METMTB1- Extractive Metallurgy
Learning unit 9. Pyrometallurgy
9.1. Introduction
Extractive metallurgical methods are generally divided into three categories such as:
pyrometallurgy, hydrometallurgy and electrometallurgy. Historically, pyrometallurgy is
characterized using high temperature to carry out smelting and refining operations to extract metals
from their minerals.
9.2. Pyrometallurgical route
Pyrometallurgical methods are commonly used to process high-grade ores, such as iron ore, while
hydrometallurgical and electrometallurgical methods are often used in combination to extract low-
grade ores, such as copper. It is possible, however, to convert a low-grade ore into a high-grade
ore (or concentrate) by using mineral processing techniques (i.e., comminution, classification and
concentration by separation processes). The concentrate can then be used as a feed material into
either a pyrometallurgical or hydrometallurgical method.
9.3. Relative comparison between pyrometallurgy, hydrometallurgy, and electrometallurgy
Factors Pyrometallurgy Hydrometallurgy Electrometallurgy
Initial capital high low intermediate
investment
Relative energy moderate high high
requirements
Primary waste Solids and air Liquids and solids Solids and gases
products
Rate of chemical high low intermediate
reaction
Production costs low intermediate high
Level of separations low high moderate
9.4. Pyrometallurgical extraction
The pyrometallurgical process includes processes such as roasting, carbothermic reduction,
reduction of sulphide ores and metallothermic reduction. The selection of the process to be used
depends mainly on the composition of the ore or concentrate and the thermodynamic, kinetic, and
environmental constraints associated with each process. Some noble metals such as gold, silver,
and platinum can commonly occur in their native (or metallic) state. Consequently, they may need
only to be liberated and separated from the gangue materials before they can be refined. Other
metals occur as oxides and /or sulphides they need to be reduced before they can be refined. Oxides
are usually carbothermically reduced by using coke, coal, or natural gas as reducing agents.
Sulphides cannot be reduced by carbon or hydrogen because metal sulphides are more stable than
carbon sulphides. Therefore, the first step in processing metal sulphides is to convert them into a
more desirable product that can be reduced. This conversion step is known as roasting.
9.5. Roasting
There are many different types of roasting processes. The most used roasting processes are:
▪ Dead roasting
▪ Sulphating roasting
▪ Partial roasting
9.5.1. Dead roasting
Dead roasting is the complete conversion of sulphides into oxides by heating the ore or concentrate
under an oxidizing atmosphere
𝟐𝐌𝐒 + 𝟑𝐎𝟐 = 𝟐𝐌𝐎 + 𝟐𝐒𝐎𝟐 (1)
𝐌𝐒 + 𝟐𝐎𝟐 = 𝐌𝐎 + 𝐒𝐎𝟑 (2)
9.5.2. Sulfating roasting
Sulfating roasting is the conversion of sulphides into soluble sulphates. This conversion is also
accomplished by heating the sulphide under an oxidizing atmosphere. The soluble metal sulphates
can then be used as the feed material for hydrometallurgical extraction processes.
𝐌𝐬 + 𝟐𝐎𝟐 = 𝐌𝐒𝐎𝟒 (3)
9.5.3. Partial roasting
Partial roasting is a common roasting operation for metal concentrates containing several metal
sulphides. In this roasting operation, the impurity metal sulphides are preferentially oxidized to
enable their easier separation from the desirable metal sulphides during the subsequent extraction
operations. For example, during the smelting operation the metal oxide would be absorbed by the
slag phase.
During the roasting operation, sulphur dioxide and trioxide are formed. Consequently, this type of
operation can pose a major environmental problem. Sulphur dioxide and trioxide released into the
atmosphere can be major causes of acid rain.
So, overall, modern roasting furnaces have highly engineered exhaust systems, and the sulphur gas
emissions are commonly used as a feed material in the production of sulfuric acid. After the
roasting operation the calcine (or roasted concentrate) may pyrometallurgically reduced or
hydrometallurgically leached. If a dead roasting process is used an oxide is formed, and the
subsequent operation may be a carbothermic reduction, as in the case of zinc and lead sulphide
ores. However, if a partial roasting process is employed the desirable metallic mineral will still be
in the form of a sulphide.
9.6. The predominance area (Ingraham Kellogg) diagrams
The isothermal behaviour of some M-S-O systems with respect to their relative stability can be
represented by predominance area diagram also referred to as Kellogg diagrams. These diagrams
indicate those solids which are in equilibrium with the gas having certain partial pressure of oxygen
and sulphur dioxide. While predominance area diagrams (PADs) are useful for the determination
of the stable phases in the metal–sulphur–oxygen system, they are constructed at constant
temperature. Varying the temperature results in shifting of the equilibrium lines and the stability
areas thereof. Since the available tools in hands of an extractive metallurgist are temperature and
oxygen potential, a more useful diagram would be one that shows the stability areas of different
phases as a function of temperature and percent of oxygen in the roast gas. Hence the diagram
helps to predict the type of solid present that would be in equilibrium with the roaster gas of a
known composition. Sulphur dioxide gas is considered because during roasting of sulphide ore
𝑆𝑂2 gas is formed.
Figure 1: PAD of Pb-S-O and Zn-S-O system
9.6. Carbothermic reduction
The blast furnace process is primarily used in the carbothermic reduction of oxides, such as iron,
zinc, and lead. Most of the iron ore bodies commercially explored consist of iron oxides.
Consequently, rich iron ore and/or iron oxide pellets formed from concentrate can be added
directly to a blast furnace. Carbothermic reduction generally relies upon the Boudouard reaction
which is expressed as;
2CO = CO2 + C (4)
And accordingly, the reduction of metal oxides may be simplistically viewed as
MO + CO = M + CO2 (5)
In the case of zinc and lead, their ores are sulfidic. Therefore, before the carbothermic reduction
can take place, the zinc and lead sulphide concentrates are converted to oxides and agglomerated.
Besides the blast furnace process the zinc and lead calcine can for example be used as feed material
to the Imperial Smelting Furnace (ISF). The major difference between a lead blast furnace and the
ISF is that in the lead blast furnace the lead oxide is reduced by carbon monoxide which is
generated by the combustion of metallurgical coke with air within the furnace. The zinc oxide
remains in the slag phase and the slag is subsequently treated by adding coal to reduce the zinc
oxide to metallic zinc. The metallic zinc is removed by vaporization because of its low boiling
point (707 °C). In the case of the ISF, the zinc oxide is simultaneously reduced with the lead oxide
by carbon monoxide. The zinc vapor is ʻʻshock-cooledʼʼ (or condensed) by spraying the hot off-
gas in the exhaust system with liquid lead at 600 °C and collected on the top of the furnace. The
lead bullion (or impure lead) is tapped from the bottom of the furnace. Both the lead bullion and
zinc‒lead alloy must be subsequently refined.
9.7. Ellingham diagram
An Ellingham diagram is a plot showing the temperature dependence of the stability of
compounds. The plot is usually used to evaluate the ease of reduction of metal oxides and
sulphides.
Figure 2: Ellingham diagram
9.7. Reduction of sulphide
Most of the sulphide ores are normally concentrated and roasted before they can be reduced. There
are several pathways for the reduction of sulphides. The copper making process illustrates well
this point. In some cases, copper extraction can be divided into three steps:
▪ roasting (which can be optional for some copper-making routes);
▪ matte smelting (reverberatory, electric, or flash smelting furnaces);
▪ converting (conversion of matte to blister copper).
There are also now available continuous copper smelting technologies such as the Mitsubishi
process that combine all the above steps.
The purpose of matte smelting is to separate the metal sulphides (Cu2 S − FeS) from the gangue.
The metal sulphides form a phase known as matte, and the gangue materials are absorbed by the
slag phase.
5
2CuFeS2 (𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑒) + 𝑂 + SiO2 (flux)
2 2
= CuS: FeS(𝑚𝑎𝑡𝑡𝑒) + FeO. SiO2 (𝑠𝑙𝑎𝑔) + 𝑆𝑂2 + Heat (6)
The converting step consists of oxidizing the liquid matte with air to obtain blister copper (an
impure form of copper). The converting process can be subdivided into two stages:
1. Slag forming stage: FeS is oxidized to iron oxide and absorbed by the slag phase. The
product of this stage is the white metal which is mainly Cu2 S
2FeS + 3O2 + SiO2 (flux) = 2FeO. SiO2 (slag) + SO2 (7)
2. Copper-making stage: the remaining sulphur is oxidized keeping the oxidation of copper
to a minimum.
Cu2 S(white metal) + O2 = 2Cu(blister) + SO2 (8)
As previously noted, three steps of copper extraction (roasting, smelting, and converting) can also
be carried out continuously in for example the Mitsubishi process. The Mitsubishi process consists
of three furnaces in series (a smelter, an electrical settling furnace, and a converter).
9.8. Metallothermic reduction
An alternative way to reduce an ore (or concentrate) is by using a metal that has a higher affinity
for oxygen or sulphur as a reducing agent. The metallothermic reduction process is exothermic
and self-sustained once it is started.
MeO + M = MO + Me (9)
For example, the aluminothermic method uses aluminium as a reductor because of its reactivity.
Aluminothermia is extensively used to reduce metal oxides of metals that have a very high melting
point and/or can form hydrides and carbides. However, the metallothermic method is not selective,
i.e., any oxides present in the ore that have less affinity for oxygen than the reactive metal will also
be reduced.
Cr2 O3 + 2Al → Al2 O3 + 2Cr (10)
3MgO + 2Al → Al2 O3 + 3Mg (11)
In addition, this is a very expensive process because highly reactive metals, such as aluminium
and silicon, are used as reductors
9.9. Pyrorefining
The objective of the pyrorefining operations is to remove impurities from a metal. The removal of
an impurity is directly related to the final cost of the metal. Therefore, refining is carried out to the
extent that is necessary to produce the desired mechanical, physical, and chemical properties in
the metal. The pyrorefining operations can be divided into slag‒metal reactions, metal‒metal
equilibria and metal‒gas reactions.
9.9.1. Slag‒Metal Reactions
Slag is a mixture of oxides such as calcium, silica and iron that is added on top of a metal to
accomplish the following main functions:
1. to flux and absorb impurities;
2. to protect the reduced metal against reoxidation; and
3. to minimize heat loss by radiation.
The flux and absorption of impurities are accomplished by designing a slag that will have a greater
capacity to chemically react, melt, and bind with the impurities. The distribution of the impurity
between slag‒metal phases should be maximized such that a minimum amount of slag is used. The
problem associated with the use of a large volume of slag is an increase in the amount of energy
used to heat and melt the slag. Steel and tin production extensively use slag‒metal reactions as a
refining method.
9.9.2. Metal‒Metal Equilibria
In some cases, impurities can be separated from the product without forming a slag. Liquation is
a metal‒metal equilibrium separation method that relies on the immiscibility between solvent and
solute in alloys when the temperature is lowered. Liquation is commonly used in refining the zinc‒
lead alloy obtained during shock- cooled exhaust gases in the ISF. The solubility of zinc in lead
decreases and the temperature decreases, therefore as the temperature is lowered second phase rich
in zinc is formed. The zinc-rich phase has a much lower density than the lead rich phase, and it
can be separated easily.
Drossing, which consists of the preferential oxidation of a metal in relation to another metal in an
alloy, can also be used to promote separation. For example, one of the refining steps of the lead
bullion is the removal of copper. This is accomplished by oxidizing copper with elemental sulphur,
since copper has a higher affinity for sulphur than lead. Consequently, a copper sulphide layer on
the top of the lead is formed which can be separated easily. However, Drossing separation is not
as good as slag‒metal separation because a large amount of metal is usually entrained in the dross.
Thus, a further treatment of the dross is normally needed to enhance metal recovery.
9.9.3. Metal‒Gas Reactions
Vacuum degassing and distillation are also common techniques used in refining operations.
Vacuum degassing is usually used in the refining of steels, especially in the removal of carbon (as
carbon monoxide) and hydrogen. The process consists of placing the liquid metal under a very low
partial pressure to promote the removal of gases and other elements present in the alloys that have
very high vapor pressures. Distillation exploits the difference in partial pressures among the
elements present in an impure metal or alloy. The impure metal or alloy is placed in a distillation
column and heated. The volatile constituents are removed from metals which have higher melting
points. A criterion for a successful distillation is that the mass distribution ratio of the component
to be separated must be greater in the vapor phase than in the condensed phase. Distillation plays
a major role in the production of zinc and mercury.
