MT 221: 10.

0 Introduction to Pyrometallurgy 2019

10.0 Introduction
The branch of Extractive metallurgy in which processes are carried out at elevated temperatures to extract and refine metals
from ores, concentrates, and recycled materials. Ores are classified into two main groups:
o Sulphide ores, in which the metals occur mostly as sulphides, deep in earth crust. Sulphide minerals (Cu-Fe-S) (most
abundant - about 80 %) are not amenable to leaching processes and therefore, extraction of metal is by pyro-metallurgy. A
typical copper ore contains between 0.5 % and 2.0 % copper.
o Oxide ores are basically ores in which metals occur chiefly as compounds containing oxygen, such as oxides, carbonates,
sulphates, phosphates and occur on the surface. Copper can be extracted from oxide ores as well using electrolysis for
low grade ores, or by the carbon reduction method of smelting for higher grade ores.
Pyro-metallurgy involves smelting, converting, fire refining and electro-refining. It is mostly applicable in the separation of one
metal from another i.e. copper and lead sulphide ores. It is also used in the removal of base metals from silver-gold bullion by
cupellation and slagging. The advantages of this process is that it offers fast reactions due to elevated temperature, thus,
allowing separation of one element from another. The other advantage is that it has got ability to extract precious metals such
as gold, silver, platinum etc.
10.1 PRE - TREATMENT
Pretreatment is done to prepare concentrates and ore for extractive metallurgy; in this instance for sintering and smelting. This
is necessary because the feed may be too wet, too fine, or too soft. Example is electric furnace, smelting of copper
concentrates. The concentrates have to be bone dried to avoid the moisture cracking into H 2 and O2 on the very hot and highly
reducing live carbon electrodes. This would result in dangerous explosions. The ordinary forms of pretreatment include drying
both partial or bone dry and may be calcining. It also involves various forms of agglomeration such as: pelletizing, briquetting,
nodulizing and sintering.
10.1.1 Drying
Drying is defined as the expulsion of relatively small amounts of water or other liquid from solid material to an acceptably low
value. Concentrates from concentrators usually contain 10-15 % water. However, in the example of reverb smelting, an
accepted value is usually 8 %. So the concentrates are dried to this level. In Outotec flash smelting, the concentrates are dried
to less than 1 % residual water. This is necessary because the concentrates are conveyed pneumatically and then have to be
injected into the furnace.
There are several types of dryers. Common ones in metallurgy are rotary dryers and flash dryers. The rotary dryer is a long
steel kiln inclined slightly to the horizontal to allow material to flow through under gravity. Feed comes in on the firing end and
goes out dried to the set consistency from the other end. The product of drying will normally be fed directly to smelting.
However, the advent of ceramic filters has in certain cases done away with the need of drying if the consistency required is not
bone dry. An example of an indirect heated steam dryer can be found at Nchanga smelter.

Figure 10.1 Direct fired, parallel flow rotary dyer (after Kram 1980)

Leonard Kabondo Page 1 of 10

MT 221: 10.0 Introduction to Pyrometallurgy 2019

10.1.2 Sintering
Sintering is high temperature agglomeration in which feed to a subsequent process is prepared by a process of heating this
feed to just below it melting point. Sintering is done on either stationary or moving grates (Dwight – Lloyd machine). Feed is put
onto the strand and then ignited on top while air is continually sucked through the sinter bed. This causes the burning to move
from one end to the other i.e. may be top to bottom thus sintering the material. The heating results in important chemical
reactions and physical changes. Materials sintered include PbS and ZnS concentrates, Fe2O3 and Fe3O4 for Iron smelting, etc.
PbS and ZnS are converted to oxides suitable for reduction smelting in the blast furnaces. The sinter product is a lumpy
cindery agglomerate which is later fed to a blast furnace and should have the following basic properties:
1) Hard and strong to bear the weight of feed on top of it.
2) Porous to allow for gas-solid reactions.
3) Reactive with large surface area.
4) Be oxidic i.e. particular chemical nature.
Naturally, concentrates do not possess these properties. They are reformed in sintering to acquire the properties. Some iron
and very rarely Cu ores (DR Congo) are pure enough to be treated straight just like that in blast furnaces.
10.1.3 Pelletizing and balling
In this process, ore or concentrates are agglomerated into pellets and or balls. Pellets may be up to several centimeters in
diameters but balls are normally a lot smaller. Pellets will normally be fired to harden them, because so often they are feed to
smelting reduction of say iron oxide to iron. Balls are normally used as feed to sintering etc. It helps sintering by lessening the
pressure drop across the bed preventing failure of sintering by the bed collapsing.
10.1.4 Nodulizing and briquetting
These are currently not being practiced in Zambia and even elsewhere are very uncommon. Nodulizing involves partially
melting rotating feed. The result is nodules. Briquetting is forming brick like forms from feed and either hot or cold pressing
them to strengthen them. These both constitute feed to smelting.
Sinter Pellets

Nodules Briquettes
Fig 10.2 Different types of agglomerates
10.1.5 Partial Roasting
Cu sulphide smelting feed in most parts of the world is chalcopyrite high Fe High S feed. Such feed when smelted in a non-
oxidation/flash type smelting process such as in a reverb, electric furnace etc tends to produce low (matte grades) % Cu in
Leonard Kabondo Page 2 of 10
MT 221: 10.0 Introduction to Pyrometallurgy 2019

matte. This type of matte results in low production rates and produces bulky slags in converting. Time for converting is long
resulting in low production rates and slag is bulky resulting in high Cu loss to slag leading to high re-circulating loads of Cu
between converter and the smelting furnaces. To get around this, partial roasting is conducted as a pretreatment stage.
Roasting is the oxidation of metal sulphides to give metal oxides and Sulphur dioxide. In the roaster, the copper concentrate is
partially oxidised at temps between 500 oC and 700 oC in air to produce "calcine" and sulfur dioxide gas. Calcine, a mixture of
solids including copper oxides, sulfides and sulfates, can then be smelted. The reaction which occurs is;
2CuFeS2(s) + 4O2(g) → 2FeO(s) + Cu2S(s) + 3SO2(g)
Typical materials that are roasted are the sulphides of copper, zinc and lead. The main purposes of roasting are:
1) Oxidizing roast to burn out Sulphur from sulphides and replace them in part or whole with oxide.
2) Volatilizing roast to eliminate other elements with volatile oxides such as As2O3 Sb2O3, or ZnO which can be recovered
as a fume.
3) Chloridizing roast to convert certain metals to chlorides. This may be carried out under oxidizing or reducing
conditions. An example is the ‘TORCO’ process.
4) Sulphating roast to convert certain sulphides from sulphides to sulphates, usually prior to leaching.
5) Magnetizing roast, usually a controlled reduction of hematite to magnetite to enable magnetic separation to be
effected.
6) Reducing roast of oxide to metal prior to leaching or smelting. An example is the extraction of mercury from cinnabar
i.e. Hg2S.
7) Carburizing roast prior to prepare calcines for chlorination. .
8) Sintering or blast roasting often with the primary purpose of modifying the physical characteristics of the feed.

10.2 Copper Smelting

This is a process in which the calcine is heated to over 1250 oC with fluxes such as silica (SiO2) and limestone (CaCO3).
Calcine melts and its compounds react with the fluxes. The product of this process is a mixture of copper, iron and sulfur that
is enriched in copper, and is called matte or copper matte. The matte, containing about 40-70 % copper, can then be fed to a
converter. Smelting can be undertaken in a variety of furnaces, including the largely obsolete blast
furnaces and reverberatory furnaces, as well as flash furnaces, Isasmelt furnaces, etc.
The purpose of the smelting stage is to eliminate as much of the unwanted iron, sulfur and gangue minerals as possible,
while minimizing the loss of copper. This is achieved by;
1) By converting any copper (I) oxide present into copper (I) sulfide since copper has a higher affinity for sulfur than it does
for oxygen. For example;
Cu2O + FeS → Cu2S + FeO
2. By reacting iron sulphide with oxygen to produce iron oxide and Sulphur dioxide. Or by reacting iron oxides with flux to
produce iron silicate as slag. The Impurities that form slag floats on the surface and are easily removed.
FeO + SiO2 → FeO.SiO2 or FeSiO3
Feed to Cu smelting will generally consist of the following;
1) Concentrates being smelted, usually several different ones are treated at the same time.
2) Fluxes, which are either silica or lime based.
3) Reverts, both primary and secondary.

Leonard Kabondo Page 3 of 10

MT 221: 10.0 Introduction to Pyrometallurgy 2019

4) Flue dusts.
5) Often return converter slag.

These materials are then blended in preset amounts before being charged to the smelting furnace. Blending is done so that
after smelting, a particular matte and slag are obtained. Particular proportions of the mixes in a particular smelting system will
always produce a definite matte and slag and gas composition.
Separation of matte and slag - Immiscibility
Slag and matte should be highly immiscible. Any miscibility would lead to either excessive Cu loss to slag or matte containing
too much slag. This is detrimental. The main way of creating this immiscibility is by bringing slag (composition) silica content
to saturation.
Although it is desired to recover all Cu to matte, practically this is impossible. Industrially, slags contain 0.5 to 2 % Cu,
increasing with increase in % Cu in the matte. This increase of Cu in slag is caused by;
1) Equal amounts of unsettled slag (matte) contain more Cu with a high % Cu in matte.
2) High grade matte contains little FeS to reduce copper oxide from the slag by reaction:
Cu2O+ FeS = Cu2S + FeO

10.3 Converting of Copper Matte

Converting is oxidation of molten Cu-Fe-S matte from smelting with air or oxygen-enriched air through submerged tuyeres to
form blister copper of about 98-99 % Cu. It is called blister copper because of bubbles of sulfur dioxide gas on the surface of
the copper that look like blisters. Objective is to further remove Fe and S from the matte to produce blister copper of about 97 -
98 % Cu which is sent to fire-refining or electro-refining after casting into blocks. The process is auto-thermal in that heat
comes from oxidation of Fe and S.
The main reactor is a rotatable Pierce Smith converter. Air is blown through submerged tuyeres. The feed to the converter
consists of Matte from the smelting process, Secondaries and reverts and silica flux or CaO for the Mitsubishi converter. The
Chemistry of converting can be represented by the reaction;
Cu-Fe-S + O2 + SiO2 = Cuo(l) + { 2FeO.SiO2, Fe3O4} + SO2

Molten Matte In air Flux Blister Cu slag for Sulphuric Acid Prod

There are two stages in converting, a slag forming stage and a copper making stage.
10.3.1 Slag forming stage
The sulfur is removed at high temperature as sulfur dioxide by blowing air through molten matte:
2 CuS + 3 O2 → 2 CuO + 2 SO2 and CuS + O2 → Cu + SO2
In a parallel reaction the iron(II) sulfide is converted to iron(II) oxide and sulfur dioxide. Iron(II) oxide, FeO, slag, is skimmed off.
2 FeS + 3 O2 → 2 FeO + 2 SO2 and 2 FeO + SiO2 → Fe2SiO4
Silica is added to fix FeO so that most of it does not form Fe 3O4. Slag forming is finished when Fe in the matte is lowered to
about 1 % leaving a bath that is mostly Cu2S i.e. white metal. Matte is charged in about two to three instalments of e.g. 3:2:2.
Each addition followed by complete blowing, fluxing and slag removal (skimming) cycle. In this way, Cu in the converter i.e.
Cu2S gradually increases until there is sufficient Cu2S to permit a copper blow. The remaining Cu2S is blown (oxidised) to
blister Cu. On the copper blow, Cu pot shells are added in addition to Cu scrap. When Cu2O begins to form ln the bath
(observed) by punch rod samples, Cu blow is terminated. Cu blister is then transferred to anode furnaces for fire refining.
Leonard Kabondo Page 4 of 10
MT 221: 10.0 Introduction to Pyrometallurgy 2019

10.3.2 Copper making reactions.

The blast creates turbulence and oxidises the white metal producing SO 2, molten Cu and Cu2O. The Cu quickly settles below
the tuyeres. Probable reactions are:
Cu2S + 3/2O2 = Cu2O + SO2
CU2S + 2CU2O = 6CuO + SO2
10.3.3 Temperature control
Heat in the converter comes from:

FeS + 3/2O2 = FeO + SO2, Ho1200oC = -5.1x105kj/kmol

Cu2S + O2 = 2Cu + SO2, Ho1200oC = -2.2x105kJ/kmol

Heat is controlled by;

1) Raising or lowering O2 enrichment.
2) Adjusting revert scrap and Cu scrap addition rates.
3) Altering blowing rate (increase or decrease of air or O2).
4) Stopping blowing for some time to allow bath to cool.
Temperatures are measured mostly by optical pyrometer strategically sited through the mouth or a two wavelength optical
pyrometer periscope sited through a tuyere. This gives better readings because there is no interference from dust and gases.

10.4 Direct to Copper Flash Smelting

Combines smelting and converting to produce copper directly in one furnace. The process is continuous and a flash furnace is
usually used. The flash furnace reaction shaft product is a mixture of over-oxidized (oxide) and under-oxidized (sulphide)
materials. An ideal direct to copper process is illustrated in figure 10.3. Over- and under-oxidized components react to give
metallic copper, as shown in the reactions below:

Figure 10.3 Ideal direct to copper illustration

Leonard Kabondo Page 5 of 10

MT 221: 10.0 Introduction to Pyrometallurgy 2019

The above visualization is what would be the ideal for a Cu extraction process. All the feed goes into one single reactor and a
final product normally blister Cu comes out to send for fire refining. At the present, there are only three plants in the world and
all employ OutoKumpu/Outotec flash smelting. One is at Glogow in Poland, the other at Olympic Dam in Australia and the third
one at KCM Nchanga in Zambia. All treat chalcocite – bornite type concentrates though the one in Nchanga may be treating a
small amount of some chalcopyrite type concentrates. The products of direct-to-copper are given in table 10.1. O2 enriched
blast into the furnace is 50-90 v/v%. Considerable fossil fuel is burnt in the reaction shaft and in the settler burners.

Table 10.1 Typical direct to copper product constituent

%Cu %S %Fe %O Temp oC

Copper 99 0.04 - 0.09 0.01 0.4 1280oC

Slag 14-24 1300oC

Off-gas 15 to 20 volume % SO2 at 1350oC

It is worth noting that it is very advantageous in Cu processing to combine the smelting and converting into one single process,
these may include:

(i) Isolation of SO2 emission to a single continuous gas stream.

(ii) Minimization of energy consumption.
(iii) Minimization of capital and operating costs.
(iv) Minimization of material handling.

However, there are problems with this kind of processing which is the reason why it has not been really adopted around the
world, there being only three plants in the world which are practicing direct to copper. These problems are:

(i) The main difference is the Cu in slag which is 14-24 % for direct to blister compared to 1-2 % for conventional smelting.
The actual slag amounts are about the same for each process type. Because of the high oxidized Cu in slag in the direct-
to copper processing, these slags have to be reduced with Carbon to recover the Copper. In all the three plants i.e.
Poland, Zambia and Australia, the slag overflows into an electric furnace where it is settled for about 10 hours under a
0.25 m blanket of metallurgical coke.

(ii) There is a cost of processing needed to recover the Cu lost in slag such that this processing will be restricted to low Fe
concentrate such as chalcocite Cu2S and bornite Cu5FeS4 rather than high Fe concentrates such as chalcopyrite.

10.5 Copper Fire Refining

Fire refining is necessary because of the need to reduce sulphur and oxygen to levels where the anodes have a chemical
composition and physical structure – thin, strong and smooth amenable to electrolytic refining. The blister copper is put into
an anode furnace, a furnace that refines the copper to anode-grade copper in two stages;
1) By removing most of the remaining iron and sulfur down to appx. 0.003 % S.
2) The second stage, often referred to as poling (Hydrocarbon reduction - removal of oxygen as CO2(g) and H2O(g) down
to appx. 0.16 % O.). This is done by blowing natural gas, or some other reducing agent, through the molten copper
oxide. When the flame burns green, indicating the copper oxidation spectrum, the oxygen has mostly been burned off.

Leonard Kabondo Page 6 of 10

MT 221: 10.0 Introduction to Pyrometallurgy 2019

This creates a product at about 99 – 99.5 % Cu with appx. 0.003 % S, 0.16 % O which is then casted into flat, thin anodes
suitable for electro-refining. This process is usually done in a typical vessel like a rotary furnace refining.
10.4.1 Rotary furnace refining
Air is used for desulphurisation while hydrocarbons or wood poles for de-oxidation. The air and hydrocarbons are blown in
through one or two tuyeres. Pressure of delivery is 2 to 5 atmospheres. The full refining cycle is 3 to 4 hours on oxidation and 2
to 3 hours on de-oxidation. High sulphur Cu from continuous processes takes much longer. The air and hydrocarbon flow rates
are at a slow rate to maximize copper composition control. A full charge is usually above 200 t.
Sequence of refining
1. Molten blister is delivered by crane in ladles from converters to the anode furnaces until a charge is made up to 200 to
300 tonnes.
2. The charge is then first de-sulphurised by air blowing down to about 0.001 % S.
3. Copper is then next deoxidised using gas, hydrocarbons or wood poles.
When O is about 0.15 % as measured by solid electrolytes or observing the setting of samples, refining is finished. Copper
with the right oxygen content sets flat.

Fig 10.4 Long View of anode fire refining furnace

10.4.2 Casting of anodes
Cast anodes contain 0.001 % S and 0.15 % O. The temperature of casting is 1150 – 1200oC. Most casting is done in open
anode shaped indentations on the top of flat copper moulds. Twenty to thirty of the moulds are placed on a large horizontally
rotating wheel, the casting wheel. The wheel is rotated to bring a mould in position for pouring in turn. Cu spillage is minimised
by using tiltable tundishes between the furnace and the wheel. Water is sprayed on the tops and bottoms of the moulds while
the wheel is rotating to cool the moulds and copper. The anodes are stripped out of the moulds after about half a rotation by an
automatic or mechanized raising pin. The empty moulds are sprayed with a mould wash to prevent sticking e.g. Barite mould
wash. At one time in Zambia it used to be graphite suspended in sodium silicate. Casting rates are 30 to 40 tonnes per hour;
the rate is limited by solidification of anodes. Required characteristics of anodes are flat surfaces and uniform thickness.

Fig 10.5 Cu anode casting

Leonard Kabondo Page 7 of 10
MT 221: 10.0 Introduction to Pyrometallurgy 2019

10.6 Electrorefining of Metals

Electrorefining of metals is a process of obtaining pure metal from the impure one by the process of electrolysis."
Electrorefining refers to the process of using electrolysis to increase the purity of a metal extracted from its ore (compound or
mixture of compounds from which a metal can be extracted commercially). The anode (casted under fire refining) (positive
electrode) is the impure metal to be purified. The cathode made of a thin metal sheet (negative electrode) is the electrode at
which the pure metal will be deposited. The electrolyte is either a molten salt or an aqueous solution of the metal ions. At the
anode, atoms of the metal lose electrons, form cations and enter the solution. The metal cations being positive, migrate
towards the cathode and get discharged. The less electropositive impurities in the anode, settle down at the bottom and are
removed as anode mud, while the more electropositive impurities pass into the solution.
10.6.1 Electrorefining of Copper
Virtually all copper produced from ore receives an electrolytic treatment at some stage either via electrorefining from impure
anodes or Electrowining from leach or solvent extraction liquors. Electrorefining produces the majority of cathode copper (ca.
95% as opposed to ca. 5 % from Electrowining). Electrorefining of copper anodes incorporates an electrolytic refining of copper
whereby impure copper anodes containing about 99.5 % - 99.7 % copper, 0.15 % oxygen and the rest impurities from the
smelting furnace are refined to pure copper cathodes of 99.99 % copper in a copper electrolyte / sulphuric acid solution.
Impure copper anodes are dissolved by means of rectified electric current while an equivalent amount of pure copper is
deposited as copper cathode on stainless steel permanent cathodes, suspended in an electrolytic cell in series as shown in
figure 10.6.

Figure 10.6 Anode – Cathode arrangement in an electrolytic cell

Normally, the copper anodes to be fed into a refinery contain impurities such as Iron, Arsenic, Bismuth, Nickel, Tellurium, Lead,
Cobalt, Selenium, Gold, and Silver among others that have a detrimental effect on copper cation deposition and cannot be
removed entirely by fire refining in the smelting furnace. As the copper anodes corrode in a cell, the contained elemental
impurities will either dissolve in the copper sulphate solution where they remain in solution and ultimately plate out at the
cathode or form insoluble compounds which fall to the bottom of the cells and recovered as anode slimes, as shown in figure
10.7. The cells are fed with electrolyte at the temperature and flowrate of 63 ºC – 65 ºC and 25 - 35 litres per minute per cell
respectively. The animation below represents one of these electrolytic cells using an aqueous solution of Cu 2+ as the
electrolyte. Oxidation occurs at the anode where copper is oxidized and electrons produced as follows:
Cu(s) → Cu2+(aq) + 2e-
These electrons and copper ions then flow from anode to the cathode and are reduced as follows;
Cu2+(aq) + 2e- → Cu(s)

Leonard Kabondo Page 8 of 10

MT 221: 10.0 Introduction to Pyrometallurgy 2019

Once the copper cathodes cycle is completed, which usually takes 10 – 13 days, the copper cathode plates are lifted from the
cells using a special attachment suspended from two hooks of the overhead crane after isolating that particular cell bank and
the contained electrolyte drained from the cell such that the bed of raw anode slimes remains behind. The harvested cathodes
are passed through the cathode stripping machine (CSM) where cathodes are washed, and copper stripped off from the
stainless-steel cathode plate/blank. The stripped copper cathodes are stacked in bundles, which are, sampled (optionally),
weighed and strapped (manually) in readiness for storage/dispatch. Stainless steel cathode blanks are then spaced and
returned to the cells by the tank house cranes for more copper production.

Figure 10.7 Electrorefining copper illustration

10.6.2 Electrolyte Impurities
 Ag, Au and Pt are more noble than copper and therefore will not dissolve anodically. They will be found as metals in the
anode slime.
 Sn, Bi and Sb dissolve anodically but will precipitate in the electrolyte as oxide or hydroxide compounds which will be
found in the anode slime.
 Pb is oxidized anodically but will form insoluble lead sulfate in the electrolyte. Again, this will fall to the slime in the base
of the cell;
Pb2+(aq)+ SO42-(aq) → PbSO4(s)
PbSO4(s) will be found in the slime at the bottom of the tank.
 As, Fe, Ni, Co and Zn all dissolve anodically and in the sulfate medium, form species which are soluble in the
electrolyte. The species formed, however, only reduce at potentials more negative than that at which the copper
deposits and therefore remain in the electrolyte, as shown in figure 10.8.

Figure 10.8 Typical electrolyte impurities

Leonard Kabondo Page 9 of 10
MT 221: 10.0 Introduction to Pyrometallurgy 2019

10.6.2.1 Impurity control

To control impurity levels such as arsenic, antimony, bismuth, nickel and iron in the electrolyte, it is necessary to continuously
purge or bleed electrolyte from the circuit. The electrolyte bleed controls the level of impurities such as copper, nickel, arsenic,
antimony and bismuth. Copper concentration, if not controlled, would increase to levels where solubility would be a concern. To
control copper in the electrolyte, it is usually circulated to the liberator circuit. The primary liberators produce saleable quality
copper by making a small reduction in the electrolyte copper concentration. The secondary liberator cathode contains
significant arsenic along with other impurities such as bismuth and antimony. Therefore, the secondary liberator cathodes are
recycled to the smelter furnace.

Efficiency of commercial electrolytic processes

Leonard Kabondo Page 10 of 10