ADVANCED MINERALS

ENGINEERING IA
MISS S. BHEBHE
DEPARTMENT OF CHEMICAL
ENGINEERING
NUST
(SEPTEMBER 2017-DECEMBER2017)

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COURSE OUTLINE
 Please refer to hand-out for details.

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EXTRACTIVE METALLURGY
Background
- Metals are found in different forms on the
earth’s crust / seabed.
- The form in which a metal is found is
dependent on its reactivity with the
environment.
- The common elements/compounds that
react with metals include oxygen, sulphur,
chlorine,
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 silica and carbon dioxide.
- Less reactive metals are usually found in the
native/metallic form (noble metals).
- The more reactive metals are always found in
compound form as:
oxides e.g.
sulphides e.g.
silicates e.g.
chlorides/halides e.g.
carbonates e.g.

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 Extractive Metallurgy therefore deals with the
extraction of metals from the above
mentioned compounds and their refinement
to levels of purity suitable for commercial use.

Raw materials (ore/scrap metal)

Products (metal/compounds of the mineral)

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QUESTION
 Why is research on extractive metallurgy
becoming increasingly more important?

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 Extractive metallurgy processes are
classified into the following categories:
(i) Pyrometallurgy
(ii) Hydrometallurgy
(iii) Electrometallurgy
 In this course we focus only on
PYROMETALLURGY.

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PYROMETALLURGY
 Refers to the use of high temperature
reactions and processes for the
extraction and refining of metals.
 The extraction of metals is a reduction
reaction/process

M+ + e- Mo
(compound) element (metal in pure form)

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 Energy is therefore required to reduce the
metal from compound form to the elemental
form.
 The processes are carried out at high
temperatures i.e. 500-2000oC, where the ore
compounds become relatively unstable, thus
facilitating the release of the metal.
 During pyrometallurgical extraction
processes the bulk of the metal is separated
from its impurities in systems which
comprise more than one phase.

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 Metals enter the metallic phase while
non-metals enter the non-metallic phase.
 The driving forces for the formation of
the different phases are governed by
thermodynamics
 The key parameters in pyrometallurgy
are:
(i) temperature
(ii) environment
 Both (i) and (ii) must favour the reduction
reactions/processes.

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 Pyrometallurgy methods of metal production
are usually cheaper and suited for large scale
production.
 The major advantages of using
pyrometallurgy are:
(i) reaction rates are greatly accelerated at
high temperatures; small units can achieve
high production rates.
(ii) some reactions which are not
thermodynamically possible at low
temperatures become possible at high
temperatures.

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(i) There is greater ease of separation of
the product metal from gangue if the
products can be melted or vaporised at
high temperatures (i.e. above m.p or b.p
of the metal)
 All relatively inexpensive metals (e.g. iron,
lead, zinc, copper, alluminium, magnesium,
sodium, antimony, e.t.c.) are usually
produced by processes where the metal
is obtained in liquid/gaseous state first.

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 Metals produced in bulk are often impure
and need to be refined in order to
improve their properties
 The refining process can also lead to the
recovery of valuable by-products (case
where metals exist with other metals in
the compound).
 The desired purity of a metal is
dependent on the intended use of the
metal.

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UNIT PROCESSES IN
PYROMETALLURGY
 Pyrometallurgical plants are made up of a
combination of any of the following unit
processes;
(i) Drying
(ii) Calcination
(iii) Roasting
(iv) Smelting
(v) Refining

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UNIT PROCESSES FOR
PRELIMINARY
TREATMENT OF ORES

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DRYING
 Generally low temperatures are used,
therefore the classification of drying as a
pyromet process is “debatable”, however
in this course this will be considered as a
pyromet process.

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 Materials containing water are often
encountered at various stages of the
conversion of ore to metal e.g. ores,
concentrates, compound intermediates
e.t.c.
 The water in these materials has to be
removed prior to further processing for
the following reasons i.e.
(i) elimination of water reduces the
weight of material to be handled.

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 (ii) if material is to be charged into a
furnace where the operating temperature is
high, charge blow off can occur.
(iii) in some cases the material becomes
more reactive when the water is removed.
(iv) the presence of water can lead to
undesirable side reactions leading to poor
product quality and yield.
(v) the presence of water in feed
introduces an unnecessary heat load in the
furnace as more heat is required to drive
off water before smelting occurs.
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 Water is present in materials as free
water or water of crystallisation.
 Drying focuses on the removal of free
water.
 For evaporation to occur the vapour
pressure of water should be higher than
the partial pressure of water in the
surrounding atmosphere.
 This can be achieved by either;
a) raising the temperature of the material
at constant/ambient pressure
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 b) subject the material to reduced
pressure at constant temperature.
 Evaporation of water is an endothermic
process.
H2O (l) H2O (g) ; ∆H298 = +43.9KJ
 Therefore total heat supplied must
include heat required for drying (raising
temperature of the material) + heat of
evaporation.

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 Drying in pyrometallurgy is usually
accomplished by passing hot combustion
gases through and above the material to
be dried.
 This is achieved by operating at
temperatures just above the boiling point
of water i.e. at 120oC.
 In most integrated metallurgical plants
there are hot gases available (a few
hundred degrees) from other processes,
these can be used for drying.
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 If there are no gases available extra fuel
has to be burned.

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TYPES OF DRYING EQUIPMENT
 Rotary dryers
https://www.911metallurgist.com/blog/rotar
y-dryer-design-working-principle
 Fluidised-bed dryers
 Fixed-bed dryers
etc

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QUESTION
 What are the likely sources of the hot
gases mentioned above?
 Why is it not necessary to use a high
grade fuel?

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CALCINATION
 This is the thermal treatment of an ore to
effect its decomposition and eliminate the
volatile product.
 Expressed by the following reaction:

solid 1 solid 2 + gas

solid 1 ---- carbonate / hydrate
solid 2 ---- oxide
gas ---- carbon dioxide / water
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 Widely used operation in process
metallurgy.
 Calcination is more endothermic than
drying hence heat must be supplied to a
relatively high temperature
e.g. CaCO3(s) CaO(s) + CO2(g)
∆H298 = +177.8 kJ
 The dissociation temperature of a given
material differs and is reached when the
equilibrium pressure of CO2/H2O
exceeds the partial pressure of the gas in
air: TCE 5107 - NUST 2013 26
QUESTION
 Identify carbonates/hydrates which are
calcined in the metallurgical industry.
 State the dissociation temperatures of
these compounds.

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CALCINATION EQUIPMENT
 Shaft Furnace
 Rotary Kiln
 Fluidised Bed

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ROASTING
 Involves heating the ore or concentrate
below the fusion point in order to change
it chemically to a form which is more
suitable for subsequent treatment leading
to the extraction of the metal.
 Temperatures between 500 – 1000oC
 Common roasting operations include:

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Oxidising Roasting
 Usually carried out to burn sulphur from
sulphides with conversion of sulphides in
whole or in part into oxides.
 Strongly exothermic process
e.g. ZnS + 1.5 O2 ZnO + SO2
∆H = -422kJ
 If the heat of reaction is combined with
the heat capacity of the reaction products
of Zn with air an adiabatic temperature of
1700oC will be produced.
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 This temperature is above the m.p and
b.p of the sulphide and oxide, therfore in
order to prevent melting of the solids,
heat losses have to be sufficiently high to
keep temperatures low, where necessary
cooling of the vessel might be necessary
to reduce the temperature.

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Volatilising roasting
 Usually done to eliminate volatile oxides
such as AS2O3, Sb2O3 or ZnO

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QUESTION
 Why is it necessary to remove these
oxides?

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Chloridizing roasting

 Conversion of metal oxides/sulphides to

chlorides from which the metal may be
subsequently obtained by reduction.
e.g. 2NaCl(s) + PbS (s) + 2O2
Na2SO4 (s) + PbCl2(s)
 Normally used for metals which are highly
reactive to oxygen.

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 Reduction of the oxide will result in a
metal with residual oxygen, thus affecting
the mechanical properties of the metal.

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Suphating roasting

 Conversion of metal sulphides to

sulphates prior to leaching (hydromet).

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ROASTING EQUIPMENT
 Multiple Hearth Furnace
 Flash Furnace
 Fluidised-bed Furnace

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UNIT PROCESSES FOR
METAL EXTRACTION

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SMELTING
 Process for the production of a metal or
a metal-rich phase such as matte.
 Involves the reduction of metal oxide to
metal.
 Carbon is the most common reducing
agent due to;
easily available
low cost

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 It forms two volatile oxides i.e. CO and
CO2.
 The lower oxide (CO) becomes more
stable at higher temperatures whereas
the metal oxides are unstable at high
temperatures.
 Therefore carbon can reduce any metal
oxide provided the temperature is
sufficiently high, however there should be
a limit to the temperature because if its
too high C can dissolve in the metal to
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 form stable carbides which are detrimental
to the properties of the metal.
 During smelting the gangue is removed as
slag with the help of fluxes.
 No reducing agent is required in matte-
smelting.
 Reduction of metal oxide by carbon is
represented as;

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MO(s,l) + C(s) M(s,l) + CO(g)
MO(s,l) + CO(g) M(s,l) + CO2(g)

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REFINING
 This is the final stage of the metal
extraction process.
 It involves the removal of the last traces
of impurities from the metal to give a
product of very high purity.
 There are a number of methods that can
be used;

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e.g.
 Addition of refining agents which react
preferentially with the impurities.
 Selective distillation/ dissolution of
impurities.
 Electrochemical methods where the
metal to be refined is made the anode
and the pure metal is deposited on the
cathode and these are dipped into a
solution of an ionizable salt of the metal.

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FUELS / SOURCES OF ENERGY
 Pyrometallurgical processes require
energy input to sustain the temperature
at which the processes take place.
 Heat energy is provided in the form of:
(i) Fossil fuel combustion
(ii) Exothermic reaction of the material (if
the heat of reaction is sufficient to maintain
required temperatures, the process is
termed ‘autogeneous’)
(iii) Electrical energy conversion to heat.
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 The maximum temperature in the reactor
is dependent on the source of energy.
- Combustion of carbonaceous fuels gives a
maximum temperature of 1 500oC.
- Electrical energy can provide
temperatures as high as 2 000oC.

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FOSSIL FUELS
 Combustion of fossil fuels is a major
source of heat in the pyrometallurgical
industry.
 Maximum temperatures of about 1 500oC
can be achieved by the burning of fossil
fuels. This corresponds to the amount of
energy available due to the breaking of
chemical bonds in the fuel.

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 When a carbonaceous fuel burns up in a
reactor or furnace heat transfer to the
charge occurs by conduction, convection
and radiation.
 The design of the reactor determines the
predominant method of heat transfer in
the system.
 The sources of oxygen for combustion in
these processes are:
- Air (20% O2 , 79% N2 , 1% other)
- Oxygen enriched with air > 20% O2
- Pure oxygen TCE 5107 - NUST 2013 48
 The commonly used source of oxygen is
air because its readily available and cheap.
 The amount of air introduced for the
combustion of the carbonaceous fuel has
to be determined with great care.
 If an exact stoichiometric amount of air is
used, a fraction of the fuel intended to
burn inevitably escapes combustion either
due to the nature of the reactor or the
reaction kinetics.

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 The failure to use all the fuel amounts to
energy loss (costly).
 Therefore in order to ensure complete
combustion of the fuel excess air should
be supplied.
 The quantity of excess air must also be
carefully regulated because the
introduction of excess air leads to higher
heat losses as more N2 is introduced into
the system. (N2 does not take part in the
reaction). QUESTION: Explain this?

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 Therefore there must be a compromise
between the amount of unutilised fuel
saved and the heat lost due to excess air.
 Fossil fuels are of three types i.e. solid,
liquid and gaseous.

These are classified as follows:

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General Grouping Primary Fuels Secondary Fuels

Natural Manufactured/by-products

Solid Anthracite coal, bituminous coal, Coke, charcoal, coke breeze, semi-
lignite, peat, wood coke, pulverised coal

Liquid Petroleum Tar, kerosene, diesel, petrol, LPG,

gasoline, naphtha, pitch

Gas Natural gas Coal gas, blast furnace gas, coke oven
gas, oil refinery gas

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FUEL SELECTION
 Given that there are a number of fuels
available that can be used as heat sources.
The selection of the best fuel to use for a
particular application is of vital
importance.

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The principal factors that have to be
taken into account are:
(i) Suitability for the process
Discuss
(ii) Supply/Availability
Discuss
(iii) Cost
Discuss

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 The economic importance of a fuel depends on:
(i) Its geographical distribution
Discuss
(ii) Costs involved in mining and
transportation
Discuss
(iii) Calorific value of the fuel
Discuss
 The commonly used fuels in the Zimbabwean
industry are the solid fuels.
QUESTION: Why are solid fuels preferred in
Zimbabwe?
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 ADVANTAGES AND DISADVANTAGES
OF SOLID FUELS
Advantages
 Easily transportable
 Convenient to store no risk
of spontaneous explosion
 Low production costs
 Moderate ignition
temperatures
 Comparatively less sulphur
content (therefore reduced
atmosphere pollution and
corrosion of equipment)
Disadvantages
 High ash content
 Low thermal efficiency
 Burns with clinker formation
 Combustion process difficult to
control
 High handling costs
 CV lower than liquid fuels
 Large excess of air needed for
complete combustion
 Enough storage space needed
 Liable to spontaneous combustion
and thus can catch fire during storage
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COAL AND COKE
 Coal is a major source of energy in the
Zimbabwean industry.
 In the pyro metallurgical industry carbon
plays an important role as a reducing
agent and coke (a product of coal
pyrolysis) is normally used as a source of
carbon.
 Due to the vast coal deposits in the
country, coal and coke are widely used in
the Zimbabwean industry.
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COAL FORMATION
 Definition: coal is a compact stratified
mass of plant debris which is a result of
combined biological, chemical and physical
degradation of accumulated plant matter
interspersed with smaller amounts of
inorganic matter.

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 Coal is formed by the burial of plant material in
swampy areas.
 The plant material termed peat is compacted,
hardened, chemically altered and metamorphosed
by heat and pressure overtime.
 After burial biochemical decomposition converts
the plant matter to peat while geochemical
decomposition converts peat to coal.
 As the depth of burial increases the plant material
undergoes coalification, releasing volatile matter as
it forms coal.
 The extent of exposure to high pressure and
temperature during the geochemical stage results in
different degrees of coalification (i.e. rank) that are
observed in the coal series. TCE 5107 - NUST 2013 59
COAL COMPOSITION
 Coal is not homogenous it is made up of
organic and inorganic components.
 Organic components of coal are made up of C,
H2 , O2 , N and S.
 These elements are bonded together to make
difficult functional groups and the arrangement
of these functional groups determines the
structure of coal.
 Oxygen functional groups are: carbonyl,
hydroxyl, carboxylic acid and methoxy.

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 Nitrogen functional groups are: thiols, dialkyl,
ary-alkly thioethers, thiophene and disulphides.
 The presence and amount of each functional
group differs from each coal maceral and also
differs with coal rank.
 Some groups tend to dominate in a specific coal
type while others exist in insignificant
quantities.
 The aromaticity of coal molecules increases
with coal rank and the number of aromatic
carbons per cluster varies from 9 in lignite to
20 in bituminous coal.
QUESTION: What are the inorganic components
of coal? TCE 5107 - NUST 2013 61
COAL MACERALS
 These are the building blocks of the
organic component of coal.
 They owe their differences to the parent
plant matter and conditions of deposition
of the plant matter.

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 The 3 maceral groups are:
Vitrinite - this is the coalification product
of woody tissues derived from stem and
roots of trees and vascular tissues of leaves.
Inertinite - this is the coalification product
of partially oxidized cellulose and lignin
from plant material.
Liptinite - this is the product of
coalification of resinous and waxy material
of plants.

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 The macerals exhibit different physical,
chemical and optical properties.
 The differences in the properties lead to
differences in their uses.
QUESTION: What are the uses of each
maceral?

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 COAL PROCESSING
 This involves coal preparation and coal
conversion.
 Coal preparation was covered in Part III
 Coal preparation is done for the following
reasons:
(i) To liberate the organic component of coal
from the inorganic mineral constituents.
(ii) To separate the different coal macerals.
(iii) To grade coal into closely sized particles
for further processing and for the market.
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COAL CONVERSION
 When coal is heated in the absence of air
(i.e. pyrolysis) it is converted into a
variety of solid, liquid and gaseous
products.
 The nature and amount of the product
will depend upon the temperature of the
pyrolysis and the type of coal.
 The principal product by weight is coke.
 Other products include:

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 Solid Liquid Gas
 Naphthalene  Water  Hydrogen
 Anthracene  Tar  Methane
 Cyanogen compounds  Various oils  Ethylene
 Carbon monoxide
 Carbon dioxide
 Hydrogen sulphide
 Ammonia
 Nitrogen

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 Pyrolysis temperatures range from 500oC
to 1200oC.
 The carbonisation process is divided into:
- Low temperature carbonisation (500oC to
800oC)
- High temperature carbonisation > 800oC
 The type of carbonisation employed in a
particular system is dependent on the
amount of gas/liquid products required.

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 Low temperature carbonisation
- High liquid production
- High gas production
 High temperature carbonisation
- Low gas production
- Low liquid production
 During pyrolysis the following processes
take place:
(1) As the temperature is raised, the
aliphatic C-C bonds are the first to break.
(2) As the temperature approaches 600 oC,
the C-H bonds are broken.TCE 5107 - NUST 2013 69
 Further increases in temperature causes
the elimination of the heterocycle
complexes and progressive aromatization.
 The average molecular weights of the
volatile intermediate products constantly
decrease as the temperature
carbonisation rises. This decrease is
marked by the evolution of water, CO, H2,
CH4 and other hydrocarbons.
 Final decompositions are at a maximum
between 600oC to 800oC

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COKE OVENS
 The coke oven is a narrow chamber
whose width tapers from one end to the
other.
 In general, coke oven are built to handle
16 to 24 tonnes of coal.
 The coke ovens are built in batteries of
10 to 100.
 The oven is built of refractory brick with
heating flues between the ovens.
TCE 5107 - NUST 2013 71
 The coking process in each oven is a
batch process, but the battery is operated
as a continuous process. The ovens are
charged at different times systematically.
 A charge of finely crushed coal is dropped
from a lorry car through charging holes at
the top and into the oven where the walls
are at approximately 1100 oC.
 Then surface of the coal is levelled and
the charging holes covered.

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 The coal charge is heated on both sides
so that heat travels toward the centre and
thus produces shorter and more solid
pieces of coke.
 The charge is coked until evolution of
volatile matter has stopped.
 The average temperature at the end of
the heating period is approximately 1000
oC and the flue temperature is about

1300 oC.

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 At the end of 18 hours, the doors on the
ends of the oven are opened and the red-
hot mass is pushed by a ram electronically
driven through the oven from end to end.
 The coke falls into a quenching car, which
travels to the quenching station where
nozzle spray about 6 000 gallons of water
onto it.
QUESTION: What is the reason for
quenching?

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 After draining it is moved to the wharf
where the coke is dumped onto
conveyors which take it to a crushing and
screening plant.
 The gas from the coking process together
with the entrained liquid particles passed
upward through a cast-iron goose neck
into a horizontal steel hydraulic collecting
main, which is connected to all the ovens.
 The gas leaving the ovens is sprayed with
weak ammonia water condensing the tar
and ammonia.
TCE 5107 - NUST 2013 75
 These move through the main along with
the gases to a settling tank.
 Some of the ammonia liquor is pumped
back in cycle and the rest of the gases are
pumped to the ammonia still for
separation.
 All the tar flows to the storage tanks.
 The rest of the gas goes for further gas
cleaning.
 After being stripped of its by-products,
the gas is burned to supply heat for
coking (heat integration)
TCE 5107 - NUST 2013 76
COAL, COKE ANALYSIS
COAL COKE

M – 0.6% C – 96.5% to 97.0%

V.M. – 22.9% H2 – 0.4% to 0.2%

F.C. – 67.3% O2 , N2 , S – 2.1% to 1.8%

Ash – 9.2% Ash – 1.0%

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 B.S. Swelling Index # - 8
Approximate yield/tonnes of coal
carbonised (i.e. high temperature)
 Coke – 1 400lb
 Coke breeze – 70 to 100lb
 Tar – 10 gallons
 Ammonium sulphate – 20lb
 Light oil (removed from gas by oil scrubbing) –
2 to 4 gallons
 Gas (550 Btu) – 11 000 cu ft
QUESTION: What are environmental effects of
the widespread use of coal and coke in
Zimbabwe? What measures can be taken to
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