Dr.

Winny Wulandari
References: Hayes, P. Process Principles in Minerals &
Materials Production, 3rd ed., 2003, Brisbane: Hayes
Publishing Co

TK4046 Dasar-dasar Metalurgi Proses/TK5035

Teknologi Proses Metalurgi Sem II 2013/2014
ž  The aim of mineral processing operation is one of
separation, separation of unwanted gangue
materials from the feed material.
ž  In case where unwanted elements are physically
inseparable from the desired material, final
separation can only be achieved by chemical
processing using high temperature, aqueous or
organic solution, or electrochemical techniques.
ž  Chemical processing also enables the process
aims of compound formation, metal production,
and metal purification to be carried out.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Reactant species & chemical equilibrium
ž  Reactor selection
ž  When investigating the possible use of chemical/
electrochemical processes, the problems should
be approached by considering the following:
¡  Are the proposed reaction thermodynamically
favourable?
¡  What are the reaction paths and possible
intermediate products?
¡  What factors are likely to affect the reaction kinetics?
¡  What are the most suitable reactor designs for these
processes?

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Pyrometallurgical processing: high
temperature processes related to metals
production.
ž  Used extensively in the production of metals
& materials:
¡  Relative stabilities of metals & their compounds
change considerably with temperature
¡  The rates of mass transport & chemical reactions
are increased with increasing thermal energy
¡  Liquid and gas phase processing, which are
possible at higher temperatures, allow separation
of product phases
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  Metal oxides, sulphides & halides are major
sources of metals and a wide variety of high
temperature pyrometallurgical processing
are available.
ž  Often combination of high temperature,
aqueous/organic solution, and
electrochemical techniques are used to
obtain the desired products.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  The inherent difficulties of handling &
processing of materials at high temperatures
significantly influence the design of reactor.
ž  Characteristics:
¡  Physical states of feed
¡  Sources of heat and how this heat transferred to
the charge in the reactor
¡  General characteristics: mechanism of mixing of
reactants, control over reactants
¡  Continuous or batch process
¡  Specific processing rates

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Rarely utilized to produce gaseous metal
compounds
ž  If homogeneous gas phase reactions do occur
at temperature on cooling, very fine
particulate resembling smoke & fume are
formed.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  During initial production of metal, refining,
or recycling.
ž  Heat sources: indirect, electrical resistance
heating elements; arc or plasma heating
ž  The liquid metal products are protected from
reaction with air through the use of liquid
fluxes or inert gases.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Increase interest in injection reaction
ž  High bath agitation created by the injection
of high velocity gas streams into melts

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
 Feed: liquid or solid & liquid
Products: liquid and gases
Heat sources: gas/fuel mixture,
Exothermic reaction, external heating
Specific processing rate: 0.5 – 5 ton/m3.h

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  In most cases, when liquid/liquid reaction are encountered, the
aim is separation by formation of immiscible liquid phases.
ž  Example: reverberatory furnace.
ž  Heat source: heat transfer from preheated gases, controlled
combustion in bed/

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Shaft Furnace
ž  Rotary Kiln
ž  Flash reactor/entrained flow reactor
ž  Fluidised bed

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
 ž  Applications: direct
gaseous reduction,
reduction roasting of
hematite ores to
magnetite, limestine
calcination
ž  Heat source: a) electric
arc, b) counter-current
heat transfer from
preheated gas, c)
combustion within shaft

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
 ž  Applications: drying/
reduction, cement kiln
ž  Heat source: hydrocarbon
burner above charge,
rotation provides heat
transfer from walls to
charge

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
ž  Chemical energy
ž  Combustion of hydrocarbon fuel
ž  Electrical energy
ž  Conserved energy, sensible heat

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Oxidation of solid or liquid metal sulphides:

ž  Oxidation
of dissolved silicon and carbon in
molten iron

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
ž  The use of electrical energy in high
temperature applications is through
resistance, inductance, arc or plasma
heating.
ž  Advantage: no contamination of fuel

ž  Temperatureis limited by reactor materials

and heat losses from the system.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Induction heating is carried out for materials
that electrical conductors
ž  In arc & plasma heating, an ionised gas
atmosphere (plasma) is created between
inner & consumable electrode. Local
temperature: 3000 – 10000 K, advantages:
high rates of energy input \
ž  Conserved energy: recycled energy to
preheat the materials

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
Characteristics
Physical & Resistance to attack by liquid and gases,
chemical thermal insulation, thermal shock resistance,
properties mechanical strength, high temperature creep
resistance, low temperature expansion
Bonding types Direct bonded
Indirect bonded: CaO – Al2O3 cements,
Chemically bonded (e.g. phosphates), organic
binders (e.g. tar, pitch)
Forms Bricks & special shapes
Castable, mouldable, ramming, gunning mixes,
ceramic fibre, blankets or preformed fibre
shapes
Costs Initial cost of refractories
Installation costs
Case of repair
TK4046 Dasar-dasar Metalurgi Service
Proses/TK5035life
Teknologi
Proses Metalurgi Sem II 2013/2014
 Separation via the vapor phase
(1) 

(2)  Chemical changes in the solid state

(3)  Liquid phase reactions

TK4046 Dasar-dasar Metalurgi Proses/TK5035

Teknologi Proses Metalurgi Sem II 2013/2014
ž  Techniques
to separate metals & metal
compounds from unwanted materials:
¡  Formation of vapor species or metals /
compounds which already exist in the system
¡  Formation of new vapor species, created by
interaction with a reactive gas mixture

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Material characteristics
¡  Desired product species
¡  Equilibrium vapor pressures of species
¡  Sensitivity of vapor pressures to reaction
temperature and pressure changes
ž  Reactor characteristics
¡  Mechanism of removal of vapour species
¡  Supply of reactant species
¡  Surface area of the solid and liquid phase
¡  Total pressure within the reactor
¡  Reaction temperature

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Equilibrium vapor pressures
¡  Species to be removed have high equilibrium
vapor pressure
¡  Vapor pressure of species depends directly to the
activities of component in the solid or liquid
solution
ž  Mass transport
¡  The
rate of removal of gas species from a surface
depends on:

km: mass transfer coefficient (m/s)

Pis, pib: partial pressure of vapor species at the
surface & bulk gas stream
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  Mass transfer coefficient may be increased
by increasing the local gas velocity &
turbulence of gas flow over the reaction
surface
ž  Increasing delta P:
¡  Increasing Pis or decreasing Pib
ž  Partial
pressure of i in the bulk gas may be
minimised by:
¡  Removing gaseous products in a continuously
pumped chamber
¡  Maintaining a flow of gas not saturated with the
gas species

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Equilibrium in the Zn-O system:

In practice, oxygen partial pressure may be

controlled by using mixtures of CO and CO2 gases:

ž  A
high zinc partial pressure may be obtained at
low PCO2/Pco ratio, high activities of ZnO, and
condition where the equilibrium constant is high.
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
ž  Purposes:
¡  The removal of certain non-metallic elements or
compounds, or
¡  Changes in the metal compounds present are
desired
ž  Usually carried put in the presence of
neutral /reactive gas mixture
ž  Gas flow over the particles is used to remove
product species, provide reactant gases,
and/or to provide efficient heat transfer
between solid & hot gas
ž  Involves kinetics of gas/solid reaction

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Heating
of sulfide materials in the presence
of oxygen gas (roasting) is a commonly used
treatment in extractive metallurgy.
¡  Oxidation of metal sulfide to oxide
​𝑀𝑆↓(𝑠) +​1.5𝑂↓2(𝑔) ↔​𝑀𝑂↓(𝑠) +​𝑆𝑂↓2(𝑔) 
¡  Formation and decomposition of metal sulfate,
oxysulfate, and sulfur trioxide
​𝑀𝑆↓(𝑠) +2​𝑂↓2(𝑔) ↔​𝑀𝑆𝑂↓4(𝑠) 
2​𝑀𝑆↓(𝑠) +​3.5𝑂↓2(𝑔) ↔​𝑀𝑂.𝑀𝑆𝑂↓4(𝑠) +​𝑆𝑂↓2(𝑔) 
​𝑆𝑂↓2(𝑔) +​0.5𝑂↓2(𝑔) ↔​𝑆𝑂↓3(𝑔) 
​𝑀𝑂↓(𝑠) +𝑆​𝑂↓3(𝑔) ↔​𝑀𝑆𝑂↓4(𝑠) 
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  In case of copper-iron sulfide minerals, two
different thermal treatments may be used to
achieve two significantly different results.
ž  The aim is to remove unwanted sulfur & iron
from the material.
¡  If the concentrate is heated in an oxidising
atmosphere at 600-700 oC, over the range of oxygen &
sulfur partial pressure pO2 = 0.01 – 0.2 atm and pSO2 =
0.01 – 1 atm, CuSO4(s) & Fe2O3 (s) are produced. The
copper may be separated from iron oxide by
selectively dissolving copper sulfate in water or dilute
acid.
¡  If oxidation is carried out at 500-550 oC, only limited
oxidation of iron to Fe2(SO4)3 takes place and CuSO4 is
also formed. If these reaction products are
subsequently melted down with the addition of silica,
further separation of iron oxides from iron/copper
sulfide is achieved by liquid/liquid separation.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
 Input: wet sulfide
Concentrates

Chemical reaction
produces heat

Reaction temperature
is controlled by adding
inert flux material

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Sulphidisation
¡  Converting metal oxide to sulfides, oxysulfides or
sulfates.
ž  Salt roasting
¡  The reaction of two solids to form a third compounds
which is readily soluble in aqueous solution. E.g.
Na2V2O6.
ž  Reduction roasting
Treatment of oxides under reducing gas conditions to
effect a change in phase:
¡  Reduction of 2O3 to Fe3O4 which can be subsequently
magnetically separated from gangue.
ž  Thermal decomposition
Heating of materials to temperature resulting in their
spontaneous decomposition into other compounds, e.g.
Decomposition of AuTe2, AuTe, AgS to Au and Ag metal
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  Separation using immiscible liquid phases
ž  Used in the processing of metals using
aqueous & organic solution and
ž  Pyrometallurgical processing:
¡  Covalently bonded metal sulfides (mattes)
¡  Covalently bonded metal oxides (slags)
¡  Covalently bonded metal salts (metal halides,
nitrates, carbonates)
¡  Metallically bonded molten metals.
ž  In
metal production & refining: metal/slag,
matte/slag, metal/matte/slag, metal/
molten salt
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  Material characteristics
¡  Liquid phases: low melting temperatures
¡  Low mutual solubilities
¡  Favourable distribution of minor elements
¡  High density difference
¡  Low viscosity
¡  High interfacial energy
¡  Low volume ratio of discard to retained phase
ž  Reactor characteristics
¡  Point of introduction of charge
¡  Point of removal of liquid phase
¡  Method of stirring or agitation
¡  Residence times, bath depth, heating & control of gas
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  Meltingtemperature can be lowered by
dissolving more compounds:
¡  Melting point of pure SiO2: 1725 oC, Al2O3:2050 oC
¡  In ternary system of SiO2-Al2O3-CaO, the lowest
melting point liquid is at 1265 oC.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
ž  Any general reaction involving M, oxygen,
liquid oxide:

ž  if
the metal forms a very stable metal oxide,
the Keq >>. E.g. CaO, SiO2, Al2O3.

ž  Formetal oxides of intermediate & low

stability, it is possible by controlling the
oxygen pressure in the system, to also
control the distribution/partitioning of metal
species between phase containing the molten
oxides (slag) and metal phase.
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
Metal – slag system: Metal: Fe-minors (Si, Al,
Ca)
Slag: FeO-Fe2O3-SiO2-Al2O3-CaO

Check: Ellingham diagram

¡  At very low oxygen partial pressure, reaction

will move to the left, resulting formation of
liquid metallic iron.
¡  Si, Al, Ca remain predominantly in the oxide
phase (slag).
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  The low oxygen partial pressure condition
will lead to separation of Fe to the metal
phase, and unwanted material may be
separated to the slag phase.
ž  Represent favourable conditions for the
recovery of metallic iron
ž  The final SiO2-Al2O3-CaO slag composition is
adjusted so the slag is completely molten at
1350-1450 oC.
ž  è basis of ironmaking process

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Partitioning of Si between slag and metal:

In the ironmaking process, if the metal is

saturated with carbon, the activity of oxygen is
determined by:

Reaction results to:

ΔGo = 591,757 – 391,2 T J/mol

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  aC and aCO at one atmosphere = 1.

ž  Fig 5.2.16 activities of SiO2

ž  Fig 5.2.17 silicon contents of carbon
saturated iron

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
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Proses Metalurgi Sem II 2013/2014
ž  Other examples of partitioning of species:
¡  Partitioning of copper in the metal, matte, and
slag
¡  Partitioning of species in Fe-S-O system
¡  L = (%wt M)phase 1 / (%wt M)phase 2

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
Example: distribution ratio of impurity elements
between slag & metal for Iron silicate & calcium ferrite slag system

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Dispersion of liquid droplets.
¡  These
droplets should be allowed to agglomerate
& from physically distinct layers
ž  Viscosity of melts
¡  Polymeric
melts, e.g. Silicates, aluminates,
borates & phospates, their viscosities is highly
dependent on melt composition and
temperature.
ž  Interfacial tension
¡  Limited data on interfacial tensions of slag/
metal, slag/matte, metal/matte.
¡  Interfacial tension is sensitive to the presence of
impurity elements.
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
TK4046 Dasar-dasar Metalurgi Proses/TK5035
Teknologi Proses Metalurgi Sem II 2013/2014
ž  Metal
compounds are used in a wide range of
applications:
¡  As a feedstock of chemical process
¡  To provide essential intermediate steps in metal
production
¡  To form useful end-products in their own right.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Calcination of limestone (CaCO3)
ž  Oxidation of zinc sulfide (ZnS)
ž  Reduction of ilmenite (FeTiO3) to produce
rutile (TiO2)

ž  Tugas
3: Buat deskripsi proses tiga proses di
atas. Rujukan utama: Hayes. Dikumpulkan
Senin, 29 Februari 2016

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Halide compounds, particularly chlorides,
have been found useful in the production of
metals that have a stable oxide.
ž  In general, halides are less stable than the
corresponding metal oxides, however, halides
can be prepared from oxides by reaction
under reducing conditions.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  A
number reasons why the use of halides
rather than oxides could be advantageous to
a process:
¡  The low solubility of halides in the metal makes
possible the production of pure metals
¡  High vapour pressure makes possible vapor phase
separation and purification
¡  Low melting points & high electrical
conductivities make possible high temperature
electrolytic process
¡  High solubilities of halides in aqueous solution
enable separation and purification of the
compounds to be carried out.
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
Proses Metalurgi Sem II 2013/2014
ž  Example: chlorination of TiO2
Rutile concentrates can be treated by chlorination in the
presence of carbon at 500 oC. The process, carried out in a
shaft furnace or fluidised bed, produces titanium
tetrachloride:

The presence of carbon is essential to the reaction by

comparing the following reaction that thermodynamically
unfavourable:

High purity titanium tetrachloride then is used in the

production of titanium metal.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Other
metal compounds that acting as a
feedstocks:
¡  Production of portland cement
¡  Production of glass

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
 Metal Production from Metal Oxides
Metal Production from Metal Sulfides
Metal Production from metal Halides

TK4046 Dasar-dasar Metalurgi Proses/TK5035

Teknologi Proses Metalurgi Sem II 2013/2014
¡  Conditions for decomposition of pure metal
compounds to pure metals are determined by
reaction temperature, and gas partial pressure.
¡  Usually only occurs at low oxygen, sulphur, or
halide partial pressure.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  How metal can be produced?
ž  Another element or compound must be
added to the system:
¡  Another metal that has a compound that more
stable than one being processed
¡  Non-metallic element or compound, e.g. Oxygen,
carbon, or carbon monoxide gases.

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
Reducing Agent:
- Carbon
-  Hydrogen /steam mixture
-  Carbon monoxide / carbon dioxide mixture

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Carbothermic reduction of iron ores (Hematite)
in blast furnace is a well know process.
ž  Iron ore oxide minerals + gangue + reductant (C)
+ flux + hot blast oxygen enriched air = pig iron
(liquid) + slag (liquid) + off gas (CO, CO2, N2).
ž  Iron ore contains Fe2O3, along gangue materials
such as SiO2 and Al2O3.
ž  Charge materials: iron ore + limestone + coke
ž  Output: pig iron (1300 oC), 4,5 %C, 0,4-0,6 %Si,
0,1-0,2%P, 0,004-0,005%S, 0,1-0,5% Mn
ž  Slag: CaO/SiO2=1.1; CaO = 30-40%, Al2O3 =
10-23%, FeO < 1%, MgO < 8%
ž  Waste gas: CO = 20-25%, CO2 = 20-25%, rest N2
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ž  Zone 1 (<950 oC): upper zone, reduction of
Fe2O3, Fe3O4:
3Fe2O3(s) + CO(g) à 2Fe3O4(s) + CO2(g)
3Fe2O3(s) + CO(g) à 3FeO(s) + CO2(g)
ž  Zone 2 (950-1000 oC): chemical reserve zone,
FeO is in equilibrium with gaseous phase:
FeO(s) + CO(g) = Fe(s) + CO2(g)
ž  Zone 3 (950<T<1050 C): the reduction of FeO
by rising CO gas takes place:
FeO(s) + CO(g) à Fe(s) + CO2(g)
TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi
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 ž  Zone 4: direct reduction of FeO to carbon
takes place:
ž  Reaction
Reaction in raceway
in raceway zone:
zone: C 𝐶++O​𝑂2↓à
2 →CO
​𝐶𝑂↓
2
2 
Followed
ž  Followed CO​𝐶
by by 2 𝑂↓
+ C2 à
+𝐶→2 𝐶𝑂(Boudoard
2 CO  (𝑏𝑜𝑢𝑑𝑜𝑎𝑟𝑑  reaction)
𝑟𝑥𝑛)
Overall: C +𝐶O+2​𝑂à
ž  Overall: ↓2 2CO
→2𝐶𝑂
ž  Boudoard reaction is thermodynamically
feasible at T >1050 °C(below zone 4). It
supports the conversion of CO2 to CO in
raceway and bosh region where T>1050 °C.

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Proses Metalurgi Sem II 2013/2014
ž  Ellingham Diagram for sulfides:
¡  Sulfides of carbon, hydrogen, and carbon
monoxide: CS2, H2S, COS
¡  Relative unstable

ž  à oxygen reacts with sulfur forming SO2 gas.

ž  Oxygen supply is controlled to avoid
complete oxidation of metal to the metal
oxides.

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ž Extraction of Lead
ž  Lead ore consists of PbS (galena) along with
Sphalerite (ZnS, pyrite (FeS2), Cu2S and some
presious metals like gold and silver as gangue
ž  First of all lead ore (3-10% lead) is
concentrated to 60-70% by froth flotation,
then roasted to remove sulfur and form
oxides, followed by reduction in blast
furnace using coke

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Proses Metalurgi Sem II 2013/2014
ž Extraction of Zinc
ž  Zinc ore consists of sphalerite (ZnS) along
with sulfides of copper, lead and cadmium
with some precious metals as gangue.
ž  Sulfide is converted to oxide by roasting
process, followed by carbothermic reduction
​𝑍ZnO
𝑛𝑂↓ (𝑠) +​𝐶↓(𝑠) ↔​𝑍𝑛↓(𝑔) +​𝐶𝑂↓(𝑔) 
(s) + C(s) = Zn(g) + CO(g)

ž  Vacuum is needed to push reaction forward.

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ž Extraction of copper
ž  The copper ore is known as chalcopyrite
(CuFeS2). Copper is less than 2%, which is
concentrated by froth flotation.
ž  Roasting of chalcopyrite is carried out to
remove iron sulfide in the form of FeO
​22CuFeS
𝐶𝑢𝐹𝑒𝑆↓ 2(𝑠) +​𝑂↓2(𝑔) ↔​𝐶𝑢↓2 𝑆+2𝐹𝑒𝑆+​𝑆𝑂↓2(𝑔) 
2(s) + O2(g) = Cu2S + 2FeS + SO2(g)
FeS+1.5
𝐹𝑒𝑆 + 1.5O
​𝑂↓2(g) = FeO
2(𝑔)  ↔𝐹𝑒​ +↓SO
(s) 𝑂 (𝑠)2(g)
 +​𝑆𝑂↓2(𝑔) 
Roasted ore is charged into a reverberatory
furnace/flash smelting unit along with silica as
a flux
Output: Cu matte along with FeO.SiO2 slag.
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ž  Converting Cu-matte in Pierce-Smith Converter
ž  It involves air oxidation of molten matte received
from smelting. Two step process:
ž  FeS removal and slag formation

ž  Blister copper (>99%Cu) formation stage:

ž  Cu loss in slag starts after sulfur in matte falls

below 0.02 %
ž  Copper conversion doesnt start till Fe in matte
below 1%
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Log Po2
(atm)

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ž  Metal production from metal halides offer
processing advantages especially for metals
having high affinitiy of oxygen.
ž  Raw material : AlCl3, VCl3, TiCl4.
ž  One complication: solid/liquid chlorides may
have high vapor pressure/react to form
volatile products à must be recycled
ž  Reducing agent: liquid magnesium, sodium,
aluminium.

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Proses Metalurgi Sem II 2013/2014
ž  Production of Titanium metal
ž  Kroll process:
​𝑇TiCl
𝑖𝐶𝑙↓ 4(𝑔) +​2𝑀𝑔↓(𝑙) →​𝑇𝑖↓(𝑠) +​2𝑀𝑔𝐶𝑙↓2(𝑙) 
4(g) + 2Mg(l) à Ti(s) + 2MgCl2(l)
Reaction is highly exothermic, feed rate of TiCl2
must be controlled to avoid exceeding
temperature.
After completion, product chloride is removed by
tapping as a liquid & inert gas flushing.
Titanium product: titanium sponge
MgCl2 is recycled.

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 Removal of impurities by forming compounds
Vacuum Refining

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ž  Classes of impurities:
¡  Economically recoverable products
¡  Elements which are not of intrinsic economic
value, but harmful to metal properties or value
¡  Impurities that can be utilized to aid subsequent
refining process
¡  Elements which do not affect the value/desired
properties

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Oxidation to remove C, Si, P, Mn etc
(steelmaking)
ž  Sulfidation to remove: Cu, Ni, Co from lead,
Cu from tin, etc.
ž  Chlorination to remove Zn from lead; Zn, Cu,
and Pb from bismuth
ž  Electrochemical method by cathodic
deposition, examples: Cu, Ag, Au, Ni, Co, Pb,
Sb, Bi, etc.

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ž  Example: steelmaking & refining

ž  Iron produced by blast furnace: 3.5-5%C at 1250-1450

oC.

¡  Need to remove sulfur dissolved in hot metal

¡  Need to remove carbon
ž  Lime (CaO) is added to form slag layer:

ž  In high carbon irons, oxygen concentration in the iron

is determined by equilibrium:

High Carbon à low oxygen concentration à

desulfurisation occurs
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 Temperature /
%C %Mn %Si %P %S %O
°C
0.06-0.1
Hot metal 4.7 0.2-0.3 0.2-1.5 0.02 0.0 1350-1400
2
0.01-0.00.01-0.0
Steel 0.05 0.1 0.0 0.06 1620-1720
2 2

ž  Next stage: lower carbon content to produce

steel.
ž  Is carried out by injection of pure oxygen
into the melt forming carbon monoxide gas.
Steelmaking reactor produces 200 ton steel
in 30 minutes.

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ž  Reactions:

Reaction produces molten slag & liquid/liquid separation is

carried out after processing is completed.
Side reaction:

Oxygen blow must be stopped before unacceptable iron

losses
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ž  Final adjustment of steel compositions:
¡  Final decarburisation & melt homogenisation
¡  Final defosforisation, deoxidation, and
desulfurisation with simultaneous inclusion
removal & shape control
¡  Vacuum degassing to remove H2, N2, C, O
¡  Alloy addition and temperature addition prior to
solidification

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ž  Lead (ρ = 11,34 ton m-3)
¡  Any refining product float & can be skimmed off
ž  First step: remove Fe, Cu, Zn.
¡  Copper-led phase diagram has a low melting point
eutectic at 99.94% lead and copper.
¡  Lead bullion from furnace at 1100 oC has 1% copper
¡  Cooling liquids slowly to 350 oC, copper solidified &
separates out from the surface of liquid lead.
¡  S can be added to form Cu2S

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ž  Next step: remove Te, Sn, Sb, Ar
¡  Inclusion is removed by oxidation à Harris process.
Other impurities that has more stable oxides than
lead are removed
ž  Silver is removed from Lead by adding zinc à
forming intermetallic compound of Zn and Ag (β
& η phase) that floats on the sulface of Pb. The
melt is cooled to 320 OC to obtain max removal
of silver.
ž  Residual zinc is removed:
¡  Oxidation with air to produce ZnO
¡  Adding NaOH to produce Na2ZnO2
¡  Injecting chlorine gas to form ZnCl2 (g), or
¡  Vacuum distillation, producing Zn metal that can be
recycled
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 Bismuth is removed by the Kroll-Betterton process. Ca & Mg
are added to form compounds with Bi.

Mg
(wt%)

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 Treatment of Gases
Environmental Regulation

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ž Productionof
harmful vapors &
fine air-borne
particles.
¡  Dust
¡  Smoke
¡  Fume: solid droplets
¡  Fog: liquid droplets

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ž  Techniques
used for removal of particulate
matters from gas stream:
¡  Settling chamber
¡  Centifugal separator
¡  Wet scrubber
¡  Bag filter
¡  Electrostatic precipitator

ž  Efficiency
of gas cleaning equipments
decreases with the decrease of size of the
particles.

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ž  Major gas emission: SO2 and SF6
¡  2tonnes of SO2 gas is produced from 1 tonne
copper extracted from chalcopyrite.
ž  For
high concentration of SO2, it is possible
to produce elemental sulfur or sulfuric acid
as by-product.

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ž  Mainly diffusion controlled. Typically at 400-1100 oC.
ž  Fluid bed roaster > hearth roaster/kiln
ž  Roaster: exothermic reaction.
¡  Total investment cost of a roaster includes material
handling, gas cooling (& possible waste-heat recovery),
gas cleaning & gas blowing.
¡  The finer particle the greater the expense
ž  Calcination:endothermic reaction, supplied in the
form of HC fuel.
ž  Maintenance: gas cooling & cleaning system has
considerable operating cost
ž  Efficiency: 90-95%. Loss of value in product collection
system.
ž  Cost of processing SO2-containing gas
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ž  Smelting reactions at high temperature: very
rapid, chemical equilibrium can be achieved in
minutes.
ž  In practice, overall rate of reaction is
determined by liquid-liquid or gas-liquid
diffusion and mixing effectiveness. for
endothermic reaction, heat transfer can be rate
limiting.
ž  Smelting reaction need to include hot dirty gases
& cleaning the gases safely is expensive.
ž  Total energy cost:
¡  Exothermic: can be negative net output energy
¡  Endothermic: can use waste heat recovery, use
chemical energy of combustion.
¡  Overall: pyrometallurgy = energy intensive process.
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ž  Main loss value in smelting:
¡  solubility of metal values in the slag phase.
¡  Excess slag can be a thermal load on smelter
¡  Smelter is not selective for very minor components.
ž  Characteristic of smelting: sensitive to slag:metal ratio.
Cost of smelting operation must be considered agains up-
stream & down-stream steps.

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Proses Metalurgi Sem II 2013/2014
ž  High temperature processing is used in a wide range
of applications in the treatment of minerals, metals
& materials. The heating of materials to high
temperature results to:
¡  Significant changes in relative stability of metals &
compounds
¡  High rates of heat & mass transfer & chemical reaction
ž  Control of thermal treatments allow both equilibrium
and non-equilibrium phases to be produced.
ž  Energy in heating reactants can be minimised by:
¡  Highly concentrated process stream
¡  Available chemical energy from exothermic reaction
¡  Fuel directly in the reactor rather than indirect heating
¡  Heat recovery system
¡  Efficient reactor system which minimise heat losses

TK4046 Dasar-dasar Metalurgi Proses/TK5035 Teknologi

Proses Metalurgi Sem II 2013/2014
ž  Hayes, Process Principles in Minerals &
Materials Production, 3rd edition, Hayes
Publishing
ž  Rosenqvist, Principles of Extractive
Metallurgy, 2004, Tapir Academic Press
ž  Treatise of Process Metallurgy, 2014, edited
by Seetharaman, Elsevier

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ž  Volume 1
¡  Chapter 1.1 Introduction to Metallurgical Processing
¡  Chapter 3.1 First, Second, & Third Laws of
Thermochemistry
¡  Chapter 3.3 Ellingham Diagram
ž  Volume 3
¡  Chapter 1.1 Ironmaking
¡  Chapter 2.1 Copper Production
¡  Chapter 2.3 Lead & Zinc Production
¡  Chapter 2.9 Rare Earth, Titanium Group Metals, &
Reactive metals production
¢  2.9.2 Titanium Group Metal
¢  2.9.3 Reactive Metals (lithium, sodium, magnesium,
calcium)
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ž  Chapter 1: Introduction
¡  Sources (ores, recycled materials, partially processed
material), Products
¡  Chapter 1a: Metallurgical thermodynamics (first &
second’s law of thermodynamics, enthaply – entropy –
Gibbs energy, ellingham diagram)
ž  Chapter 2: Physical Processing of Minerals
¡  Size reductions (fracture of materials, size reduction
processes, choice of size reduction sequence)
¡  Particle Selection (on the basis of Size, density,
magnetic properties, electrical properties, surface
chemistry
¡  Bulk material handling, treatment of waste, economic
characteristics of mineral processing operation
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ž  Chapter 3: Pyrometallurgy
¡  General characteristics of pyrometallurgical
process
¡  Process aimed at separation (vapor phase
separation, chemical changes in solid state,
liquid/liquid separation)
¡  Compound formation
¡  Metal production (from metal oxides, sulfides,
and halides)
¡  Metal refining
¡  Environmental problems & economic
characteristics of pyrometallurgical processes
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