UNIVERSITY OF MINES &

TECHNOLOGY, (UMaT), TARKWA

MINERALS ENGINEERING
DEPARTMENT
EXTRACTIVE METALLURGY (MN 270)
Compiled by

Dr J J K Gordon
Revised by

Emefa Awuye Desire

June, 2024
 Course Aims and Objectives
The main aim of this course is;
• To prepare students to become competent mining
engineers by them with extractive metallurgical processes
essential in mineral processing.

Course objectives include:

• To educate students on extractive metallurgy

• To introduce students to various branches and process

involved in extractive metallurgy

• To encourage students to make good use of the

knowledge acquired during this lectures in their
profession as mining engineers
 Expected Outcome of the Course
At the end of the course, students are expected to:

• Gain good knowledge of extractive metallurgy

• Apply the principles learnt during course delivery in

practical work both as a student and a professional
engineer
 Course Presentation and Assessment
• This course will be delivered through lectures with
supporting lecture notes and practical work at the
laboratory to aid students’ understanding of the
course
• Assignments will be given after each chapter to test
students’ understanding.
• These assignments should be presented to the
lecturer before the commencement of a new chapter

• Students will be assessed through:

✓ Continuous Assessment 40%
✓ Final exams 60%
• The continuous assessment will comprise class
attendance, assignments, class test, announced and
unannounced quizzes
 Course Content
1. Chapter 1 – Introduction and overview of
extractive metallurgy

2. Chapter 2 – Hydrometallurgy

3. Chapter 3 – Pyrometallurgy

4. Chapter 4 – Electrometallurgy

5. Chapter 5 – Extractive metallurgy of gold

6. Reference
 CHAPTER ONE

INTRODUCTION AND
OVERVIEW
 CHAPTER ONE - INTRODUCTION
• Extractive metallurgy deals with metallurgical
processes that target the chemical make-up of the
ore or concentrate in order to liberate, recover and
extract the mineral of interest.

• Thus, comminution is carried out to reduce the ore

to sizes fine enough to liberate the mineral of
interest after which concentration is conducted to
upgrade the ore.

• However, some of the minerals, due to the

fineness in size, do not respond favourably to the
physical methods of concentration.

• There are even some minerals, which are not

liberated at all by any of the mechanical methods
of mineral processing.
 CHAPTER ONE - INTRODUCTION
• Hence, extractive metallurgical processes are
employed to fully liberate, recover and extract the
mineral of interest.

• In most cases of metal recovery, the marketable

product is always yielded after extractive
metallurgy.

• Extractive metallurgy has three main branches;

pyrometallurgy, hydrometallurgy and
electrometallurgy

• This course therefore looks at the basic principles

of extractive metallurgy for mining students.

• The fundamentals of extractive metallurgy of gold

are also considered since gold is the mineral
mostly exploited in Ghana.
CHAPTER ONE – BRANCHES IN EXTRACTIVE METALLURGY
PYROMETALLURGY
• Pyrometallurgy is a branch of extractive metallurgy
which deals with the extraction of metals from their
ores by thermal methods.

• Thus, it employs heat in the treatment of minerals and

metallurgical ores and concentrates to bring about
physical and chemical transformations in the materials
to enable recovery of valuable metals.

• Pyrometallurgical treatment may produce saleable

products such as pure metals, or intermediate
compounds or alloys, suitable as feed for further
processing.

• Pyrometallurgical processes are generally grouped

into one or more of the following categories: Drying,
Calcining, Roasting, Smelting and Refining.
CHAPTER ONE – BRANCHES IN EXTRACTIVE METALLURGY
PYROMETALLURGY
• Most of the processes require energy input to
sustain the temperature at which the process
takes place.

• The energy is usually provided in the form of

combustion of carbonaceous fuel or from
electrical heat.

• Carbonaceous fuels are the main sources of

energy in pyrometallurgy and the furnaces that are
used are lined with refractories
CHAPTER ONE – BRANCHES IN EXTRACTIVE METALLURGY
HYDROMETALLURGY
• Hydrometallurgy is a branch of extractive metallurgy
that extracts metals from ores by aqueous methods.

• In hydrometallurgy, a condition is developed that helps

to extract the mineral of interest leaving the gangue
mineral by making use of a suitable extractant (or
solvent).

• It involves three (3) processes or steps namely;

✓ Leaching (e.g. Agitation, Heap, Dump and In-situ
Leaching)
✓ Solution Purification (e.g. Adsorption, Ion
exchange, Ion flotation, Solvent extraction and
Precipitation)
✓ Metal Recovery (e.g. Crystallization, Adsorption,
Electrolysis and Precipitation)
CHAPTER ONE – BRANCHES IN EXTRACTIVE METALLURGY
ELECTROMETALLURGY
• Electrometallurgy is the branch of electrochemical
engineering, which deals with the extraction and
refining of metals from aqueous and molten
solutions.

• It uses the medium of electricity and is based on

the principle of electrochemistry
 CHAPTER TWO

HYDROMETALLURGY
 CHAPTER TWO – INTRODUCTION
• Hydrometallurgy is a branch of extractive metallurgy
that extracts metals from ores by aqueous methods.

• In hydrometallurgy, a condition is developed that helps

to extract the mineral of interest leaving the gangue
mineral by making use of a suitable extractant (or
solvent).

• It involves three (3) processes or steps namely;

• Leaching (e.g. Agitation, Heap, Dump and In-situ
Leaching)
• Solution Purification (e.g. Adsorption, Ion
exchange, Ion flotation, Solvent extraction and
Precipitation)
• Metal Recovery (e.g. Crystallization, Adsorption,
Electrolysis and Precipitation)
 CHAPTER TWO – LEACHING
• It is the process of selectively dissolving a desired
soluble constituent (e.g. gold) from a solid
material (e.g. ore, concentrate, calcine, matte) by
means of a solvent (lixiviant) to produce a
concentrated pregnant solution from which the
dissolved metal can be recovered

• The pregnant solution contains some impurities

that have been co-leached and there is the need to
get rid of them through solution purification to
obtain a pure solution from which the metal can be
recovered.
CHAPTER TWO – LEACHING
CHAPTER TWO – LEACHING REAGENTS
Lixiviants are salts/liquids used in mineral
dissolution. Examples of these are:
• Water: for leaching common salt, calcines from
sulphide roasting or chloridised roast. In lead
sulphide ores water can leach sulphide under high
pressure to produce sulphates which act as
lixiviant for leaching lead at high temperature.

• NaCN: To leach Au and Ag in a complex mediated

oxidising leaching.

• NaCO3: To leach Uranium.

• Acidified ferric sulphate: To leach sulphides

especially copper sulphides.
CHAPTER TWO – LEACHING REAGENTS
Lixiviants are salts used in mineral dissolution.
Examples of these are:
• NaCl: To leach lead sulphate.

• Dilute H2SO4: To leach oxidised Cu ores and MnO2.

• NaOH: To leach bauxite.

• Ammonia: To leach Cu ores; mostly used when

acid consuming gangues are present. Though NH3
has high vapour pressure it leads to losses and
forms complex with copper (Cu).
CHAPTER TWO – CHOICE OF LIXIVIANT
Depending on the chemistry of the material to be
leached in association with the leaching methods
various reagents could be used in the leaching of ores.
The choice of reagents depends on the following:

• Chemical and physical nature of the material to be

leached.

• Selectivity: the reagent should dissolve only the

mineral of interest and not the gangue.

• Corrosive nature of the reagent: it should not be so

corrosive to attack the tanks and other accessories

• Toxicity: it should not be toxic. However, if its vapour

pressure is low and toxic effects can be controlled,
then it could be acceptable.
CHAPTER TWO – CHOICE OF LIXIVIANT
• Stability: the reagent should not break down or
polymerise

• Cost: it should not be too expensive. It should be

cost effective e.g., both cyanide and thiourea can
be used to leach gold. Thiourea is not poisonous
but its price is about ten times that of CN and its
concentration is 2 kg/ton as against 0.5 kg/ton of
CN.

• Regeneration: it should have the ability to go

through restoration and re-use. This helps cut
down cost and decrease environmental impact.

• Viscosity: aqueous solutions of the reagent

should be able to flow freely. Viscosity modifiers
may be used if the slurry does not respond well.
CHAPTER TWO – CHOICE OF LIXIVIANT
• Capacity: The reagent should have a high
capacity, that is, a small amount should be able to
leach large quantities of ore.

✓ Salts used in leaching may be that of a weak

base and strong acid or a strong base and a
weak acid. Such salts hydrolyse in aqueous
media.
✓ To counterbalance the effects of hydrolysis, pH
modifiers are introduced.
✓ For example sodium cyanide is the salt of a
strong base and weak acid and undergoes
hydrolysis to produce HCN, which aside
leading to solution losses, is a very toxic gas.
✓ Studies show that in moist air or aqueous
solution more than 50 % of NaCN exist as HCN
gas below the pH of 9.5.
CHAPTER TWO– CHOICE OF LIXIVIANT
✓ Some minerals like gold cannot dissolve in the
absence of oxygen or other oxidising agents.
For such minerals hydrogen peroxide or oxygen
(may be from the air) should be introduced
during leaching

100

80
Molar Fraction (%)

60

HCN-
40 CN-

20

0
0 2 4 6 8 10 12 14 16

pH
CHAPTER TWO – FACTORS AFFECTING LEACHING RATE
• Pulp density: Rate of leaching increase with
decreasing pulp density.

• Particle size: Generally the finer the particle size,

the higher the surface area exposed for contact
and thus the faster the leaching rate.
✓ Coarse particle take longer time to leach
✓ However, over-grinding must be avoided since it
produces large amount of fines that complicate
solid liquid separation; gangue material is also
activated when ground too fine.
✓ Over-grinding also increases grinding cost and
thus milling cost.
CHAPTER TWO – FACTORS AFFECTING LEACHING RATE
• Temperature: Generally, leaching rate increases
with increase in temperature. It is a linear
increase, anyway since leaching reaction is
diffusion controlled. Excessive temperatures
should however be avoided since it may lead to
co-leaching of gangue minerals.

• Pressure: Leaching could be carried out under

atmospheric or higher pressures. Under
atmospheric conditions it is termed open leaching,
otherwise it is pressure leaching. Higher
pressures increase rate of leaching.

• Concentration: Rate of leaching increases with

increasing concentration of lixiviant at constant
feed rate. However, very high concentrations lead
to co-leaching of gangue materials. This causes
purification problems.
CHAPTER TWO – FACTORS AFFECTING LEACHING RATE
• Agitation: The primary aim of agitation is to keep
the particles in suspension and expose them to
the solvent as much as possible. It also increases
the diffusion rate by decreasing the interfacial
boundary layer.
CHAPTER TWO – LEACHING TECHNOLOGY
The leaching process can be a continuous or a
batch process.

• For Batch Leaching:

✓ the material is allowed enough time to leach

completely before it is discharged for
separation

✓ It is relatively expensive and is normally used

in the lab for test work, e.g., bottle rolling.
CHAPTER TWO – LEACHING TECHNOLOGY
• For Continuous Process:
✓ leaching is done in series where an ore in one
tank is leached to a certain extent before it
enters another and by the time it gets to the
last tank the mineral is considered to have
been leached to a level where separation can
be done.

✓ It is relatively cheaper and used for large

quantities of high-grade ore.

✓ In practice ores are leached in two ways;

choice of leaching method is closely linked
with the grade of ore and the rate of
dissolution of mineral values in the lixiviant.
CHAPTER TWO – LEACHING TECHNOLOGY
Agitation leaching
• This deals with high grade ores and is used where
finely divided ore is mixed with water and agitated
in a suitable vessel.

• The agitation is done by mechanical impellers or

pneumatic means these help to suspend the
mineral particles thus exposing them to the
influence of the lixiviant.

• The leaching time here is shorter; it can be 16-36

hours.
CHAPTER TWO – LEACHING TECHNOLOGY
Non-agitation leaching
• It deals with low-grade ores.

• These systems are fixed bed reactors (heap, vat,

dump, in-situ), where lixiviant is made to leach the
ore by percolation.

• It is important that the ore is permeable to the

lixiviant, and the technology cheap for the process
to be viable.
CHAPTER TWO – Types of Non-Agitation Leaching
In-situ leaching, Solution mining or leaching in
place
• The grade of the ore is too low to justify mining
and transportation expenses.

• It is thus simply shuttered and left in place.

Lixiviant is pumped into the ground to leach the
ore, whilst pregnant solution is pumped out.

• It is an important requirement that the underlying

rock be of impervious nature.

• Leaching time may be in years

CHAPTER TWO – Types of Non-Agitation Leaching
In-situ leaching, Solution mining or leaching in
place
CHAPTER TWO – Types of Non-Agitation Leaching
Dump Leaching
• The grade here is too low to justify crushing
expenses, though higher than in-situ leaching.

• The ore is mined transported and dumped (without

crushing) on a suitable site (impervious pad);
lixiviant is sprinkled to leach the ore.

• This may take months to years

CHAPTER TWO – Types of Non-Agitation Leaching
Heap Leaching
• The grade of the ore is too low to justify grinding
expenses

• The ore is mined, crushed to suitable size and

heaped on an impervious terrain sloped at an
angle of about 70 to ensure flow under gravity.

• Lixiviant is sprinkled on the heap to percolate

through the ore and leach metal values.

• The pregnant solution is collected at the base for

subsequent purification and metal recovery.
CHAPTER TWO – Types of Non-Agitation Leaching
Heap Leaching

• The solution collected may be circulated several

times to increase the grade or get the required
grade for purification and/or recovery.

• The ore must be porous to ensure proper

dissolution and extraction of mineral values.
CHAPTER TWO – Types of Non-Agitation Leaching
Heap Leaching
• The fines produced should be screened off in:

✓ non-agglomeration leaching or
✓ agglomerated (agglomeration heap leach).

• This is done to ensure proper percolation through

the heap, avoid retention and channelling of
lixiviant and offset filtration of too much fines in
pregnant solution.

• Once agglomerated, curing time of up to about 72

hours is allowed.
CHAPTER TWO – Types of Non-Agitation Leaching
Heap Leaching
• It can take up to about 40 days. Heaps can be
several meters in length and about 50 m high

• Heap leaching is cheaper – there is no filtration,

needs less attention – few people can man it, it
has higher retention time due to several cycles,
low recovery – 70-80% about - high losses,
retention of values in voids due to high capillary
action
CHAPTER TWO – Types of Non-Agitation Leaching
Heap Leaching – Types Leach Pads
• Reusable pad – Exhausted ore is unloaded for
disposal and fresh ore heaped on pad.
CHAPTER TWO – Types of Non-Agitation Leaching
Heap Leaching – Types Leach Pads
• Valley-Leach Method – The ore is heaped behind a
retaining wall built in a valley.
CHAPTER TWO – Types of Non-Agitation Leaching
Heap Leaching – Types Leach Pads
• Expanding pad – Exhausted heap flattened and
fresh ore added, or abandoned and new pads
prepared for fresh ore
CHAPTER TWO – Types of Non-Agitation Leaching
Heap Leaching – Leach Pad Design
• Firm ground to withstand the weight of material.
• Removal of top soil and vegetation (kept for re-
vegetation)

• Grading, filling and compacting of the ground.

• Inclination lengthwise and sideways.

• Uniform strength of the entire area – avoid points

of stress concentration and tearing of layer.
• The prepared floor is laid with impermeable layer,
asphalt, concrete, compacted clay or HDPE. In the
case of HDPE – joints must be welded. The pad
may be double to reduce seepage during
perforation.
CHAPTER TWO – Types of Non-Agitation Leaching
Vat Leaching
• This is similar to heap leaching, but in this case
the crushed ore is submerged in large tanks filled
with lixiviant.

• The ore must be porous and uniformly sized.

Fines and slimes must also be checked.
CHAPTER TWO – Types of Non-Agitation Leaching
Vat Leaching - Advantages

• To reduce leaching time, increase gold extraction

and gold content of the pregnant solution.

• Smaller plant site per ton of ore

• Closer metallurgical control

• Lower capital and operating cost

 CHAPTER TWO – Agitation Leaching
This is used for
✓ High-grade ore
✓ Fast leaching ore (can take 24 h)
✓ Pre-treated ore
✓ Slimy ore
• The high-grade ore is mined, crushed, ground finely to
liberate the leachable ore. The pulp is conditioned and
pumped into a suitable vessel for leaching under
agitation. This type is referred to as open leaching with
100oC as the maximum attainable temperature as a
result of inter-reaction with atmospheric pressure.

• Agitation is done to suspend mineral particles and

expose them to the influence of the lixiviant. The type
practiced in the mine is the continuous leaching where
the ore move from one tank to another as leaching
goes on.
CHAPTER TWO – Agitation Leaching
 CHAPTER TWO – Agitation Leaching
Pressure Leaching

• This is a special case of agitation leaching used

normally for ores like sulphide minerals
(asenopyrite, pyrite, etc) that require high
temperatures and pressures.

• Pressure leaching is done in enclosed vessels,

which can retain heat and built-up pressure.
Example is the autoclave – steel vessels with very
thick refractory walls to withstand high pressure
and temperature.
 CHAPTER TWO – Agitation Leaching
Pressure Leaching

• Though the reaction is faster than open leach, it is

relatively expensive due to the need to set up
equipment to take care of too high temperature
and pressure.

• The grade of the ore does necessarily have to be

high enough to pay for the expenses to make
profit.

• Autoclaves are lined with anti-corrosion materials

like Pb since H2SO4 acid is produced and heat
resistant material like titanium all of which make
the process expensive.
CHAPTER TWO– SOLUTION PURIFICATION/METAL
RECOVERY
• After leaching, the pregnant solution containing
about 2 – 15 ppm and 1 ppm from agitation and
non-agitation leaching respectively is purified to
get rid of unwanted substances that were co-
leached.

• The extent of purification will depend on the level

of impurities present in the solution.

• The pregnant solution can also be purified

(concentrated further) to increase the grade
 CHAPTER TWO – SOLUTION PURIFICATION/METAL
RECOVERY

METAL
RECOVERY

SOLVENT
ADSORPTION CRYSTALLISATION ION EXCHANGE CEMENTATION
EXCHANGE
CHAPTER TWO – SOLUTION PURIFICATION/METAL
RECOVERY
ADSORPTION
• This is the concentration or purification of ions or
molecules of mineral of interest in a liquid phase onto
a substance in a solid phase.

• The solid phase is called adsorbent and the liquid

phase is called the adsorbate.

• Being a surface phenomenon, the rate of adsorption

depends on the surface area of the adsorbent (solid;
e.g. activated carbon, Biomass and inorganic
materials like clay, zeolite etc).

• There are three types of adsorption:

CHAPTER TWO – SOLUTION PURIFICATION/METAL
RECOVERY
✓ Exchange adsorption – This is as a result of
electric attraction between adsorbate (liquid or
component) and adsorbent due to difference in
charges. The higher the charge, the greater the
attraction.

✓ Physical adsorption – This is due to weak

forces or Vander Waal forces between
molecules. The position of adsorbed molecule
is not fixed and it can be multi-layered. It is also
reversible (can be desorbed).

✓ Chemical adsorption – This is due to much

stronger forces like chemical bonds. Adsorbate
and adsorbent surfaces share electrons. It
forms a monolayer and is irreversible.
CHAPTER TWO – SOLUTION PURIFICATION/METAL
RECOVERY
CEMENTATION
• This is the process of precipitating a metal ion in
solution by the use of another metal. The
precipitated metal cements on the foreign metal.

• This reaction is electrochemical and works on the

principle that metals with more positive electro-
potential or oxidation will pass into solution and
cement a metal ion with a less positive potential.

• For example finely divided copper is displaced by

an iron scrap and cadmium can also be displaced
by zinc as shown;
CHAPTER TWO – SOLUTION PURIFICATION/METAL
RECOVERY

2+ 2+
Cu + Fe → Cu + Fe o

2+
OHC Fe → Fe + 2e
2+
RHC Cu + 2e → Cu o

Cd ++ + Zn ° →Cd ° + Zn ++
 CHAPTER THREE

PYROMETALLURGY
CHAPTER THREE – INTRO TO PYROMETALLURGY
• Pyrometallurgy consists of the thermal treatment
of minerals and metallurgical ores and
concentrates to bring about
✓ Physical and
✓ Chemical transformations in the materials to
enable recovery of valuable metals.

• Pyrometallurgical treatment may produce saleable

products such as pure metals or intermediate
compounds or alloys suitable as feed for further
processing.
 CHAPTER THREE – PROCESSES IN PYROMETALLURGY
• Pyrometallurgical processes are generally grouped into one
or more of the following categories:
✓ Drying
✓ Calcination
✓ Roasting
✓ Smelting
✓ Refining
• Most of the processes require energy input to sustain the
temperature at which the process takes place.
• The energy is usually provided in the form of combustion of
carbonaceous fuel or from electrical heat.
 CHAPTER THREE – FUEL IN PYROMETALLURGY
Definition of Fuel:
• Fuel is any material that is burned or altered in order to
obtain energy to produce heat that is enough to be
applied in industrial operation.

• Fuel releases its energy either through a chemical

reaction such as combustion or nuclear means, such as
nuclear fission or nuclear fusion.

• An important property of a useful fuel is that its energy

can be stored and released only when needed.
 CHAPTER THREE – FUEL IN PYROMETALLURGY
• Examples: Methane, Petrol, Wood, Coal, etc.

• The major sources of energy used in pyrometallurgy

are electrical energy and by combustion of
carbonaceous fuels
 CHAPTER THREE – TYPES OF FUELS
Electrical Energy:

• This is generated mainly from waterfall or

waterpower, burning of carbonaceous fuels
(e.g. coal, oil,) and by uranium fission in a
nuclear reactor.

• It is mainly generated by public utility

companies and made available for purchase by
domestic users and industries.
 CHAPTER THREE – TYPES OF FUELS
Carbonaceous Fuels:

• This is any substance that may be burned rapidly

enough in air during the process of combustion
(oxidation) to generate heat capable of being
applied in industrial operation.

• Examples of fossil fuels available for industrial

use are coal, crude oil and natural gas, which are
primary sources, and their products
 CHAPTER THREE – TYPES OF FUELS
Classification Carbonaceous Fuels:
Primary Fuel
Coal
(obtained directly
from the earth
crust
Crude oil
Carbonaceous
Fuels
Secondary Fuel –
synthetically Coke, Charcoal,
obtained from Kerosene, etc.
primary fuels
 CHAPTER THREE – TYPES OF FUELS
Classification Carbonaceous Fuels:
• Coal is a fossil fuel formed in ecosystems where plant
remains were preserved by water and mud from
oxidization and biodegradation, thus sequestering
atmospheric carbon.
• Coal is a readily combustible black or brownish-black rock

• It is composed primarily of carbon and hydrogen along

with small quantities of other elements, notably sulfur.

• Coal is extracted from the ground by coal mining, either

underground mining or open pit mining (surface mining).
 CHAPTER THREE – TYPES OF FUELS
For coal to be qualified as a good coking coal it must
possess the following properties:

• Volatile matter component should be 22-33% to make

it hard, strong and chemically unreactive coke that can
withstand crushing in the furnace.

• Ash content should be less than 10% - as ash from coal

is transferred to coke in coking.
 CHAPTER THREE – TYPES OF FUELS
For coal to be qualified as a good coking coal it must
possess the following properties:

• Sulphur content should be less than 2 % since excess

sulphur remains with coke and readily associates with
some metals present and its subsequent removal is
expensive.
 CHAPTER THREE – TYPES OF FUELS
Classification Carbonaceous Fuels:
• Coke is a solid carbonaceous residue derived from low-ash,
low-sulfur bituminous coal from which the volatile
constituents are driven off by baking in an oven without
oxygen at temperatures as high as 1000°C (1832°F) so that
the fixed carbon and residual ash are fused together.

• Metallurgical coke is used as a fuel and as a reducing agent

in smelting iron ore in a blast furnace

• Coke from coal is grey, hard, and porous

 CHAPTER THREE – TYPES OF FUELS
Classification Carbonaceous Fuels:
• Some coke making processes produce valuable by-
products that include coal tar, ammonia, light oils,
and "coal gas”.

• Petroleum coke is the solid residue obtained in oil

refining, which resembles coke but contains too
many impurities to be useful in metallurgical
applications
 CHAPTER THREE – TYPES OF FUELS
Fuels may be sub grouped into:

• Solid fuels – coke, coal, charcoal, firewood

• Liquid fuels – petrol, diesel, kerosene, crude oil,

• Gaseous fuels have easy distribution and easy control

of composition and calorific value.
 CHAPTER THREE – TYPES OF FUELS
Fuels may be sub grouped into:

• Natural Gas Fuel - drawn from gas deposits in the earth

normally in connection with hydrocarbons e.g., CH4 and Ethane.

✓ Artificial Gas Fuel – Oxyacetylene, coke oven gases

(methane, H, CO), Blast Furnace gas (CO, CO2, N), refinery
gas (butane, propane), etc.

✓ Butane and propane can be liquefied with petroleum to

produce bottled gas.
 CHAPTER THREE – TYPES OF FUELS
GROUP ASSIGNMENT 1

Discuss the environmental effects of secondary

fuel production and suggest ways to avert its
adverse impact on the environment
 CHAPTER THREE – COMBUSTION
• This is used to define burning of fuel – oxidation of fuel
at such a rate as to cause an appreciable rise in
temperature (of several hundreds of degrees) in the
substance involved in the process.

• The combustion of a fuel is a chemical reaction of the

fuel or certain constituents of it with oxygen, usually
accompanied by a release of energy in the form of heat.

• The combustible elements are carbon, hydrogen,

sulphur or their compounds
 CHAPTER THREE – COMBUSTION
Note the following Definitions
• Flue Gases are the gaseous products produced after
combustion.

• Ash is the non-combustible inorganic matter in solid fuel,

which is the solid residue that remains after all the
combustible, and volatile materials have been burnt off. It
contains silicon, lime, ferric oxides, etc.

• Complete Combustion is the burning of a fuel in excess air

in excess of up to 50% of the theoretical air. Combustion
can be complete or incomplete depending on the amount
of oxygen or air available.
 CHAPTER THREE – COMBUSTION
• Ignition Temperature is the temperature at
which combustion begins. It depends on a
number of factors, for example the ignition
temperature of a
✓ Solid fuel depends on particle size, nature of surface
and porosity.

✓ That of a liquid fuel depends on the vapour pressure

of the liquid and the proportion of vapour to air
needed to form an ignitable mixture.

✓ With gaseous fuels, ignition temperature varies

directly with concentration and decreases with
increasing pressure.
 CHAPTER THREE – COMBUSTION
• Moisture Content of a fuel is that matter content
of the substance which can be removed by
evaporation.

• Calorific Value is the heat resulting from a unit

quantity (mass or volume) of fuel. It has a direct
relation with the chemical composition of the fuel;
the standard unit for heating values is now joules
per kilogram or cubic metre.
CHAPTER THREE – DESIRABLE PROPERTIES OF FUEL
• Easy ignition

• High calorific value

• Suitable and controllable combustion

rate characteristics

• Low and controllable impurity content

• Low smoke emission

CHAPTER THREE – DESIRABLE PROPERTIES OF FUEL
• Availability

• Cost effectiveness

• Uniformity in property and consistency.

 CHAPTER THREE – AGGLOMERATION
• It is a process by which fine grain materials are
converted into coarser lumps.

• The comminution of ore to produce material of

reasonable particle size for subsequent extraction
processes inevitably lead to the production of too fine
particles being part of the product, which needs to be
reformed into bigger particles.

• These extremely fine particles are not desirable since in

roasting, for example, they can block air spurges and
also lead to caking and losses of dust-laden minerals.
 CHAPTER THREE – AGGLOMERATION
• Also in leaching /hydrometallurgy, too much
fines may lead to sliming, difficulty in
percolation, problems in solid-liquid separation,
etc.

• It is therefore necessary to agglomerate fines or

bridge them to produce bigger aggregates.
Agglomeration therefore is the process used in
re-forming fine particles into larger lumps.
CHAPTER THREE – AGGLOMERATION PROCESSES

Agglomeration Processes
Briquetting

Nodulising

Pelletising

Sintering
 CHAPTER THREE – AGGLOMERATION
BRIQUETTING
• The feed is mixed well with water and usually binding agents.

• Binders may be inorganic - clay, lime, cement and metal salt, or

organic – oil, tar pitch, etc.

• Before agglomeration, the material should have a certain

amount of moisture content depending on the type of material
and the binder.
✓ When lime or cement is used as a binder the briquette may
be hardened at room temperatures (curing).
✓ When clay is used as a binder, the briquette is hardened at
elevated temperature by firing (e.g. in a kiln).
 CHAPTER THREE – AGGLOMERATION
BRIQUETTING
• Briquetting may be done without a binder in
which case the hardening is done by firing.

• It may also be done by first heating the substance

to the required temperature and then pressing
the hot material in the machine.

• Coal and Zinc ores may be agglomerated by

briquetting.
 CHAPTER THREE – AGGLOMERATION
NODULISING
• It is the conversion of fine grain materials into bigger
lumps by heating the material in a rotary kiln to a
temperature at which a partial fusion of the material
starts.

• Nodulising is restricted to the agglomeration of metallic

fines where there is insignificant amount of low-melting
gangue material constituents which tend to fuse into
forming irregularly shaped nodules of low permeability.
• It therefore has limited applications.
 CHAPTER THREE – AGGLOMERATION
NODULISING

• Low-grade manganese carbonate can be nodulised into

high-grade manganese oxide.

• The kiln is inclined to help easy movement and it has

liners or refractories, which helps to lift the material.
 CHAPTER THREE – AGGLOMERATION
Hot air
Preheated
air

Feed

Agglomerated
material

NODULISING
 CHAPTER THREE – AGGLOMERATION
PELLETISING
• Applied to a lot of iron ore concentrate.

• The fines are mixed thoroughly with a suitable amount

of moisture and the binding agent usually clayey
material such as bentonite.

• The mixture is rolled on an inclined drum, disc, etc.

causing the ore particles to cling together and roll up
into small spheres. Internal pores are reduced by
mechanical interlocking which increase the strength of
the ball.
 CHAPTER THREE – AGGLOMERATION
PELLETISING
• The ball may be hardened at room temperature
(curing) or by heating (firing) between 650 and 13000C.

• Firing causes recrystallisation of the material and thus

formation of stronger bonds.

• The heating may be done in a kiln / grate or oven firing

it at around 1200oC (in duration) to harden.
 CHAPTER THREE – AGGLOMERATION
SINTERING
• This is similar to Nodulising but the material is
stationary.

• This is done at a relatively higher temperature where

partial melting and re-crystallisation cause the fine
particles to adhere into bigger lumps.

• The fines may be mixed with some amount of coal,

which will cause a self-sustaining burning on the
surface
 CHAPTER THREE – DRYING
• Drying simply means evaporation of water.

• It is a dewatering process normally to remove

physical moisture content of zero.

• It is defined as the removal of mechanically held or

physically combined water.

• Ideally minerals or the ore in mineral processing

should be dry since crushing is essentially done dry.
 CHAPTER THREE – DRYING
• This is however not the case in real practical
situations. Totally dry minerals are rare.

• In the mining and mineral companies important

calculations such as throughput, recovery, etc.,
are based on dry mass thus samples are taken
across shifts to determine the moisture content
so as to get the actual (dry) mass of the ore
processed.
 CHAPTER THREE – DRYING
• Drying can be achieved through:

✓ Exposing to sun and air

✓ Heating the ore or substance above the normal

boiling point of water at atmospheric pressure.

✓ Reducing the atmospheric pressure with respect

to the vapour pressure of water at the
temperature in question.
 CHAPTER THREE – DRYING
• Drying can be performed as a separate process
✓ In drying furnace or kilns or as an auxiliary
process
✓ In the roasters wet ore charge is preheated
and dried by flue gases before it gets to the
actual reaction chamber.

• In drying a solid by evaporation, no fixed

temperature is required except that the
temperature of the source must be greater than
that of the material.
 CHAPTER THREE – DRYING
• The higher the temperature the more rapid the
evaporation; however the temperature must not
be high enough to start any chemical reaction such
as the roasting of sulphide particles or to cause
any fusion of the solid
 CHAPTER THREE – CALCINATION
• Calcination, also referred to as calcining is a thermal
treatment process applied to ores and other solid
materials in order to bring about a thermal
decomposition, phase transition or removal of a
volatile fraction.

• The calcination process normally takes place at

temperatures below the melting point of the
product materials.
 CHAPTER THREE – CALCINATION
• It is more endothermic than drying.

• Calcination is to be distinguished from roasting, in

which more complex gas-solid reactions take place
between the furnace atmosphere and the solids, as
calcination takes place in the absence of air

• The process of calcination derives its name from its

most common application, the decomposition of
calcium carbonate (limestone) to calcium oxide
(lime).
 CHAPTER THREE – CALCINATION
• The product of calcination is usually referred to in
general as "calcine," regardless of the actual
minerals undergoing thermal treatment.

• Calcination is carried out as separate process in

furnaces or reactors sometimes referred to as
kilns of various designs including shaft furnaces,
rotary kilns, multiple hearth furnaces, and
fluidized bed reactors and/or as an auxiliary
process in roasters and smelters
 CHAPTER THREE – CALCINATION
Examples of calcination processes include the following:
• Decomposition of hydrated minerals, as in calcination of
bauxite, to remove crystalline water as water vapour;

• Decomposition of carbonate minerals, as in the calcination of

limestone to drive off carbon dioxide;

• Decomposition of volatile matter contained in raw petroleum

coke;

• Heat treatment to effect phase transformations, as in

conversion of anatase to rutile or devitrification of glass
materials
 CHAPTER THREE – ROASTING
• Involves the heating of a substance or an ore below its fusion temperature
in the presence of air to decompose the material or change the physical and
chemical properties to make it suitable for subsequent process.

• It is usually a preparatory treatment of an ore for subsequent leaching or

smelting.

• Roasting in the auriferous industry involves the heating of complex gold ore
containing sulphidic minerals mainly pyrite and arsenopyrite and
carbonaceous materials in air to produce volatile arsenous oxide (As2O3,),
sulphur dioxide (S02), and carbon dioxide (CO2).

• The iron is also oxidised into hematite, which contains the gold and is
porous enough to be leachable by cyanide
CHAPTER THREE – PURPOSE OF ROASTING
• To convert sulphides to sulphates (Sulphating)

• To convert sulphides to oxide (Oxidation)

• To convert sulphides to chlorine (Chloridising)

• To convert sulphides to metals (Reduction)

• All these are done to effect liberation and to make the ore
amenable to leaching or other subsequent processes
CHAPTER THREE – TYPES OF ROASTING
OXIDISING ROASTING
• This is the replacement of sulphides with oxygen. Oxidising
roasting is the most important of all the roasting processes
as far as pyrometallurgy is concerned

𝟐𝒁𝒏𝑺 + 𝟑𝑶𝟐 = 𝟐𝒁𝒏𝑶 + 𝟐𝑺𝑶𝟐

• In sulfide roasting, if the temperature and gas conditions

are such that the sulphide feed is completely oxidized, the
process is known as “dead roasting”.

• However if the roasting process is performed with less than

the required amount of oxygen to fully oxidize the feed, it
is called "partial roasting" because the sulfur is only
partially removed
CHAPTER THREE – TYPES OF ROASTING
REDUCING ROASTING
• This is the heating of an ore or concentrate in contact with
a reducing agent so as to convert it into metals or effect
reduction in certain compounds.

• This is not common in modern times

𝒁𝒏𝑺 + 𝑪 + 𝑶𝟐 = 𝒁𝒏 + 𝑪𝑶𝟐 + 𝑺𝑶𝟐

CHAPTER THREE – TYPES OF ROASTING
Chloridising ROASTING
• This consists of heating the ore or concentrates in contact
with chlorine (e.g. NaCl, HCl, Cl2, CaOCl2) to convert into
chlorides, which may be leachable by water.

𝒁𝒏𝑺 + 𝑪𝒍𝟐 + 𝑶𝟐 = 𝒁𝒏𝑪𝒍𝟐 + 𝑺𝑶𝟐

2𝑴𝒈𝑶 + 𝑪 + 𝑪𝒍𝟐 = 𝟐𝑴𝒈𝑪𝒍 + 𝑪𝑶𝟐

CHAPTER THREE – TYPES OF ROASTING
SULPHATING ROASTING
• This is a modification of oxidising roasting where
temperature and gas conditions are controlled such that
the sulphides in the feed react to form metal sulphates
instead of metal oxides.

• Sulphates are more soluble in water.

𝒁𝒏𝑺 + 𝟐𝑶𝟐 = 𝒁𝒏𝑺𝑶𝟒

CHAPTER THREE – TYPES OF ROASTING
MAGNETISING ROASTING
• This is a modified form of reducing roasting where
haematite is reduced under controlled conditions to form
magnetite to aid in magnetic separation but this is
expensive for commercial purposes.

• Gravity method is rather used to concentrate Fe2O3 since it

is heavy.

𝟑𝑭𝒆𝟐 𝑶𝟑 + 𝟏ൗ𝟐 𝑪 = 𝟐𝑭𝒆𝟑 𝑶𝟒 + 𝟏ൗ𝟐 𝑪𝑶𝟐

CHAPTER THREE – TYPES OF ROASTING
SINTER OR BLAST ROASTING

• Sinter or Blast roast is just a type of oxidizing roast in which

the end product is sintered and agglomerated as well.

• Material may be mixed with coal.

𝟑𝑭𝒆𝟐 𝑶𝟑 + 𝟏ൗ𝟐 𝑪 = 𝟐𝑭𝒆𝟑 𝑶𝟒 + 𝟏ൗ𝟐 𝑪𝑶𝟐

CHAPTER THREE – TYPES OF ROASTING
SINTER OR BLAST ROASTING

• Sinter or Blast roast is just a type of oxidizing roast in which

the end product is sintered and agglomerated as well.

• Material may be mixed with coal.

𝟑𝑭𝒆𝟐 𝑶𝟑 + 𝟏ൗ𝟐 𝑪 = 𝟐𝑭𝒆𝟑 𝑶𝟒 + 𝟏ൗ𝟐 𝑪𝑶𝟐

CHAPTER THREE – COMMON METHODS OF ROASTING
HEARTH ROASTING
• It is carried out in a multi-hearth system in which about 8-12
hearths are enclosed in the large cylindrical shell having
diameter (6.1-7.6) and is about 9.14m high (Figure 2.2).

• Air enters from the bottom and is heated when it get into
contact with the roasted material leaving the roaster.

• The ore enters at the top and drops from hearth to hearth while
the sulphide ore particles are roasted as they come into contact
with the rising gases.

• Often the first hearth serves as a dryer

CHAPTER THREE – COMMON METHODS OF ROASTING
HEARTH ROASTING
• In order to promote oxidation of the material in the roaster, the
roaster is equipped with rotating rubble, which is attached to the
central shaft.

• The rabble has arms, which serve to stir the charge as well as
plough it towards the opening through which it drops to the next
lower hearth.

• For example, on the first hearth, the rubbles plough through the
material to push it towards the centre where there is an opening
and hence allowing the materials to fall on the second hearth.

• The vertical hearth furnace can roast between 100-200 tons of

material per day. Heat can be supplied by fuel but usually the
process is autogenous. It is cooled by sending cold air through
the central shaft and the arms
CHAPTER THREE – COMMON METHODS OF ROASTING
FLASH ROASTING
• The concentrate, which is often wet, is dried on the first upper
hearth or the second (Figure 2.3). It then falls through a
combustion chamber where roasting takes place rapidly.

• Auxiliary fuel is burnt in the unit to maintain the process

temperature in a case where combustion is not autogeneous.
After settling on the lower hearth the calcine (product) is
collected and discharged from the roaster.
• Flash roasting requires that the ore or the concentrate be
ground to fine size and as a result the dust lost on the roaster is
likely to be high.

• A flash roaster has much greater capacity than hearth roaster

of the same size because the materials are roasted rapidly in a
flash.
CHAPTER THREE – COMMON METHODS OF ROASTING
FLUIDISED BED ROASTING
• A fluidized bed reactor (FBR) is a type of reactor device that
can be used to carry out a variety of multiphase chemical
reactions.

• In this type of reactor, a fluid (gas or liquid) is passed

through a granular solid material (usually a catalyst possibly
shaped as tiny spheres) at high enough velocities to
suspend the solid and cause it to behave as though it were
a fluid.

• This process, known as fluidization, imparts many

important advantages to the FBR. As a result, the fluidized
bed reactor (figure 2.4) is now used in many industrial
applications.
CHAPTER THREE – COMMON METHODS OF ROASTING
BLAST ROASTING
• In the multi hearth roaster the air circulate by natural draft
and is not forced through the charge.

• In blast roasting (fig. 2.5) the charge to be roasted is held

stationary and a current of air is drawn or blasted through
it hence the name “blast furnace”.

• A certain amount of limestone is mixed with the roaster

charge.

• The limestone serves to lower the temperature to a point

where fusion from the charge could be avoided. This is
achieved as a result of heat absorbed in heating and
decomposing the limestone
CHAPTER THREE – COMMON METHODS OF ROASTING
BLAST ROASTING
• The charge must be coarse enough to prevent channelling
and increase permeability of air through them.

• The roasted material is removed by means of rotating disc

or a horizontally moving spiral.

• It is 60 meters high and can roast about 10 000 tons of

material per day.

• At present Dwight–Lloyd process which is an improved

version has replaced the Blast roasting and it is called
Sinter Roasting.
CHAPTER THREE – FACTORS TO CONSIDER IN ENSURING
WELL ROASTED PRODUCT
• Particles should be relatively small to increase rate of
reaction (it should however not be over ground).

• The correct temperature should be ensured and

maintained to prevent melting and formation of unwanted
product.

• The charge should have the right composition and good

contact with the hot air
 CHAPTER THREE – SMELTING
• It is a metallurgical process of melting a rock normally
under reducing conditions to reduce some of the metallic
oxides and at the same time to produce two main
immixable fluids; molten metal and slag.

• Separation is thus effected in a melt i.e. when the metal is

in the molten form.

• A smelting operation may yield 4 products – molten metal,

matte, speiss and slag which separate partially into layers
with increasing specific gravity as Slag (silicate S.G. = 3.6)
Matte (sulphide S.G.= 5.2) Speiss (arsenide S.G.= 6.0) and
the impure metal or bullion.
 CHAPTER THREE – SMELTING
• The material to be smelted is charged in the solid state but
the product from a smelter is in the liquid state.

• The only solid material that escapes is the dust carried out
in the furnace gases.

• There are two important types of smelting; reduction and

matte smelting.
CHAPTER THREE – REDUCTION SMELTING
• It takes place strictly under reducing conditions or in
contact with a reducing agent so as to reduce the mineral
of interest into a metal.

• It results in molten metal and slag.

 CHAPTER THREE – MATTE SMELTING
• This is a method of smelting of sulphide ores which results
in molten metallic sulphides and slag.

• Molten matte is a solution of metallic sulphides with high

electrical conductivity, low melting point and high specific
gravity.

• It contains some oxides (impurities) and thus requires

recleaning or refining. It is normally an intermediate
product in the extraction of polymetallic ores.

• For example, Fe-Cu-Matte is the intermediate product in

the extraction of Cu from chalcopyrite (FeCuS2).
 CHAPTER THREE – MATTE SMELTING
• It is also the standard treatment of the concentrate of Cu -
Ni sulphide. [Cu –Ni – matte (20 – 70 % Cu, 20 – 25 % S, and
the rest is Fe)].

• Antimony could be treated in this way (only when it

becomes necessary). This is carried out in the reveberatory
furnace.

• Shaft or blast furnace can be used but in copper and nickel,

the most commonly used one is the reveberatory.

• Blast is used for lead and iron.

 CHAPTER THREE – MATTE SMELTING
• Smelting may be conducted in a blast furnace,
reverberatory furnace or electric furnace.

• Reduction smelting is usually carried out in blast furnaces

and matte in reverberatory but there are exceptions in
both cases and each type may be performed in an electric
furnace.

• The necessary heat for smelting may be supplied from fuel

or electricity or the process may be autogeneous
CHAPTER THREE – FLUXES IN SMELTING
• This is normally added to the smelting process in order to
give the slag the required properties.

• A flux is a material, which is added to a furnace charge,

and it has the primary duty of reacting with the oxidised
portions (impurities) to form a fluid slag.

• It also lowers the melting point of the slag forming

constituents so they can melt easily and float. The slag
forming impurities must have a higher affinity for the flux
than the metal and thus dissociate from the metal.
• The composition and amount of flux to be added therefore
is determined by the impurities and thus the slag
envisaged. Examples of fluxes are lime, magnesia, and
silica.
CHAPTER THREE – FLUXES IN SMELTING
• Flux can be grouped into acidic, basic and neutral.

• Acid fluxes are used for basic impurities and vice versa,
whilst neutral gives more fluidity.

• Some of the common fluxes used are:

• Lime, magnesia iron, steel making
• Fluorspar steel making
• Silica copper smelting
• Borax copper smelting
• Hematite/Pyrite Lead smelting

• For smelting operations, silica is used to flux metal oxides

and calcium or iron oxide for fluxing siliceous material
 CHAPTER THREE – SLAG
• During smelting the bottom layer of the smelted material is
the molten metal or matte or speiss.

• Slag is the substance that forms the top layer after

smelting. It is glasslike in nature and thus can be
hammered off.

• It normally contains siliceous or oxide materials (e.g. SiO2,

Al2O3, CaO, FeO and sometimes phosphates, borates,
aluminates and sulphates) supposed to be unwanted in
most cases but not all, e.g.
• Antimony, and in the smelting of iron for example, high
limestone content in the slag can be used to produce
clinker or Portland cement. Generally slags are commonly
black, brown or dark green in colour, the colouration is
largely due to the presence of oxides of iron
CHAPTER THREE – FUNCTION OF SLAG
• Receptacle for gangue and or reduced oxides in primary
extraction (remove impurities).

• Prevents matte and molten metal from oxidation to retain

some sulphur for refining.

• Prevents heat loses from the crude metal.

• In refining process, the slag serves to absorb all the

extracted impurities.

• In the electric smelting furnace the slag could be used as a

heating resistor
CHAPTER THREE – PROPERTIES OF SLAG
• Melting temperature: should have a proper melting point;
and should melt at that temperature.

• Specific Gravity: should have low specific gravity as this

aids separation. Example Magnesia slag (S.G = 2.0) and
Lead (S.G = 3.6).

• Low viscosity: some valuable metals suspended in the slag

will be able to sink into the molten metal if the slag is fluid
i.e. less viscous.

• Low solubility for metal or matte: molten metal should not

be dissolved in the slag
 CHAPTER THREE – REFRACTORIES
• A refractory is a material that retains its strength at high
temperatures

• It is defined as materials having those chemical and

physical properties that made them applicable for
structures or as components of systems that are exposed
to environments above 1000 0F (538 0C).

• Refractory materials are used in linings for furnaces, kilns,

incinerators and reactors. They are also used to make
crucibles

• Refractory materials must be chemically and physically

stable at high temperatures.
 CHAPTER THREE – REFRACTORIES
• Depending on the operating environment, they need to be
resistant to thermal shock, be chemically inert, and/or
have specific values of thermal conductivity and of the
coefficient of thermal expansion

• Zirconia is used when the material must withstand

extremely high temperatures.
• Silicon carbide and carbon are two other refractory
materials used in some very severe temperature
conditions, but they cannot be used in contact with
oxygen, as they will oxidize and burn.

• Examples of materials used in making refractories include

quartzite, sandstone, kaolin, bauxite, forsterite, magnesite,
dolomite and graphite.
CHAPTER THREE – FACTORS AFFECTING THE CHOICE OF
REFRACTORY
• Price
• Melting
• Strength (mechanical and physical)
• Chemical Composition
• Thermal Conductivity
• Electrical Conductivity
• Expansion and Thermal Shock
• Porosity
• Resistance to Chemical Attack
• Softening Point
 CHAPTER FOUR

ELECTROROMETALLURGY
CHAPTER THREE – SOLUTION PURIFICATION/METAL
RECOVERY
CEMENTATION
• This is the process of precipitating a metal ion in solution
by the use of another metal. The precipitated metal
cements on the foreign metal.

• This reaction is electrochemical and works on the principle

that metals with more positive electro-potential or
oxidation will pass into solution and cement a metal ion
with a less positive potential.

• For example finely divided copper is displaced by an iron

scrap and cadmium can also be displaced by zinc as shown;