
decomposition.
• Furnaces for calcination processes:
• Calcination is done in the solid state in the absence or limited
• shaft furnaces, rotary kilns, and fluidized bed reactors.
supply of air or oxygen
[Link] [Link]

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Applications of Calcination Heat/Energy Balance in Calcination

• To produce lime from CaCO3 in cement production • Calcination requires thermal energy.
• CaCO3 = CaO + CO2
• For calculation, we need several thermo-chemical values
• To cause decomposition of hydrated minerals
like heat of formation, specific heat, and heat content.
• 2Al(OH)3 = Al2O3 + 3H2O

• To cause decomposition of volatile matter contained in

petroleum coke

• Heat treatment of minerals to effect phase transformation

• Devitrification of glass materials

[Link] [Link]

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Assignment 1 (Due 17/09/18) Roasting

1. Calculate the heat energy required to calcine 1000 kg limestone of • Roasting consist of thermal gas-solid reactions.
composition 84% CaCO3, 8% MgCO3 and 8% H2O charged at
298K. Lime is discharged at 1178K and gases leave at 473K. • It includes oxidation of metal sulphides to give metal
oxides and sulphur dioxide.
2. It is desired to produce 10 [Link] lime from calcinations of
CaCO3 (pure) in a rotary kiln. Producer gas of composition 7.2%
CO2, 1.6% O2, 16.6% CO and 74.6% N2 is combusted with 20% • It is strongly exothermic process
excess air to obtain the desired temperature in the kiln. The
limestone and air are supplied at 298K, whereas producer gas is • Roasting is carried out below melting points of sulphides
heated to 900K. Lime is discharged at 1200K and at 500K. and oxides involved (i.e 900 – 1000oC)
Calculate the amount of the producer gas (1atm and 273K).

Note: Use thermochemical values from literature

[Link] [Link]

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Roasting Types of Roasting

Typical examples are: • The solid product from roasting is often called “calcine”

• When all sulphides are converted into oxides - dead roasting

ZnS + 1.5O2 = ZnO + SO2 ΔH298 = -459.8 kJ/mol • Example: extraction of Zn from its ore

2FeS2 + 5.5O2 = Fe2O3 + 4SO2 ΔH298 = -1713.8 kJ/mol • When less than required amount of oxygen is supplied to fully
oxidize the feed (Sulphur is partially removed) – partial roasting
Cu2S + 1.5O2 = Cu2O + SO2 ΔH298 = -397.1 kJ/mol
• When sulphide is converted into sulphate as sulphate can be
In addition, other reactions may take place: formation of SO3 and dissolved easily into an aqueous solution – sulphating roasting
metal sulphates and formation of complex oxides such as ZnO.Fe2O3. • Typically used for hydrometallurgical extraction of lead sulphide ores

Both reactants and products are in solid states. • Roasting can be carried out in a number of furnaces, including
multiple hearth furnace, fluid bed roasting.
[Link] [Link]

Sources of Thermal Energy for Roasting Heat of formation of

some compounds
1. Heat of reaction:
• S → SO2 ≈ -70940 kcal/[Link]
• S → SO3 ≈ -93900 kcal/[Link] Calculate the heat released for
the following reactions:
• Several oxidation reactions possible (release heat):
• Fe – Fe2O3
ZnS + 1.5O2 = ZnO + SO2
• FeS – FeO
• ZnS – ZnO

• Calculated from heat of formation.

[Link] [Link]

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Sources of Thermal Energy for Roasting Sources of Thermal Energy for Roasting
2. Combustion of fuel: 2. Combustion of fuel:
• Ore concentrate is mixed with solid fuel • Fuel characterized by calorific value (CV – kJ/kg)
• Solid fuels contain combustible mass (mainly carbon,
• The Dulong’s formula gives the heat of combustion
hydrogen and Sulphur) and non-combustible mass (water and
ash) as:
• Fuel are divided according to the physical state:
• Solids (coal and coke)
• Liquid (fuel oil) where NCP is the net calorific power, and C, H, O, S and W
represent the mass percent of the four elements and moisture in the
• Gaseous (CO, H, hydrocarbons, hydrogen sulphide, etc)
fuel.

[Link] [Link]

Sources of Thermal Energy for Roasting Sources of Thermal Energy for Roasting
2. Combustion of fuel: 2. Combustion of fuel:
• For gross calorific power (Dulong’s formula) • Determination of CV of gaseous fuels
GCP • Combustion components include CO, H2, NH3, etc
• O2, CO2, N2 are diluents

Question
Question
Write combustion equations for CH4, C2H6 and C3H8 and
Calculate the gross calorific value for a coal with the following calculate the heat of combustion values.
analyses:
74%C; 6%H; 1%N; 9%O; 0.8%S; 2.2% moisture and 8% ash
[Link] [Link]

Sources of Thermal Energy for Roasting

2. Combustion of fuel:
• Amount of air
• In roasting, air is used for the oxidation of sulphides as
well as combustion of coal
• Calculation of amount of air (theoretical air) is important
• Consider the following reactions:
C + O2 = CO2
H2 + 0.5O2 = H2O
ZnS + 1.5O2 = ZnO + SO2
PbS + 1.5O2 = PbO + SO2
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Sources of Thermal Energy for Roasting Sources of Thermal Energy for Roasting
2. Combustion of fuel:
2. Combustion of fuel:
• Amount of air • Amount of air
• For the purposes of combustion calculations the • Ultimate analysis gives the percentage by mass of each
composition of air is approximated as a simple mixture of element present in the fuel.
oxygen and nitrogen:
• An example of an ultimate analysis of a liquid fuel (oil)
• oxygen = 21% might be :
• nitrogen = 79%
Component % by mass
Carbon (C) 86
Hydrogen (H2) 14

[Link] [Link]
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Sources of Thermal Energy for Roasting Sources of Thermal Energy for Roasting
2. Combustion of fuel: 2. Combustion of fuel:
• Amount of air • Amount of air
• Each constituent is considered separately via its own • Similarly
combustion equation. H2 + ½ O2 → H2O
For the carbon:
2kg 16kg 18kg
C + O2 → CO2
12kg 32kg 44kg or per kg of fuel
16 18
or for 1 kg of fuel 0.14  0.14   0.14  (kg)
2 2
32 44
0.86  0.86  0.86  (kg) • In order to burn the hydrogen content of the oil 1.12
12 12
kg oxygen are needed and 1.26 kg water is formed.
• So each kg of oil requires 2.29 kg oxygen for combustion of its
carbon and produces 3.15 kg CO2 as product.
[Link] [Link]

Sources of Thermal Energy for Roasting Sources of Thermal Energy for Roasting
2. Combustion of fuel: 2. Combustion of fuel:
• Amount of air • Amount of air
 The total oxygen requirement is thus (2.29 + 1.12) • We can now establish that 3.41 kg oxygen, which
or 3.41 kg. is the stoichiometric requirement, will be
A given quantity of air consists of 21% by volume associated with:
of oxygen. 0.767
3.41  11.23 kg nitrogen
0.233
 We can simply transform to a mass basis thus:
Component vol fraction(vf) vf × MW Mass fraction
Oxygen 0.21 6.72 6.72
 0.233
28.84
• The stoichiometric air-to-fuel ratio is thus 3.41 +
22.12 11.23 = 14.6 : 1
Nitrogen 0.79 22.12  0.767
28.84
[Link] [Link]

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Assignment 2 (Due 17/09/18)

1. A fuel has the following composition by mass; carbon 86% and
hydrogen 14%. Calculate the theoretical air supply per kg of fuel.
2. A fuel has the following composition by mass; carbon 86%,
hydrogen 11.75%, Oxygen 2.25%. Calculate the theoretical air
supply per kg of fuel and the mass of products of combustion per
kg of fuel.
3. A slurry of chalcopyrite is continuously fed into a fluid bed roaster.
Enough air is supplied to the roaster. The slurry containing 10%
water is continuously fed into the roaster at a rate of 12,000kg/h.
a) Write a balanced equation for the reactor.
b) Calculate the amount of air required.
c) Calculate the amount of gas produced.
d) Amount of solid products formed.
[Link]