Technical Report

on
Principles and Applications of Pyrometallurgy

Submitted to:
Engr. Rudolph Joshua Candare

Submitted by:
Luengas, Cristopher
Macarayan, Karen Joy
Ocon, Russel Lloyd T.
Pagudar, Ruth Caryl
Ruperez, Chamel
Trugillo, Irish
 Summary

Pyrometallurgy is a branch of extractive metallurgy that consist of the thermal treatment

of minerals and metallurgical ores and concentrates to bring about physical and chemical
transformation in the materials to enable recovery of valuable metals. This treatment may produce
pure metals, intermediate compounds, alloy, and suitable feed for further processing. The
treatment of minerals and metallurgical ores and concentrates are generally grouped into one or
more pyrometallurgical process: smelting, roasting, refining, and calcination.
 Smelting is one of the most heavily used process in pyrometallurgy. In this process, the ore
is mixed with flux and fuel and heat strongly at blast furnace. Therefore, flux is a material
which combines with the impurities like gangue and convert them to fusible material called
sag.
 Roasting is heating the ore in the presence of air or oxygen in a special furnace. It is
generally used for the sulphide ore to convert them fully or partially in to the oxides.
 Refining is the thermal process of removing of impurities from the metallurgical material.
This required covers a wide range of processes, involving different kinds of furnace or
other plant.
 Unlike roasting, calcination is a heating of ore without the presence of air or oxygen. The
thermal decomposition of a metallurgical material expels the organic matter and moisture
present in the ore as well as carbon dioxide from a carbonate ore or water from a hydrate
ore.
 Contents
Introduction………………………………………………………………………1
1
1. Pyrometallurgy………………………………………………………………2
2
1.1.Classifications of Pyrometallurgical Processes…………………… 2
1.2.Pyrometallurgical Processes……………………………………….. 3
1.2.1. Smelting……………………………………………………......3
1.2.2. Roasting……………………………………………………… 5
1.2.3. Refining……………………………………………………… 6
1.2.4. Calcination…………………………………………………….7
Conclusion………………………………………………………………………8
References…………………………………………………………………… 8
Bibliography…………………………………………………………………. 9
 Acknowledgements

We would like to extend our gratitude to our very own instructor, Engr. Rudolph Joshua
Candare for his consideration to extend the submission of this report and we wish to thank our
groupmates for their contribution to this report.
Introduction

Metal has been as important material in the story of human’s control of his/her
environment. Innovations that are made in progressing the fields of agriculture, transportation,
warfare, industrialization, even cookery are impossible without the use of metals. But metals did
not exist purely, it usually found in ores that are from the crust of the Earth through mining. In
order to extract metal from the ore, extractive metallurgy is applied.

Extractive metallurgy is the practice of removing valuable metals from an ore and refining
the extracted raw metals into a purer form. This report will discuss about one of the branches of
extractive metallurgy which is the pyrometallurgy which is a process of recovering valuable metals
through thermal treatments of metallurgical ores and concentrates.

This report will give insights on the different types of pyrometallurgical process and its
subtopics, some of apparatus used and how they work, what are the common metals that undergone
this process, and the reaction process that can be presented in equation. These will invite the
understanding of the readers for the principles of pyrometallurgy. The knowledge inquired in this
report may help making an avenue in carrying the principles to the applications of pyrometallurgy
when dealing the extraction of minerals.

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1. Pyrometallurgy
The process of pyrometallurgy derives its name from the Greek word “pyr” meaning
a fire and “metallurgy” which is the scientific study and technology of extracting metals from
ores, refining them for use, and making useful materials from it. To sum up these derivations,
pyrometallurgy is a process of extracting metal from a metallurgical material by exposing the
material to high temperatures. This exposure enables the metallurgical material to undergo a
chemical reactions that will result to a product of purely metal or a metal compound that can
be easily be separated when subjected to further processing. The high temperature treatment
on material will give sufficient amount of energy, which is the heat energy, for a compound
to proceed into the expected products.

1.1 Classification of Pyrometallurgical Processes

Pyrometallurgy can be further classified in terms of the unit processes. The two
classification will be as follows:
1. Solid-state processing: This does not involved any melting. It is typically carried out in
the temperature range of 500-1200ºC. Roasting of sulphides, calcination, solid-state
reduction of metal oxides by H2 and CO are examples of this process. Solids are mostly
immiscible and therefore the product of solid-state processing is either pure or is
mechanical mixture. In latter case, it requires further processing.
2. Liquid-state processing: This involves melting of at least the metallurgical material and is
on the whole carried out at a higher temperature. Blast furnace smelting, steelmaking,
distillation of refining of zinc from impure lead are some examples of liquid-state process.
Liquid-state processing separates out the metal either in pure or in pure. Appreciable
compositional changes in the liquid are possible due to miscibility, rapid diffusion, and
mixing.

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1.2 Pyrometallurgical Processes
After a massive extraction of ore or any metallurgical minerals in the Earth’s crust,
the material is then subjected to mineral process such as comminution (breaking down the
ore), dewatering (removal of water), or concentration (separation by physical and chemical
properties) in order for the metallurgical mineral is then ready for further processing which is
the separation of metal from the ore.
One of process of separation the metal from its ore is pyrometallurgy. Pyrometallurgy
are performed in this processes: smelting, roasting, refining, and calcination. These processes
are commonly used in further process of separation.

1.2.1. Smelting
Smelting is a process of extracting metals from their ores at high temperatures allowing
the ore to melt. The metal liberates as an impure molten metal and separates it from the molten
waste rock called slag. There are three types of smelting: Reduction, Matte, and Flash.

1. Reduction Smelting
The reduction smelting process involves the reduction of metal oxides with carbon
in the presence of a flux. The metallurgical material is charged into a furnace together
with reducing agent and flux to support the combustion reaction then eventually
producing a metal, slag, and gases. This can be presented in an equation:

mineral + reducing agent + flux = metal + slag + gases

There are many types of

furnaces are used for reduction
smelting but the most commonly used
is the blast furnace. The blast furnace
is universally used in the reduction of
iron oxides, zinc oxide, and lead
oxides compound. Figure 1 shows an
image of blast furnace. Figure 1.Schematic diagram of blast furnace (right)
and hot-blast stove (left)

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2. Matte Smelting
The matte smelting process involves the fusion of metal sulfides with a flux without
the use of reducing agent. The primary purpose of matte smelting is to melt and recombine
the charge into homogeneous matte of metallic copper, nickel, cobalt, and iron sulfides
and to give an iron or silicon oxide slag. Matte
is molten mixture of sulfides. It is usually done
in reverberatory furnace.
The reverberatory furnace is essentially a
rectangular refractory-brick box equipped with
end-wall burners to provide heat for melting.
The matte is tapped periodically from the center
taphole, while the slag runs off continuously at
Figure 2: Reverberatory Furnace from
the furnace flue end. An example of matte slideplayer.com

smelting process of extracting copper sulfide

and iron sulfide can be presented:

2FeS + 3O2 2FeO + 2SO2

2Cu2S + O2 Cu2O + SO2

3. Flash Smelting
Flash smelting results from the combination of two processes: the flash roasting
and the smelting operations. In this process, the sulfide concentrates react with oxygen at
high temperatures. The oxidation process
itself generates sufficient heat for the
smelting process to occur simultaneously.

Figure 3: Flash Furnace. Image from slideplayer.com

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 1.2.2. Roasting
Roasting is a pyrometallurgical process involving gas-solid reactions at elevated
temperatures with the goal of purifying the metal component. The ore is heated in a regular
supply of air in a furnace at a temperature below the melting point of the metal, usually
below 900-1000 degree celsius and both reactants and products are in a solid state. The
following are the operations of performing roasting:
1. Oxidizing roast: The most commonly practiced roasting process, involves
heating the ore in excess of air or oxygen, which remove all or part of the sulfur
from sulfide metal compounds, replacing the sulfides with oxides.
Examples: Roasting of sphalerite to zincite:
ZnS + 3/2O2  ZnO + SO2
Roasting of chalcopyrite to cuprite:
6CuFeS2 + 18O2  3Cu2O + 3Fe2O3 + 12SO2
2. Reducing roast: The process of reducing partially the oxide state of the ore
before the actual smelting process or reducing completely the oxide to a metal.
3. Chloridizing roast: A process of transforming certain metal compound to
chlorides, through oxidation or reduction. Some metals such as Uranium,
Titanium, Beryllium and some rare earths are processed in their chloride form.
Types:
Direct Chlorination (sulfide ore involving an exothermic reaction):
2NaCl + MS + 2O2  Na2SO4 + MCl2
Indirect Chlorination (oxide ore is facilitated by addition of element sulfur):
4NaCl + 2MO + S2 + 3O2  2Na2SO4 + 2MCl2
4. Volatizing roast: This eliminates easily volatized oxides by converting them to
gases. It involves careful oxidation at elevated temperatures of the ores, to
eliminate impurities in the form of their volatile oxides such as As2O3, Sb2O3, ZnO
and sulfur oxides. Failure to control the oxygen content may result to non-volatile
oxides

5. Magnetic roasting: It involves controlled roasting of the ore to convert it into a

magnetic form, thus enabling easy separation and processing in subsequent steps.

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 For example, controlled reduction of hematite (non-magnetic Fe2O3) to magnetite
(magnetic Fe3O4)

6. Blast Roasting: Involves heating the fine ores at high temperatures, where
simultaneous oxidation and agglomeration of the ores take place. For example, lead
sulfide ores are subjected to sinter roasting in a continuous process after froth
floatation to convert the fine ores to workable agglomerates for further smelting
process.

1.2.3. Refining
Refining is the process of removing impurities from materials by thermal process.
This covers a wide range of processes, involving different kinds of furnace or other plant.
As its main objective, it relatively impure metal product from a metallurgical process to
improve its purity and to define its composition better.
Refining is different from other processes such as smelting and calcining in that
those two involve chemical change to the raw material, whereas in refining, the final
material is usually identical chemically to the original one, only it is purer. The following
are the types of refining that involves thermal treatments:

1. Cupellation
A separation of gold and silver from impurities by
melting the impure metal in a cupel and then directing a
blast of hot air on it in a special furnace. The impurities
, including lead, copper, tin, and other unwanted metals,
are oxidized and partly vaporized and partly absorbed
into the pores of the cupel. A cupel is a flat, porous dish
made of a refractory, or high-temperature-resistant
Figure 4: 16th century cupellation
furnaces. image from wikipedia.org material.

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 2. Pattinson Process
Patented by Hugh Lee Pattinson. This process formerly used for
desilvering and purifying lead, in which the metal is repeatedly subjected to
a cycle of melting, recrystallizing the purer lead, and separating the silver-
rich alloy that is still fluid.

3. Parkes Process
This process is used for extracting silver and gold from molten lead
by adding zinc which forms an alloy with the precious metals that collects
on alloy the surface.

4. Fire Refining
Iron, copper, and lead are fire-refined by selective oxidation. In this
process, oxygen or air is added to the impure liquid metal; the impurities
oxidize before the metal and are removed as an oxide slag or a volatile oxide
gas.

1.2.4. Calcination
Calcination a heating of ore without the presence of air or oxygen. The process of
calcination derives its name from the latin word “calcinare” which means to burn lime.
Calcination process is commonly used in the decomposition of calcium carbonate
(limestone) to calcium oxide, in order to create cement. The product of calcination is
usually referred to in general as “calcine”, regardless of the actual minerals undergoing
thermal treatment. Calcination reactions usually take place at or above the thermal
decomposition temperature or the transition temperature.

Examples of calcination processes:

 decomposition of carbonate minerals, as in the calcination of limestone to
drive off carbon dioxide;

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  decomposition of hydrated minerals, as in the calcination of bauxite and
gypsum, to remove crystalline water vapor;
 decomposition of volatile matter contained in raw petroleum coke;
 heat treatment to effect phase transformation, as in conversion of anatase
to rutile or devitrification of glass;
 removal of ammonium ions in the synthesis of zeolites.

Conclusion

Over the past centuries, pyrometallurgy has become one of the significant process in the
extraction of metals since the discovery of metal plays an essential role in the evolution of human
history. Most of the metals that exist today are the products of pyrometallurgical processes:
smelting, roasting, refining, and calcining. These processes are important to be accustomed with
in order for the application of these processes will performed correctly because pyrometallurgical
process will continue to sustain the demand of the universe on metals.

References

Books:
1. H.S. Ray, A. Gosh, Principles of Extractive Metallurgy, New Age International, 1991
2. S.K. Dutta, A. Lele,Y. Choksi,Extractive Metallurgy: Processes and Applications,
PHI Learning Pvt. Ltd., 2018

3. Gilchrist, J.D. (1989). Extraction Metallurgy (3rd ed.). Oxford: Pergamon Press.
p. 145.

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 Internet:
4. https://www.britannica.com/science/metallurgy
5. https://www.google.com/amp/slideplayer.com/amp/681750/

6. https://www.lenntech.com/chemistry/calcination.htm#ixzz5BewroxLA

7. http://en.m.wikipedia.org/wiki/Pyrometallurgy
8. http://nptel.ac.in/courses/113104060/MHB_pdf/Lecture14.pdf
9. https://www.slideshare.net/akshatc/principals-of-roasting-and-its-types

Bibliography
1. Reinhardt Schuhmann,Jr.:Metallurgical Engineering, Vol.I, Addison –Wesley
Publishing Co., Reading,Mass,U.S.A., 1952, Ch.1.
2. J.M. Smith, Chemical engineering kinetics, McGraw-Hill Book Co., New York,2nd
edition,1970, Ch.1 and Ch.2