Non Ferrous Metal
Extraction
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Non Ferrous Metal Extraction Course Syllabus
L-T-P Structure 3-1-0 Credits / # of period4 / 40 Periods Course number(Code) CMT43 Status (Core/Elective) Core
Pre-requisites (course no./title) Metallurgical Thermodynamics and kinetics
Unit-1
Introduction to Pyro-metallurgy, Hydrometallurgy and Electrometallurgy. General methods of extraction in Pyro-metallurgy - Drying, Calcination,
Roasting, Smelting, Carbothermic and Metallothermic reduction.
Unit-2
Principles of hydro and electrometallurgy with suitable examples. Leaching techniques, Leaching solvents, Theory of leaching, Bacterial leaching,
Electrochemical nature of leaching, Pressure leaching.
Unit-3
Electrometallurgy - Electrolysis of aqueous solutions and fused salts, Cell design. Recovery of metals by Cementation, Electro-winning, Electro-
refining. Gold and silver extraction, Sherritt-Gorden process for Copper, Nickel, Cobalt; Solvent extraction, Ion exchange. etc.
Unit-4
Extraction of metals from oxides-Magnesium and Titanium extraction, Aluminum extraction-Bayer’s process and Hall-Heroult process. Extraction
of metals from sulphides; Extraction of Copper, Lead, Zinc, Nickel. General methods of refining, Principles of Refining, Sublimation, Distillation
and Vacuum Distillation, fractional distillation, crystallization, chemical precipitations, Ion exchange, Fire Refining and Liquation.
Text Books:-
Extraction of Non- Ferrous Metals – [Link], K.P. Abraham and R. Sridhar, Affiliated East-West press Pvt, ltd, New
Delhi,1985.
Principles of Extractive Metallurgy, [Link] and A. Ghosh, New Age International(P) limited, 1995
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Introduction to unit processes
• MINERAL: It is a naturally occurring inorganic compound of one or more metals in
association with nonmetals such as oxygen, Sulphur and the halogens. A mineral has fixed
composition and well defined physical and chemical properties.
• ORE: It is the naturally occurring aggregate or combination of minerals from which one or
more metals or minerals may be extracted economically (profitably).
• UNIT OPERATIONS: The physical processes like crushing, grinding, classification,
concentration etc. are called unit operations.
• UNIT PROCESSES: The chemical processes like calcination, smelting, roasting, leaching
etc. are called unit processes.
Based on the process adopted to extract the metal:
• Mineral processing (crushing, milling,, concentration techniques)
• Pyrometallurgy
• Hydrometallurgy
• Electrometallurgy 3
UNIT PROCESS
PYROMETALLURGY HYDROMETALLURGY ELECTROMETALLURGY
• Utilization of high temperatures to • Utilization of aqueous environments to “leach” • utilization of electricity to
modify the chemistry of minerals, metals from minerals, to separate dissolved recover and/or to refine
to reduce minerals to metals, and metals from each other or dissolved impurities, metals in aqueous or molten
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to refine metals. and to recover metals from solution. salt solutions.
PYROMETALLURGY
• Pyrometallurgy is the branch of extractive metallurgy.
• Pyrometallurgy deals with the methods of extraction of metals from
their ores and their refining and is based on physical and chemical
changes occurring at high temperatures.
• This treatment may produce pure metals, intermediate compounds,
alloys, suitable feed for further processing.
• Pyrometallurgical processes require energy to take place .
• The energy is provided by fuel combustion, electrical heat, exothermic
reaction of materials.
• Autogenous - exothermic.
Extraction of reactive metals: Can’t use aqueous methods
• Pyrometallurgy – direct reduction or fused salt methods
• Pyrometallurgy can deal with heavy quantities 5
What are the advantages of high temperature?
• As at high temperature, the reaction rate is accelerated which leads
to more metal production.
• Also at high temperature the inexpensive reducing agent can be used
and cheaper raw material can be used.
• As we know that the reaction rate doubles in each 10ºC rise of
temperature which requires small activation energy.
• It helps in fast reaction. 25C towards left
• Shift of reaction is possible. ZnO+C Zn + CO 1200C towards right (above 900C)
• Brings about a reduction which cannot takes place in presence of
water.
• Only Pyrometallurgy and fused salt electrolysis can extract reactive
metals namely the alkaline earth metals zirconium and titanium.
• Ability to treat a large tonnage of ore in a compact space, which
leads to a saving in capital cost.
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Pyrometallurgy includes
1. Calcination thermal decomposition of a material
2. Roasting thermal gas/solid reactions, which can include oxidation, reduction, chlorination, sulfation, and
pyrohydrolysis.
3. Smelting thermal reactions in which at least one product is a molten phase
4. Refining removal of impurities from materials by a thermal process. This covers a wide range of
processes, involving different kinds of furnace or other plant.
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CALCINATION
Calcination - denote thermal decomposition of solids and eliminate
volatile product i.e. carbon dioxide and water.
Solid 1 = Solid 2 + Gas
Decomposition of a carbonate: MCO3 (s) = MO (s) + CO2 (g)
• Temperature required for this process can be calculated from free
energy temperature relationship for the reaction under consideration.
• CaCO3 (s) = CaO (s) + CO2 (g) ΔGoT (cal) = 42,300 – 37.7 T
• When CO2 pressure is 1 atm and ΔGoT =0 then T = 1123 K (850 oC)
• As the most decomposition reaction is endothermic, so the
temperature of calcination is generally depends on the transfer of heat
into the particle.
• This result in even high temperature of the furnace (kiln) at the
expanse of some fuel. 8
Pyrometallurgy_Calcination Calcination temperature
(i) Calcination
• The temperature required for calcination can be calculated from the free energy-temperature
relationship for the reaction under consideration.
• For example, the reaction for the decomposition of calcium carbonate in a kiln is
CaCO3 (s) ⇌ CaO (s) + CO2 (g), ∆G0T (cal) = 42300- 37.7T
• When the CO2 pressure is at 1 atm, ∆G0T becomes equal to zero and T becomes equal to 850oC so
that a kiln temperature of 1000oC would be sufficient to provide a rapid temperature rise in the
mineral particles and to reach the decomposition temperature.
• Since the calcination reaction is endothermic, the rate of decomposition is controlled by the rate of
heat transfer into the mineral particles. As a result even higher kiln temperatures can be expected
so as to increase the production rate, but at some cost in fuel. Since the solid residual product is
likely to be porous in texture and permeable, the gaseous product can easily escape.
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Pyrometallurgy_Calcination
Calcination temperature
• Let us consider the decomposition of a carbonate. Assuming the solid phases as to be pure, the equilibrium pressure of
carbon dioxide is then a function only of temperature:
where K is the equilibrium constant and ∆G0 is the standard free energy change for the reaction.
• A plot of the equilibrium pressure of carbon dioxide as a function of temperature is
shown in Figure.
• It is observed that as the temperature rises, the equilibrium pressure of carbon
dioxide exhibits a rapid increase. The temperature at which the equilibrium
pressure reaches 1 atm (101 kPa) differs from substance to substance, but all these
temperatures are readily attainable in practice.
• While the temperature required in the case of FeCO3 is only 200°C, those required for MgCO3 and CaCO3 are
400 °C and 900 °C respectively; the temperature requirements for SrCO3, whilst some others (not shown)
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such as BaCO3 and Na2CO3 are even higher.
Pyrometallurgy_Calcination Calcination temperature
• In air, the dissociation of a carbonate can be considered to begin at the
temperature at which the dissociation pressure (equilibrium pressure of
carbon dioxide) of the carbonate exceeds the partial pressure of carbon
dioxide in air (~ 0.03%).
• However, vigorous decomposition of carbonates occurs at temperatures at
which the dissociation pressure exceeds the atmospheric pressure (1 atm).
• The decomposition point for carbonates thus refers to the temperature at which PCO2=1 atm.
• It is obvious the some carbonates actually start to decompose at temperatures lower than the decomposition
temperature of CaCO3. This fact can be utilized for differential calcination.
• For example, a magnesium ore that contains MgCO3 and CaCO3 can be beneficiated by calcining the ore
around the decomposition temperature of MgCO3. Water is used to leach out the resulting MgO, and the
undecomposed CaCO3 is left behind.
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Pyrometallurgy_Calcination
Calcination temperature
• Let the points A and B in Figure be considered for a description of calcination of limestone which occurs as : CaCO3 = CaO
+ CO2
• Provided that the temperature and the carbon dioxide pressure conditions in the calcination furnace are such that they
correspond to the point A, or to any point above the calcium carbonate line, no dissociation occurs because in such a
situation,
• On the other hand, if the conditions correspond to the point B, or to any point
beneath the calcium carbonate line, then
-ve
• This condition is favorable for the dissociation to occur.
• The decomposition behavior of all the carbonates can be explained in a similar manner, and the conditions
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necessary for their decomposition are entirely desirable.
Pyrometallurgy_Calcination Effect of impurities
• The presence of impurities can cause a shift in the dissociation point. It implies that the equilibrium temperature and pressure of
the carbonate decomposition reaction are shifted.
• For example, if silica is present as an impurity, it lowers the decomposition point of limestone and thus makes the
decomposition of CaCO3 far easier.
• The acid anhydride silica slags combines with the basic calcium oxide according to following reaction:
and the equilibrium constant becomes,
• Since the value of K is fixed at a fixed temperature, and since aCaO is less than unity, the value of the decomposition
pressure PCO2 for the calcium carbonate decomposition reaction at a given temperature is greater in the presence of
silica than in its absence in limestone.
• The occurrence of silica thus makes the decomposition of calcium carbonate far easier. 13
Pyrometallurgy_Calcination Furnaces
• Three different types of furnaces are generally in use for calcination.
• The shaft furnace is considered to be the most suited for calcining coarse limestone.
• Furnaces of the rotary kiln type are used for handling materials of mixed particle sizes and lumps which
disintegrate during the process.
• Calcination can be carried out in a fluidized bed reactor for materials of small and uniform particle size.
• These furnaces are usually fired with gas, oil or coke; in some cases electric heating is resorted to.
• Furnaces of the rotary kiln type are used for handling materials of mixed particle sizes and lumps which
disintegrate during the process.
• Calcination can be carried out in a fluidized bed reactor for materials of small and uniform particle size.
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Pyrometallurgy
(ii) Roasting Introduction
• Roasting of a mineral or a concentrate is usually an oxidizing process and in most cases its main purpose is to
oxidize sulphide minerals. This process is carried out by heating the sulphides in air or in oxygen.
• The roasting process precedes smelting in pyrometallurgy and leaching in hydrometallurgy.
• In general, very few minerals and concentrates in their native form are suitable for direct conversion to the
metal.
• An oxide mineral is more easily reduced to the metal than a sulphide mineral, and leaching becomes easier if the
metal were present as a sulphate, chloride, or oxide. Therefore, the sulphide mineral must be converted into
another chemical form. Such a conversion can be brought by roasting.
• Roasting usually involves heating of sulphide minerals below the melting point or sintering temperature in
presence of excess air, to change it chemically to a form more amenable to subsequent treatments for ultimate
extraction of the metal.
• The main purpose of calcination is to decompose a mineral whereas roasting by employing oxygen or some
other element aims at the chemical conversion of a mineral. 15
Pyrometallurgy
(ii) Roasting Introduction
• In addition to common metals like Cu, Pb, Zn, and Ni, a number of other metals such as Sb, Bi, Cd, Co, and
Mo occur as sulfide minerals.
• Sulfides are not reduced with the most widely used reducing agents, C and H, because the free energy change
for the reactions 2MS + C = 2M + CS2 and MS + H2 = M + H2S (where M represents a metal) is positive
due to the lesser stability of CS2 and H2S, compared to most sulfides.
• Since the free energy of formation of SO2 and SO3 is lower than the free energy of formation of many
sulfides (CuS, Cu2S, NiS, FeS, PbS, ZnS, MnS, and so on under standard conditions), oxygen is
conveniently used to remove sulfur from sulfides. Hence, the typical step, roasting (controlled oxidation) is
employed to remove sulfur from sulfide minerals by forming SO2 and SO3. (2MS + 3O2 = 2MO + 2SO2)
• Traditionally roasting was chiefly used to remove S or other elements such as As and Te in the form of a
volatile oxide from a mineral.
• Nowadays, however, roasting encompasses a wide variety of operations including oxidation, reduction,
sulphation, and chloridization, wherein the mineral is heated to a temperature below the fusion point of its
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constituents.
Calcination Roasting
• It is used for carbonates, oxide and hydroxide • It is used for sulphide ores
ores • Ore is heated in the presence of air
• Ore is heated in the absence or limited supply • SO is produced along with the metal oxide
2
of air
• ZnS+O2----- ZnO+SO2
• CO2 and H2O produce along with metal oxide
• Al2O3.2H2O-----Al2O3+2H2O
2 PbS( s ) 3 O2 ( g ) heat
2 PbO( s ) SO2 ( g )
• ZnCO3------------ ZnO+CO2
HgS( s ) O2 ( g ) heat
Hg (l ) SO2 ( g )
PbCO3 ( s ) PbO( s ) CO2 ( g )
Fe2O3 2 Fe(OH)3 ( s ) 2 Fe2O3( s ) 3 H 2O( g )
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Pyrometallurgy
(ii) Roasting Mechanism of Roasting
• Roasting is essentially a surface reaction where the oxide layer is formed first and continues to remain as a porous
layer through which oxygen can pass into the still unreacted inner sulphide portion of the particle, and the SO2 gas
formed comes out.
2MS + 3O2 = 2MO + 2SO2
• Once the roasting has started it is autogenous, that is, no external fuel is required, because of the exothermicity of
the roasting reactions. The burning of the sulfides often provides more heat than required to self-sustain the
roasting process.
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Mechanism of Roasting
Pyrometallurgy
(ii) Roasting
• Whatever method of roasting used, the sulphide mineral particles
must be exposed to a current of air and heat.
• As the air strikes the heated particles of metal sulphide, they
begin to burn by the general reaction:
2MS + 3O2 = 2MO + 2SO2
• As shown in Figure, the roasting reaction begins at the surface of MS particle to form MO. As the reaction
continues the product MO remains as a somewhat porous layer on the surface of MS and diffusion of gases (O2 and
SO2) takes place through the MO layer.
• The O2 gas diffuses from outside to inside and SO2 gas formed diffuses from inside to outside, through the porous
MO layer.
• As the roasting proceeds, the thickness of oxide layer (MO) increases and hence diffusion of gases become
difficult. Ultimately at the MS–MO interface concentration of O2 decreases and concentration of SO2 gas
increases; due to this condition reaction can go in backward direction, i.e., again there is a chance of MS formation.
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To avoid backward reaction, i.e., MS formation, SO2 gas must be removed from the roasting chamber.
Pyrometallurgy
(ii) Roasting Rate of Roasting
• Rate of roasting of a metal sulphide (MS) can be increased by
increasing the rate of diffusion of O2 gas through MO layer by the
following ways:
• (i) Grinding the MS lump before roasting: This increases the ratio of surface area to unit weight of the MS
particle. Fine particles can have thinner oxide layer than that for coarse particles.
• (ii) Increasing the temperature (below melting point): This increases the rate of diffusion of gases through pores
in the oxide layer.
• (iii) Increasing the partial pressure of O2 (than that of SO2): It favors the forward reaction for formation of MO.
• Hence, metal sulphide particles falling down or floating in the air or gas are roasted quicker than those lying in the
bed. Thus, a high rate of roasting is obtained in case of falling or floating particles. The roasting rate of particles
lying in bed may be increased by stirring the charge with rabbles. 20
Types of roasting
1. OXIDIZING ROASTING:
• Oxidizing roasting, the most commonly practiced roasting process, involves heating the ore in
excess of air or oxygen, to burn out or replace the impurity element, generally sulfur, partly or
completely by oxygen.
• For sulfide roasting, the general reaction can be given by:
MS(s) + 3/2 O2 (g) → MO(s) +SO2 (g)
• Roasting the sulfide ore, until almost complete removal of the sulfur from the ore, results in a
dead roast.
• Quartz and other gangue material acts as catalyzer.
2. VOLATILIZING ROASTING:
Careful oxidation at elevated temperatures
To eliminate impurity elements in the form of their volatile oxides
such as As2O2, Sb2O3 and ZnO from an ore. 21
3. CHLORIDIZING ROASTING
• In this roasting process the ores are converted to chlorides either in oxidizing or reducing
condition.
• Metals like uranium, beryllium, niobium, zirconium and titanium are extracted from their
chlorides.
• The reactions is of the type
2NaCl(s)+PbS(s)+2O2(g)= Na2SO4(s)+PbCl2(l)
4. Autogenous roasting: Some of the high sulphide minerals and concentrates may be roasted
autogeneously, i.e., heat generated by oxidation of the sulphides is sufficient for reaction to
proceed. In other cases, this heat is not sufficient and some fuel used for roasting furnace to
maintain the required temperature.
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Pyrometallurgy
(ii) Roasting Types of roasting
• (v) Other kinds of roasting: Apart from oxidizing roasting, volatilizing roasting, and
chloridizing roasting, there are other kinds of roasting processes such as below ones.
• Sulphating roasting converts certain sulphide minerals to sulphates, usually prior to leaching.
• Magnetic roasting involves controlled roasting of the mineral to convert it into a magnetic
form, for example from non magnetic hematite (Fe2O3) to magnetic magnetite (Fe3O4).
• Reduction roasting is the partial reduction of an oxide mineral prior to actual reduction
smelting.
• Blast roasting or sinter roasting involves heating the fine mineral particles at high
temperatures, where simultaneous oxidation and agglomeration of the particles take place.
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Pyrometallurgy
(ii) Roasting Chemistry of roasting
• The roasting process is the most complex of all the pyrometallurgical unit operations.
• Where more than one metal sulfide is present in the concentrate, numerous reactions may occur, important of which are as
follows:
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Pyrometallurgy
(ii) Roasting Chemistry of roasting
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Pyrometallurgy
(ii) Roasting Chemistry of roasting
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Pyrometallurgy
(ii) Roasting Thermodynamics of Roasting
• Roasting is gas/solid reaction in which a metal sulphide is converted to metal oxide or metal sulphate or even to metal.
• The composition of a product in sulphide roasting depends not only on the chemical and mineralogical composition of the
concentrate, temperature, and partial pressures of O2, SO2, and SO3 but also on the other process parameters such as particle
size, mixing, time duration of reaction, and the technique of roasting.
• The necessary conditions for the formation of different
products (metal, oxide, sulfide, or sulfate) can be illustrated by
the equilibrium relationships in any metal-sulfur-oxygen (M-
S-O) system.
• It is possible to show the equilibrium relationships of the M-S-
O system on a 2D plot called predominance area diagram.
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Pyrometallurgy
(ii) Roasting Thermodynamics of Roasting
• The most important roasting reactions are those concerning metal sulphide (MS) concentrates and involve
chemical combination with the roasting atmosphere as below:
• By examination of the equilibrium constant K for each of these roasting
reactions, as activity for pure solids in their standard state is equal to 1, it
is possible to determine the values of pO2 and pSO2 at which each of the
roasting products (roast) is in equilibrium with the metal sulphide at a
constant temperature.
• Increasing or decreasing the pO2 or pSO2 results in either the roast
(product) or metal sulphide (reactant) being stable. Further changes in pO2
and pSO2 may produce other roasting reactions.
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Pyrometallurgy
(ii) Roasting Thermodynamics of Roasting
• Roasting is a gas/solid reaction in which a metal sulphide is converted to metal oxide or metal sulphate or even to
metal.
• The temperature at which roasting is carried out is an important factor in determining the nature of the product
obtained.
• In order to get a desired product, we can determine the best operating temperature by knowing both the
composition of the gas used in an industrial roaster and the equilibrium phase relationship in an M-S-O system.
• At any specified temperature the composition of the roaster
gas is defined by the partial pressure of gaseous components,
pO2 and pSO2. Further, for any fixed gas composition, the
composition of the condensed phase gets fixed.
• For a given temperature, those solids which are in equilibrium
with a roaster gas of known composition and having specified
partial pressures of oxygen and sulphur dioxide can be
predicted by predominance area diagrams (PADs).
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Pyrometallurgy
(ii) Roasting Thermodynamics - Gibbs phase rule
• The equilibrium state of a material is always that which has the lowest
free energy. It may be thought of as lying at the bottom of a free energy
well.
• At equilibrium, the compositions, structures, and amounts of the phases
do not vary with time at a given T and P.
• Most minerals are multicomponent systems and the most stable phase at
any temperature will be the one with the lowest free energy.
• The number of phases that can co-exist in equilibrium is described by the Gibbs phase rule.
F=C–P+2
• The phase rule relates the number of equilibrium phases (P), the number of chemical entities in the system (or
components, C) and the total degrees of freedom (F) i.e. the number of intensive thermodynamic variables that are
independent. The integer in the phase rule is related to the intensive parameters T and P that are being considered.
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Pyrometallurgy
(ii) Roasting Thermodynamics of Roasting
• In the M-S-O system, there are 3 components, that is metal, sulphur and oxygen. Also pressure has no effect on
condensed phases and mostly roasting is carried out at a constant pressure.
• The phase rule as applied to a 3 component system at constant temperature and pressure reduces to F = 0 = 3-P.
Thus P = 3 and a maximum of 3 condensed phases can co-exist.
• The PAD shows the ranges of gas compositions (partial pressures of SO2 and
O2) over which each phase (M, MS, MO, MSO4) exists singly, or in
equilibrium with another phase or phases.
• The co-existence of 3 condensed phases in the M–S–O system as per phase
rule is indicated by the point of co-existence of M, MO and MS, as well as by
the point at which MS, MO and MSO4 co-exist in the figure.
• At the fixed temperature, the values of pO2 and pSO2 necessary for the
maintenance of equilibrium between any two condensed phases are
represented by the lines. The areas bounded by the lines represent the pO2 and
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pSO2 values over which only a single condensed phase is stable.
Pyrometallurgy
(ii) Roasting Thermodynamics of Roasting
• Reactions which involve both SO2 and O2 are seen to have a diagonal line
since the equilibrium phases produced will depend on the partial pressure
of both gases. The roasting of a metal sulphide to a sulphate will produce a
vertical reaction line since only O2 will take part in the reaction.
• The PAD provides the predominance areas for each phase within which pO2
and pSO2 can be varied without altering the roasting product.
• For example, if the conditions of roasting correspond to any point in the region marked MO in the figure, the end
product will be an oxide; if the conditions correspond to a point on the line separating the MO and the MSO4
regions, then a mixture of the sulfate and the oxide will be obtained by roasting. The metal will be the end product
of roasting if at the temperature T the values of pO2 and pSO2 are maintained within the M region.
• In the predominance area for a particular condensed phase, both pO2 & pSO2 can be varied independently, and the
system has 2 degrees of freedom (bivariant). Along the lines, the system has 1 degree of freedom (univariant) as
either pO2 or pSO2 can be varied. The system is invariant when 3 condensed phases are at equilibrium for particular
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value of pO2 & pSO2 .
Pyrometallurgy
(ii) Roasting Thermodynamics of Roasting
NiSO4
• PADs, which are plotted from available thermodynamic data, provide
information that help control roasting conditions so that the desired end
products can be obtained.
• The PAD for Ni-S-O system is shown in Figure at a temperature of 1000
K.
• In operation at 1 atm total pressure, gas compositions from 3–19% O2 and
3–10% SO2 would yield NiSO4 as the stable solid phase.
• At a gas composition of 1% O2 and 1% SO2, NiO would be stable. At the univariant point (pSO2 = 2.5×10–5 atm and pO2 = 5×10–
16 atm), the required conditions are so reducing that it is unlikely that metallic Ni would be formed in roasting operation.
• The influence of temperature on these equilibria also can be used advantageously to produce a desired end product by shifting
the location of the predominance area. The effect of temperature on the roasting equilibria may be given in a two-dimensional
diagram (T vs pSO2 or T vs pO2) for constant values of pO2 or pSO2.
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Pyrometallurgy
(ii) Roasting
Thermodynamics of Roasting
• If a metal forms several sulfides and oxides, additional
1100 K
equilibria would have to be considered for the formation
of MS2, M2O3 and M2(SO4)3 and so on. In addition,
basic sulfates, such as MO·MSO4, may exist.
• For example, in the Pb-S-O system, PbO can form
several basic sulphates, namely, PbSO4·4PbO,
PbSO4·2PbO, and PbSO4·PbO before it is converted to
PbSO4.
• This figure also gives the composition of the roaster gas
in a conventional roaster operating at 827oC and shows
that the stable product obtained by roasting PbS should
be PbSO4.
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Pyrometallurgy
(ii) Roasting
Thermodynamics of Roasting
• Since the PbS and PbO fields do not have a common boundary, PbO
cannot be produced by roasting PbS in oxygen without some PbSO4 1100 K
also being formed. This accounts for the difficulty encountered in
dead roasting to PbO at 827oC, which explains why PbSO4 is
predominant in lead fumes rather than PbO.
• On the other hand, a sulphatizing roasting of PbS to yield PbSO4 can
be carried out, but it is not desirable, as PbSO4 is insoluble in water.
• The possibility of a roast reduction reaction in which PbS is
converted to metallic Pb by controlling pO2 and pSO2 is also
indicated in the Figure.
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Pyrometallurgy
(ii) Roasting Thermodynamics of Roasting
• By studying the PADs drawn for different temperatures, we can select the most suitable temperature for a given
roasting operation and to get a desired product.
• In a PAD, at a given temperature, the predominance areas for a given compound may have different locations for
different metals. This means that the position of the equilibrium lines may change and, consequently, the size and
the position of the areas between the lines. 36
Pyrometallurgy
(ii) Roasting Partial Roasting
• Oxidizing roast is carried out to prepare a totally or a partly oxide product. For example, dead roasting of sphalerite
(ZnS) concentrate to an all-oxide product is the prerequisite for the pyrometallurgical smelting processes. For
copper and nickel extraction, only partial roasting is practiced.
• Even in the case of partial roasting, where equilibrium conditions do not prevail, the PADs can be used to identify
the type of the product formed as the reaction proceeds towards equilibrium.
• The ore concentrate will undoubtedly contain other metal sulphides each with their own phase predominance areas
dependent upon pO2, pSO2 and temperature.
• By examination of the appropriate diagrams it is possible to obtain information which will enable the roasting
operator to select the most appropriate roasting conditions for each particular concentrate.
• In this way selective roasting of one metal sulphide to its oxide may be achieved while another metal present in the
concentrate remains as the sulphide.
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Pyrometallurgy
(ii) Roasting Partial Roasting
• One of the most common roasting operations is that of
partial roasting in which the metal concentrate containing
several metal sulphides is roasted to preferentially
oxidize the impurity metal sulphides and to reduce the
level of sulphur present.
• In the ∆Go-T diagram for sulphide roasting reactions
(Figure), the reaction lines lower down the diagram
indicate those metal sulphides which are more readily
converted to an oxide.
• For example, in the case of a mixed sulphide such as Fe-
Cu sulphide, partial roasting will selectively oxidize Fe to
Fe3O4 while retaining Cu as a sulphide.
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Pyrometallurgy
(ii) Roasting Partial Roasting
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