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Pyrometallurgy

Chapter · January 2016

DOI: 10.1016/B978-0-12-803581-8.03609-2

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Pyrometallurgy
C. G. Anderson
Kroll Institute for Extractive Metallurgy
George S. Ansell Department of Metallurgical and Materials Engineering
Colorado School of Mines, Golden, Colorado

The Earthʼs crust is the source of almost all the metals. The average concentrations
of metals in the Earthʼs crust can be relatively low. Fortunately natural geological
phenomena, such as igneous intrusions, weathering and sedimentary deposits, have
helped produce local areas of enrichment of metallic minerals, i.e., resources,
deposits, ore and ore bodies. Many factors must be taken into consideration to
determine if it is economically viable to develop a deposit, such as:

 valuable metal content of the resource;

 commercial value of the desired metal;

 potential by product metal production;

 levels of undesirable and desirable impurities;

 location of the ore body in relation to infrastructure, fuel, electricity, labor and
transportation;
 permitting, geopolitical risks and social license to operate;

Once it is determined that a deposit is economically viable as an orebody, the

choice of the extractive metallurgy method to be used to exploit this ore body can
be made. Extractive metallurgical methods are generally divided into three
categories: pyrometallurgy, hydrometallurgy, and electrometallurgy. Historically,
pyrometallurgy employs high temperatures to carry out smelting and refining
operations to extract metals from their minerals. The relatively new technology of
hydrometallurgy uses aqueous solutions to separate the desired metals. Finally,
electrometallurgy, which is often classified as a subset of hydrometallurgy, employs
electrical energy to extract and refine metals. Several factors play a role in
determining the extractive method to be used. Among the most important factors
are the orebody grade and tonnage, the orebody location, the orebody mineralogy,
the initial capital investment, the operating costs, the energy requirements, water
requirements, environmental constraints, political and social constraints, and the
purity, grade and type of the metal or metallic compound produced. A comparison of
the three extractive metallurgical methods is shown in Table 1.

Table 1.
Relative comparisons between pyrometallurgy, hydrometallurgy, and
electrometallurgy.
Factors Pyrometallurgy Hydrometallurgy Electrometallurgy
Initial capital investment high low intermediate
Relative energy requirements moderate high high
Primary waste products solids and air liquids and solids solids and gases
Rate of chemical reaction high low intermediate
Production costs low intermediate high
Level of separations low high moderate

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.

1. Pyrometallurgical Extraction
Pyrometallurgical extraction involves several processes such as: roasting,
carbothermic reduction, reduction of sulfide ores, and metallothermic reduction. The
selection of the processes 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 (i.e., useless minerals associated with any ore)
before they can be refined. Other metals occur as oxides and/or sulfides, and 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. Sulfides cannot be
reduced by carbon or hydrogen because metal sulfides are more stable than carbon
sulfides (CS and CS2), carbon oxosulfides (COS), and hydrogen sulfide (H2S).
Therefore, the first step in processing metal sulfides is to convert them into a more
desirable product that can be reduced. This conversion step is known as roasting.

1.1. Roasting
There are several different types of roasting processes. The most commonly used
roasting processes are:

(a). Dead roasting

Dead roasting is the complete conversion of sulfides into oxides by heating the ore
or concentrate under an oxidizing atmosphere.

(1). 2MS + 3O2 = 2MO + 2SO2 

(2). MS + 2O2 = MO + SO3

(b). Sulfating roasting

Sulfating roasting is the conversion of sulfides into soluble sulfates. This conversion
is also accomplished by heating the sulfide under an oxidizing atmosphere. The
soluble metal sulfates can then be used as the feed material for hydrometallurgical
extraction processes (see Hydrometallurgical Principles).

(3). MS + 2O2 = MSO4

(c). Partial roasting
Partial roasting is a common roasting operation for metal concentrates containing
several metal sulfides. In this roasting operation, the impurity metal sulfides are
preferentially oxidized to enable their easier separation from the desirable metal
sulfides 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, sulfur dioxide and trioxide are formed. Consequently,
this type of operation can pose a major environmental problem. Sulfur dioxide and
trioxide released into the atmosphere can be major causes of acid rain. Fortunately,
much of this can be abated with modern technologies such as baghouses,
electrostatic precipitators, scrubbers and sulfuric acid plants. So, overall, modern
roasting furnaces have highly engineered exhaust systems, and the sulfur 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
pyrometallurgicaly 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 sulfide ores. However, if a
partial roasting process is employed the desirable metallic mineral will still be in the
form of a sulfide.

1.2. 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 (see Iron Production).
Carbothermic reduction generally relies upon the Boudouard reaction which is
expressed as;

(4). 2 CO = CO2 + C

And accordingly the reduction of metal oxides may be simplistically viewed as

(5). MO + CO = M + CO2

In the case of zinc and lead, their ores are sulfidic. Therefore, before the
carbothermic reduction can take place, the zinc and lead sulfide 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 (see Lead Production;
Zinc Production).

1.3. Reduction of Sulfides

Most of the sulfide ores are normally concentrated and roasted before they can be
reduced. There are several pathways for the reduction of sulfides. The copper-
making process illustrates well this point. In some cases copper extraction can be
divided into three steps:

 (i) roasting (which can be optional for some copper-making routes);

 (ii) matte smelting (reverberatory, electric, or flash smelting furnaces);
 (iii) converting (conversion of matte to blister copper).

There are also now available continuous copper smelting technologies such as the
Mitsubishi process that combine all of the above steps.
The purpose of matte smelting is to separate the metal sulfides (Cu2S‒FeS) from
the gangue. The metal sulfides form a phase known as matte, and the gangue
materials are absorbed by the slag phase.
(6). 2CuFeS2(concentrate) + 5/2 O2 + SiO2(flux) = CuS:FeS(matte) + FeO.SiO2(slag) + SO2 + heat

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:

 (i) Slag-forming stage̶FeS is oxidized to iron oxide and absorbed by the slag
phase. The product of this stage is the white metal which is mainly Cu2S.

(7). 2FeS + 3O2  + SiO2(flux) = 2FeO.SiO2(slag) + SO2

 (ii) Copper-making stage̶the remaining sulfur is oxidized keeping the

oxidation of copper to a minimum.

(8). Cu2S(white metal) + O2  = 2Cu(blister) + SO2

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). (see also Copper
Production).

1.4. Metallothermic Reduction

An alternative way to reduce an ore (or concentrate) is by using a metal that has a
higher affinity for oxygen or sulfur as a reducing agent. The metallothermic
reduction process is exothermic and self-sustained once it is started. For example,
the aluminothermic method uses aluminum 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. In addition, this
is a very expensive process because highly reactive metals, such as aluminum and
silicon, are used as reductors.

2. 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.

2.1. 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:

 (i) to flux and absorb impurities;

 (ii) to protect the reduced metal against reoxidation; and
 (iii) 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 (see also Steel Production and Refining; Tin Production).

2.2. 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 ʻʻshock-
cooledʼʼ exhaust gases in the ISF. The solubility of zinc in lead decreases and the
temperature decreases, therefore as the temperature is lowered a 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 sulfur, since copper has a higher
affinity for sulfur than lead. Consequently, a copper sulfide 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.

2.3. 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.

3. Concluding Remarks
Pyrometallurgy will continue to be a dominant extractive metallurgical method of
choice for treating high-grade clean ores and concentrates, such as iron ore or
copper. However, in the case of low-grade ores or complex concentrates with
abundant impurities, a combination of the use of hydrometallurgical and aqueous
 electrowinning are gaining momentum. The recent shift from pyrometallurgy to
hydrometallurgy combined with electrometallurgy is increasingly desirable for
lower-grade ores and complex concentrates with abundant impurities due to better
separations.

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C. G. Anderson

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