CHAPTER

ONE
INTRODUCTION

The art of extracting metals from their ores dates back to the dawn of human
civilization. The first metals used by man were gold and copper, which were
found in nature in metallic or native form. Around 4000 B.C. man learned to
produce copper and bronze by the smelting of copper and tin ores in a charcoal
fire. Throughout the history of mankind the processes of extractive metallurgy
were developed further by trial and error. The knowledge of the smelter or the
blacksmith passed on from father to son. New developments were sometimes
the result of an ingenious imagination, but perhaps more frequently a result of
accidents. A visitor to a modern metallurgical plant wiJl be struck by the large
number of complex operations. Particularly in the field of nonferrous metallurgy
the operations vary considerably from one metal to another and even between
different plants producing the same metal. In this text we shall see bow tbe
many different metallurgical processes may be understood as the result of a
relatively small number of fundamental principles. But first a few words about
the ores.

1-1 ORES

According to traditional definition an ore is a rock which can be mined eco-

nomically to serve as raw material for tbe production of metals. The economic
aspect is an important point, which makes the limit between what is ore and
what is worthless rock or gravel depend on the existing state of technology and
by the market price for the metal in question. A hundred years ago a copper

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2 PRINCIPLES OF EXTRACTIVE METALLURGY

ore had to contain at least 50/0 of copper in order to be accepted as an ore.

Today, due to improved technology, rocks with as little as 0.50/0 copper may be
mined and processed economically in spite of the market price for copper,
relative to other commodities, in the meantime having decreased. In the future
we may expect other rocks which today are considered worthless, such as the
aluminum silicates or the deep-sea nodules, to becomes ores for aluminum,
copper, nickel, and cobalt.
The question of what is called ore and what is rock depends also on
alternative uses of the rock. Traditionally rocks like limestone, dolomite, quartz,
and rock salt are not called ores even though, in addition to other uses, they
may also serve as raw materials for the production of metals like calcium,
magnesium, silicon, and sodium. On the other hand bauxite should definitely be
called an ore as it is mined mainly to serve as a raw material for the production
of aluminum. Seawater, which contains 0.130/0 Mg and may be used as a raw
material for the production of magnesium, can hardly be called an ore, other
uses being much more dominating.

Ore Types
A great many metals are present in nature as oxides. Most important are the
iron ores, which usually contain the mineral hematite, Fe203, but which also
may contain magnetite, Fe304. Iron hydroxides and carbonates, such as limo-
nite and siderite, may also be classified as oxide ores as the bound water and
carbon dioxide are easily expelled during the iron-making processes. Other
heavy metals which are mainly produced from oxide ores are manqanese,
chromium, titanium, tungsten, uranium, and tin. Aluminum is, as already men-
tioned, almost exclusively derived from bauxite, which is a hydroxide, whereas
some magnesium is derived from dolomite, which is a carbonate. Silicon is
produced from quartz. Some copper and nickel is derived from oxide ores,
which have been formed by weathering of sulfide deposits, but in general these
metals are derived mainly from sulfide ores.
The sulfide ores represent a large and important group. Most important are
the copper ores, which often consist of mixed sulfides of copper and iron. Other
metals which are mainly derived from sulfides are nickel, zinc, Lead, mercury, and
molybdenum. Even though sulfide ores often contain iron, e.g., as pyrite, FeS2,
they serve only in exceptional cases as sources for iron. Sulfide ores often
contain metalloids like arsenic, antimony, selenium, and teliurium. Of greater
economic importance is the fact that sulfide ores often contain smaller or larger
amounts of silver, gold, and the platinum metals. These noble metals may in
some cases also occur in nature in the metallic state, i.e., as native ores.
The last imported group of ores are the halides, such as rock salt for
sodium, and magnesium chloride brine which, together with seawater, serve as
sources for maqnesium.
Most crystalline ores contain a number of different minerals, i.e., crystals of
given composition. Thus a typical sulfide ore may contain chalcopyrite, CuFeS2,

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 INTRODUCTION 3

together with sphalerite, (Zn,Fe)S, and galena, PbS, as well as pyrite and sili-
cates or other gangue minerals. Such ores are usually first treated to separate
the different minerals, to give separate concentrates of copper, zinc, and lead, as
well as to discbarge the worthless gangue minerals. This treatment, which is
called ore-dressing, will be discussed further in Chap. 7, whereas in the present
chapter a brief and general discussion on metal-producing processes will be
given.

1-2 FLOW SHEETS

The process or combination of processes which is used in a given plant is

illustrated conveniently by means of a flow sheet. An example of such a flow
sheet is shown in Fig. 1-1 which illustrates the production of copper from a
low-grade copper sulfide ore. If flow sheets for different copper smelters are
examined they usually show some variations. This may be the result of differ-
ences in the composition of the ore, differences in the local supply of energy
such as fuel and electric power, differences in the demand for final products, and
differences in the size of the plant. Flow sheets for the production of steel and
zinc are shown in Figs. 1-2 and J -3. These differ again considerably from the
copper flow sheet, and it would seem that every metal and every locality re-
quired its own extraction process.

Unit Processes and Unit Operations

If the flow sheets are examined more closely it is seen that they consist of
combinations of steps or operations, and that some of the same steps or oper-
ations are found in the production of different metals and in different locations.
Thus for the copper flow sheet (Fig. 1-1) we have first some steps which involve
crushing, grinding, and flotation. The purpose of these steps, commonly called
ore-dressing, is to separate the ore mineral from the gangue or from other ore
minerals. The next step may be a roasting operation where some of the sulfur in
the ore is removed. This is followed by a smelting operation where copper is
enriched in a sulfide melt (matte), whereas iron and gangue minerals are dis-
carded in a slag. The matte is then blown in a converter where the remaining
iron is stagged and copper sulfide is oxidized to a crude metal (blister copper).
This is refined further in a refining furnace and finally refined by electrolysis to
produce the commercial product. Some deviations from this flow sheet are
found in different plants. In some plants the roasting step is omitted. In other
cases the electrolytic refining step is omitted, whereas sometimes the crude
blister copper is cast directly into anodes for electrolytic refining.
If we look at the flow sheets for the production of steel, zinc, or lead we
find some of the same steps as in copper production: roasting is used also in the
production of zinc and lead, a smelting operation is used for the production of
most metals, the blowing in a converter is used in the steel industry, etc. Thus a

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4 PRINCIPLES OF EXTRACTIVE METALLURGY

large variety of flow sheets is possible by combinations of a relatively small

number of different single steps. In analogy with the usage in chemical engineer-
ing we call these steps" Unit Processes" or "Unit Operations." Unfortunately
there is no generally accepted definition of the two terms. By "Unit Operation"
is usually understood a step which is characterized by certain physical features.
Thus crushing, screening, and transportation are typical unit operations. "Unit

Cu ore (1-2 %ICu)

Crushing. grinding

Tailing
Flotation
(O.1-O.2%ICu)

~
Cu concentrate (20-30% Cu)
t
Air Partial roast S02 to sulfuric
acid plant

Fluxes
t
Matte Slag to waste
smelting (0.3-1% Cu)

Cu matte (30-70% ICu)

Fluxes
Slag
t ~
Blowing in .S02 to sulfuric
Bessemer converter acid plant
E:s I
-E..
II>
I
I
I
Air
•
Blister copper (98 + % Cu)
tnl
I Slag
L - - _,._- - Fire relining

Anodes (99.5% ('u)

~
Waste electrolyte
Electrolytic refining
(Recovery of Ni. ctc.)

Cu cathodes Anode mud

(99.9+ % Cu) for recovery
Usually remelted of noble metals

Figure 1-1 Typical flow sheet for the production of copper from a low-grade copper sulfide ore.

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 INTRODUCTION 5

Iron ore
/' <,
High grade Low grade

Flue
lump fines
1
dust ~
Ore-dressing Tailing
1-

... Sintering, pelletizing

Coke and fluxes

Smelting in blast furnace Slag to waste

~

Scrap
'"
Pig iron (hot metal)

.-- _._ ---,.___ .......~} Slag to waste

.....Refining in open Refining in LD or r-
hearth furnace Bessemer converter
(Some may be returned
to BF. High-phosphorus
slag may be sold as
Open-hearth steel lD or Bessemer steel fertilizer. )

Figure 1-2 Flow sheet for iron- and steel-making. Left: open hearth; right: pneumatic steel-making,

Zinc sulfide concen rrate

I
Partial roast :
~
_X
Sulfating roast·
}S02 to
sulfuric acid

Sintering Leaching

Coal

r
Carbo thermic reduction Purification of Impurities to
solution Cd recovery

Carbothermic zinc Electrolytic Electr olyte returned

(may be refined reduction to lea ching
by distillation)
+
Electrolytic zinc
(high purity)

Figure 1-3 Flow sheet for production of zinc from zinc sulfide concentrate. Left: carbothermic
reduction; right: leaching and electrolysis.

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6 PRINCIPLES OF EXTRACTIVE METALLURGY

Processes" on the other hand means steps characterized by a certain chemical

reaction. Roasting of a sulfide ore or gas reduction of an oxide ore could be
called unit processes. It is evident that there will be a number of borderline
cases, and also cases where different steps have characteristic physical features
in common but differ with respect to their chemistry and vice versa. Thus a
blast furnace may be used for reduction of oxides, but may also be used for
oxidation of sulfides. A retort may be used for the coking of coal as welJ as for
the reduction of zinc oxide, and an electrolytic cell may be used for electrolytic
reduction as well as for electrolytic refining.
Even with tbe vague definition of unit operations and unit processes given
above, classification is more difficult in extractive metallurgy than in chemical
engineering. Three major types of classification could be considered:
1. According to pbases involved
a. Gas-solid. Examples: Roasting, gas reduction.
b. Gas-liquid. Examples: Bessemer blowing, distillation.
c. Liquid-liquid. Examples: Slag-metal reactions.
d. Solid-liquid. Examples: Liquation, leaching, and precipitation.
2. According to equipment
a. Fixed bed. Examples: Sintering, percolation leaching.
b. Fluidized bed. Examples: Fl uidized roasting and reduction.
c. Shaft furnace. Examples: Iron blast furnace, lime kiln.
d. Rotary kiln. Examples: Drying and calcination.
e. Retort. Examples: Coke-oven, carbo thermic zinc production.
f Reverberatory furnace. Examples: M.atte smelting, open-hearth steel-
making.
g. Electric furnace. Examples: Electric matte smelting and steel-making.
h. Cell for fused salt electrolysis. Examples: Production and refining of alu-
mmum.
i. CeU for aqueous electrolysis. Examples: Electrolytic reduction and refin-
mg.
3. According to chemical reactions
a. Oxidation. Examples: Roasting, sintering, Bessemer blowing.
b. Reduction. Examples: Iron-making, carbotherrnic zinc production.
c. Slag-metal reactions. Examples: Steel-making, matte smelting.
d. Chlorination. Examples: Production of titanium tetrachloride.
e. Electrolytic reduction. Examples: Electrolytic zinc and aluminum pro-
duction.
f Electrolytic refining. Examples: Refining of copper and nickel.
Further processes could be added to the above list.
It appears that whatever system of classification is used, it will tend to
emphasize certain similarities, whereas it will separate others. In the present text
the classification will mainly be according to the type of chemical reactions. It is
almost impossible to follow this classification consistently, however, and certain
digressions will be made into other systems of classification.

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 INTRODUCTION 7

Before the different unit processes are discussed, it will be necessary for the
reader to be familiar with some fundamental chemical and physical principles. A
unit process has as its main purpose to carry out a given chemical reaction. It is
therefore necessary to know how to make a reaction run in the desired direc-
tion, and how to avoid unwanted side reactions. This is first of all a question of
chemical thermodynamics and chemical kinetics. Furthermore, a certain reac-
tion temperature is needed. This requires a knowledge of heats of reactions and
of the principles of heat transfer. From the heats of reactions also the theo-
retical energy requirements may be calculated. Finally, the process has as its
purpose to produce the wanted product preferably as fast as possible. An evalu-
ation of the production capacity and of the factors which determine the size and
design of the reactors is obtained partly from chemical kinetics and partly from
heat transfer and fluid flow considerations. The first six chapters in this text
will, therefore, be devoted to the fundamental chemical and physical principles
which are common to all unit processes.
In the discussion of the individual unit processes, which will follow in later
chapters, emphasis will be put on the prevailing chemical equilibria and heat
balances. Furthermore, examples will be given of industrial applications, illus-
trated by the production of important metals: iron and steel, copper, lead, zinc,
light metals, and others.

1-3 FEATURES OF METAL EXTRACTION

The final combination of unit processes into a complete flow sheet is to a large
extent dependent on economic considerations: the cost of raw materials and
market conditions. Very often the same metal can be produced by several
different methods. This was shown in Figs. 1-2 and 1-3 for iron (steel) and for
zinc. Zinc may be produced from zinc sulfide ores either by a carbothermic
process (roasting, sintering, and reduction) or by hydrometallurgy (roasting,
leaching, and electrolysis). The choice will depend first of all on the cost of fuel
relative to electricity, second on the market conditions. Carbothermic zinc con-
tains impurities such as lead, arsenic, etc., and is used for making brasses and
also for galvanizing purposes. In these cases the impurities are not particularly
harmful and may be tolerated. Electrolytic zinc is preferably used for the pro-
duction of special zinc alloys, where a low impurity content is essential. Car-
bothermic zinc could meet the requirements of the alloy industry if it were
purified by redistillation, but that would add to the fuel bill.
The above two alternatives illustrate another feature of extractive metal-
lurgy: most metals are produced from impure ores. Most commonly these are
reduced to give an impure metal: pig iron, blister copper, lead bullion, or crude
zinc, etc. The impure metal may then be refined further to remove impurities
and give a product of the required purity. Alternatively the ores couid be
treated to give an essentially pure chemical compound of the metal, and the
compound may be reduced to give pure metal directly. The latter procedure,

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8 PRINCIPLES OF EXTRACTIVE METALLURGY

which is illustrated in hydrometallurgical zinc production, is more commonly

used for the more reactive metals: titanium, niobium, and the light metals.
These metals are more reactive than the impurities, which means that in most
refining processes the metal will be attacked before the impurities. The only way
to obtain a pure metal would, in that case, be to do the purification before the
reduction.
If we examine various flow sheets, we will observe certain other common
features. One of these is the circulation or return of intermediate products, slags,
etc., to previous steps. This is done in order to recover, as completely as pos-
sible, the valuable constituents. Thus in the flow sheet for copper (Fig. 1-1), the
slags from the Bessemer converter and from the fire-refining furnace are re-
turned to the matte smelting stage. Here the copper content of the slags is
recovered, and the only slag which is discarded is that from the matte smelting
stage. This slag contains almost all the impurities and as little as possible of the
valuable copper.
Recirculation cannot be used in all cases, however. In iron- and steel-
making (Fig. 1-2) one could consider the possibiJity of returning the steel-
making slag to the blast furnace in order to recover the iron and manganese
contents. This would be all right if the ore had been free of phosphorus. If
phosphorus is present in the ore, however, it will be reduced in the blast furnace
and enter the pig iron. In the steel-making processes phosphorus is oxidized and
transferred to the slag. If this slag were returned to the blast furnace, phos-
phorus would accumulate in a closed circuit. Therefore, for every element intro-
duced into the flow sheet, there has to be an outlet.
The return of refining slags to previous steps is an example of the so-called
counter-current principle, which is used extensively in extractive metallurgy.
Thus if the wanted metal preferentially dissolves in one phase, and the impu-
rities preferentially in another phase, the best separation is obtained by letting
the two phases flow counter-current to each other. This gives the highest pos-
sible concentration of the wanted product in the product phase and the lowest
possible concentration in the unwanted or discarded phase, i.e., the highest
recovery. Thus in the hydrometallurgical leaching of certain ores the raw ore is
first brought into contact with a solution of relatively high content of the
valuable element. The partly leached ore then passes through stages where it is
treated with solutions with successively lower contents of the valuable element,
these solutions being enriched, and the ore being washed out before it is dis-
carded. Another example of the counter-current system is in heal exchange,
which will be discussed in more detail in Sec. 6-7. When heat is transferred from
one phase to another, as in the heating of a solid burden by means of hot
combustion gases, the solids and the gases are made to flow counter-current to
each other, the cold solids first being brought into contact with the partly
cooled gases and then gradually into contact with gases of increasing temper-
ature.
In many flow sheets we observe the recovery of by-products. Thus, in Fig. 1-1
sulfur is recovered in the roasting and Bessemer steps, gold and silver from the

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 INTRODUCTION 9

anode mud, and nickel from the spent electrolyte. Most other ores also contain,
in addition to the major elements, smaller or larger quantities of by-product
elements. These are enriched in certain phases at certain stages in the treatment:
volatile metals in the flue dust, metals with high affinity for oxygen in the
refining slags, noble metals in anode mud, etc. Also, special processes may be
developed to recover valuable by-products which do not separate out during
the normal refining processes. Thus small amounts of silver will usually do no
harm in lead, but because of its value special methods have been developed for
desilverization of lead.
If the plant produces more than one main product, we may talk about
integrated processes. In an integrated plant the by-product from one part may
serve as raw material for another. Thus, in a plant which treats both zinc and
lead concentrates, the ashes from the zinc plant usually contain some lead, and
are passed on to the lead smelter, whereas the slag from the lead smelter may
contain enough zinc to justify its recovery and utilization in the zinc plant. The
efficient utilization of by-products in an integrated plant contributes greatly to
the economy of such a plant.
The recovery, both of the main product and of the by-products, will always
depend on economic considerations. Even though it may be technically possible
to get close to 100 percent recovery this is not necessarily the most economic
solution. Sometimes it is better to let some of the valuable elements go to the
slag dumps. When extraction techniques have improved or when the market
conditions have changed, these slag dumps may once again be "mined" to
recover with profit those elements which earlier generations could only recover
with loss.

1-4 UNITS OF MEASURE

The remaining part of this chapter will be devoted to some general consider-
ations of importance for the quantitative evaluation of metallurgical processes.
One difference between the art and the science of metallurgy is that the latter
tries to express the phenomena in a form which may be subject to quantitative
evaluation: measurement and calculation. This requires a wen-established
system of measuring units. It is true that the choice of units in numerical
calculations is immaterial as long as they are consistent. Certain unit systems
are more convenient tban others, however, and in recent years the SI system
(Systeme International d'Unites) has been adopted almost exclusively in the
industrialized countries and will be used in the present text.

Units for Length and Mass

The basic units in the SI system are the meter (m) and the kilogram (kg). For
larger masses the metric ton (1000 kg), commonly written tonne, for smaller
masses the gram (10-3 kg) are used.

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10 PRINCIPLES OF EXTRACTIVE METALLURGY

In chemistry the mass is sometimes expressed by the number of moles of

the various constituents. One mole is equal to as many grams of the substance
as is given by its atomic or molecular weight. Thus for iron, one mole is equal
to 55.84 grams, and one kilogram of iron is equal to 17.9 moles. Sometimes a
substance may be described by different formulas. Thus oxygen may be de-
scribed by the symbol 0, with an atomic weight of 16, or by O2 with a
molecular weight of 32. One kilogram of oxygen is then equal to 62.5 moles of
o or 31.25 moles of O2•

Units for Force, Pressure, and Energy

The unit for force is the newton (N), which is the force which gives a mass of
one kilogram an acceleration of one meter per second per second. As the
acceleration of gravity on Earth is about 9.81 mjs2 this means that the weight of
a one kilogram mass on Earth is about 9.81 N, whereas it is considerably less
on the Moon and considerably more on Jupiter.
The consistent unit for pressure would be the pascal (= 1 N/m2). Compared
to atmospheric pressure this is a very small unit, however. More common is,
therefore, the kilopascal (= 103 Pa) or the bar (= 105 Pa). Atmospheric pressure
(1 atm) corresponds to 1.013 bar. For chemical thermodynamic calculations a
speciaJ problem arises as all available thermodynamic data are based on atmos-
pheric pressure as the standard state. AU derived pressures will, therefore, also
appear in atmospheres. Actually, however, the derived pressures may be con-
sidered dimensionless, as they are given relative to the chosen standard state
which is 1.013 x lOs Pa, and will in this text be denoted by the symbol p.
For energy, heat, and work, the consistent unit is the joule (J) which is
equal to one newton-meter, and also equal to one watt-second. This unit will be
used exclusively in this text, even though most available thermodynamic data
are published elsewhere in the more traditional unit, the calorie, which is equal
to 4.184 joules. t Other units for energy which are still in use are the kilowatt-
hour and the liter-atmosphere, as well as the traditional British unit (Btu) and
foot-pound, and in Table 1-1 conversion factors for the various units for energy
are summarized.

Units for Temperature

We distinguish between temperature scale and temperature units. The temper-
ature scale expresses how a temperature difference at one temperature level
relates to temperature differences at other temperature levels. Thus we need to
establish a temperature scale in order to compare the temperature difference

This number applies for the thermochemical

I calorie relative to the absolute joule. See footnote
to Table J-1.

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Copynghted material
12 PRINCIPLES OF EXTRACTIVE METALLURGY

between, say, the melting and boiling points of water with the temperature
difference between the melting and boiling points of, say, zinc. The thermody-
namic temperature scale, which we use, is derived from the equation of state for
a perfect gas, that is, the thermodynamic (absolute) temperature is defined by
the relation T = PVM/R. Here R is a constant, whereas PVM represents the
limiting value which the product of pressure and molar volume of any gas
approaches when the pressure approaches zero. The temperature unit depends
on the numerical value for the constant R. For the Kelvin unit this constant is
chosen to make the difference between the normal melting and boiling points of
water equal to 100 units (degrees). This gives R the numerical value of
0.082 liter-atm/(K . mol) = 8.314 J/(K' mol) and the temperature for the ice
point equal to 273.16 K.
In practical work the temperature is often expressed in the Celsius scale.
This has the same unit as the Kelvin scale, but the zero point is chosen at the
melting point of water. This fixes the boiling point of water to 100°C and, in
general, °C = K - 273.16.

Gases and Gas Compositions

Whereas for solids and liquids the quantities and the concentrations are usually
given by masses and weight percentages, a different procedure is used for gases.
Most gases will under ordinary conditions obey the perfect gas law, that is, for
a given temperature and pressure the gas volume is proportional to the number
of moles. The quantity of a gas may then be expressed by its volume at some
standardized temperature and pressure. Most common is ooe and one atmo-
sphere pressure, where one cubic meter contains 1000/22.4 = 44.6 moles of gas,
and is denoted one normal cubic meter (Nm3) or m? (STP). By means of the
perfect gas law the volume at any other temperature and pressure may be
calculated.
The concentration of a component in a gas mixture is usually expressed by
its volume percentage which is equal to its mole percentage. Thus (vol % x) =
100· n.-r:/l1tot where n, is the number of moles of component x and nlOl is the
total number of moles in the gas mixture. Also, the relative partial pressure of a
component in a gas mixture is given by the relation Px = (nX/n1ot)ptot, where Ptot
is the relative total gas pressure. The two last reLations are independent of the
temperature of the gas.
It should be pointed out that the above relations are strictly valid only for
gases which obey the perfect gas Law, but they are usually rather closely obeyed
at and above room temperature and at pressures up to a few atmospheres. For
higher pressures and extremely low temperatures special equations will have to
be applied.
Combustion gases often contain water vapor. The composition may then be
expressed either on wet or on dry basis. The wet composition includes the water
vapor, whereas in the dry composition the water vapor is disregarded, the
amounts of the remaining components adding up to 100 percent.

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 INTRODUCTIOr-: 13

1-5 STOICHIOMETRY

In chemical and metallurgical calculations we often need to calculate the rela-

tive amounts of reactants that are needed for a given reaction, as well as the
amounts of products. Such calculations, which are based on the chemical reac-
tion equations and the molar weights of the various compounds, are called
stoichiometry. The questions that \ve want to answer by such calculations are:

I. What are the relative quantities of reactants to go into a certain process?

2. What are the quantities of products obtained?
3. What is the composition of these products?

Stoichiometric calculations may be carried out in many different ways and

each person will, by experience, find his own method. The following procedure
is therefore not the only way to do such calculations, but is a way which has
proved to be most useful and gives few possibilities for mistakes.
As a typical case we shall consider the combustion of methane with air to
give carbon dioxide and water vapor according to the reaction:
CH4(g) + 202 = CO2 + 2H 20(g)
We may then proceed as follows:

1. Choose as a basis a given amount of reactant. This could be one mole, one
kilogram, one tonne, or any other quantity.
2. Calculate the number of moles of reactants in the chosen basis.
3. From the reaction equation calculate the number of moles of otber reactants
and the number of moles of products.
4. Convert the number of moles of reactants and products into suitable units,
weights, or volumes.
5. Calculate the composition of the product in suitable units.

As an example we may choose as our basis I Nm3 of methane, which we

consider to be an ideal gas giving 44.6 mol of CH~. This reacts with 89.2 mol of
O2 to give 44.6 mol of CO2 and 89.2 mol of H20. However, since air contains
21 mol percent of O2 and 79 mol percent of N2, 335.3 moles of nitrogen will
enter with the air and appear in the product. The air volume will be
(89.2 + 335.3) 22.4 = 9.5 x IO~N I = 9.5 Nm3 per unit. The corresponding com-
bustion gas volume will be (44.6 + 89.2 + 335.3}22.4 = 10.5 x 103 Nl = 10.5 Nm3,
and the wet composition will be 9.5 mole percent of CO2, L9 mole percent of
H 20(g) and 7l.5 mole percent of N 2' The corresponding dry volume and com-
position will be 8.5 Nm3 with 11.75 mole percent of CO2 and 88.25 mole
percent of Nz· Notice that it is perfectly legitimate to give the wet gas volume
in normal cubic meters, even though most of the water would condense at O°C.

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14 PRINCIPLES OF EXTRACTIVE METALLURGY

In most combustion processes a surplus of air is used. If for example a 10

percent surplus was used in the above case, an additional 8.9 mol of O2 and
33.5 mol of N2 would have to be added to the air as well as to the combustion
gas. If, on the other hand, a deficiency of air is used the matter becomes more
complicated. For a moderate deficiency the combustion gas will consist of a
mixture of CO2, CO, H20, and H2• If the percentage of each product in the
gas were known the corresponding amount of air can be easily calculated. If, on
the other hand, only the amount of air per unit of methane were known, only
the number of moles of CO2 + CO and of H20 + H2 as well as the ratio
between the number of moles of CO + H2 and of CO2 + H20 can be calcu-
lated. In order to know the percentage of each gaseous component it will be
necessary to know the relevant chemical equilibria, as will be discussed in
Chap. 3.

Example 1-1 Limestone with 56 percent CaO and 44 percent CO2 is cal-
cined in a rotary kiln giving a calcine of pure CaO. For each kilogram of
limestone, 0.15 kg of fuel oil, with 85 percent carbon and 15 percent hy-
drogen is used, and the volume of the combustion air is 2.10 Nm3. The fuel
burns completely to CO2 and H20, which mix with CO2 expelled from the
limestone. Calculate the volume (in Nm3) of the furnace gas, as well as its
wet and dry composition. Air is regarded as containing 21 volume percent
O2 and 79 volume percent N2.

SOLUTrON For a basis of 1 kg of limestone the amount of CO2 in the

limestone is 0.44 kg = 10 mol, the amount of carbon in the fuel is
0.1275 kg = 10.63 mol, and the amount of hydrogen in the fuel is
0.0225 kg = 11.17 mol of H2• The combustion air corresponds to a total of
93.8 moles with 19.7 mol of O2 and 74.1 mol of N2. For the burning of the
fuel 10.63 + 5.59 = 16.22 mol of O2 are needed, leaving 3.48 mol of O2
unused. The furnace gas, therefore, contains 10 + 10.63 = 20.63 mol of
CO2, 11.17 mol of H20, 3.48 mol of O2, and 74.1 mol of N2, or a total of
109.4 moles, corresponding to 2.45 Nm3 with the wet composition: 18.8
percent CO2, 10.2 percent H20(g), 3.2 percent O2, and 67.8 percent N2.
The corresponding dry composition will be 21.0 percent CO2, 3.5 percent
O2, and 75.5 percent N 2.

1-6 MATERIAL BALANCES

We distinguish between material balances and charge calculations. In charge

calculations the necessary amounts of raw materials are calculated. This re-
quires a knowledge of chemical equilibria and kinetics, heats of reaction and
heat losses, as they will be discussed in the following chapters. j\t[ aterial bal-
ances, on the other hand, is a form of bookkeeping for a process which is

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 fNTRODUCTION 15

already operating. The basic equation in material balances is the law of conser-
vation of matter. For each element x we have:
I=n }=m

L 111/(% x) = L n1j(% x) + Sm ;
1=1 j:;l

input = output + accumulation

Here m, represents the mass of each type of raw material wbich enters, and mj
the mass of each product which leaves tbe process over a given period of time.
(% x) is the weight percentage of element x in that raw material or product,
and tsm, is the mass of x which accumulates in the process. Notice that under
certain conditions, for example when a furnace lining is being eroded, Sm, may
be negative. If Sm; is zero, we say that steady state conditions exist. In Table 1-2
is illustrated steady state conditions for components x, y, and z in a process
with the raw materials A, B, and C and the products L, M, and N.
Very often we do not know all the masses or all the concentrations. During
a slag refining process, for example, we may know the weights and composition
of all raw materials, as well as the weight and composition of the refined metal,
but we do not know the weight and composition of the slag. Assuming that
there has been no exchange of material with the atmosphere, or assuming that
this exchange is known, the missing data may in that case be calculated from
the material balance.
Similarly, if the composition but not the mass of the slag is known, the
latter may be calculated. In that case we will have one equation for each
element, and we may calculate several values for the slag weight. If aU weights
and analyses were exact, these slag weights would agree. Usually this will not be
the case. We must then choose the values which give the highest accuracy. This
means choosing the elements for which the chemical analyses are most reliable,
and also the elements which occur in the larger quantities in the slag. Having
assessed the slag weight on this basis, the amount and concentration of the
remaining elements in the slag may be calculated and compared with the ana-
lytical values. If the two sets of values differ by much more than the expected
accuracy of the procedure, this may indicate that some element has been ac-
cumulated in the furnace, alternatively dissolved from the furnace lining, or lost
in some yet unknown reaction product, for example, the flue dust.
The efficiency of an extraction process may conveniently be expressed by
two figures: the recovery and the ratio of concentration. The recovery is the

Table 1-2 Material balance under steady state conditions

Raw materials Products

Component A 8 c L M N

x I1IA(%X) + mB(%x) + mc(%x) = 111,.(% x] + mM(%x) + 111....(% x)

y m,.(% y) + 1118(% y) + mC(%)I) = mI.(% y) + tIIM(% y) + Itlo\.( % y)
z 111,4(% z} + 1118(% z) + Itlc(% z) = m,.(% z) + mM(% z) + 111....(% z)

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16 PRINCIPLES OF EXTRACTIVE METALLURGY

amount of a given element in a given product relative to the total amount of

the same element in the raw materials. In principle we may speak about the
recovery in all products (metal, slag, and gases), which necessarily must add up
to 100 percent, but usually we are only interested in the recovery of the valu-
able element in the valuable product. The remaining amounts then represent the
loss.
The ratio of concentration is of particular importance in, ore-dressing, and
is equal to the weigbt of the raw material (the ore) relative to the weight of the
valuable product (the concentrate). For a given process there is a kind of
inverse relationship between the recovery and the ratio of concentration, a high
recovery giving a low ratio of concentration and vice versa. Of several processes
the one is the most efficient which combines a high recovery with a high ratio
of concentration.

Example 1·2 A copper ore contains 1.5 percent Cu. After ore-dressing,
4.5 kg of concentrate with 30 percent Cu is obtained from 100 kg of ore.
Calculate (a) the ratio of concentration, (b) the recovery, and (c) the weight
and Cu-percentage of the discarded gangue (tailing).

SOLUTION (a) The ratio of concentration

is given by 100/4.5 = 22.2.
(b) The ore contains a total of 0.015 x 100 = 1.5 kg Cu. The concentrate
contains 0.30 x 4.5 = 1.35 kg Cu. This gives the recovery = 1.35/1.5 =
0.90 or 90 percent.
(c) The weight of the tailing is 100 - 4.5 = 95.5 kg, and its copper content
0.15 kg. This gives its Cu-percentage eq ual to 0.157.
Example 1-3 A zinc sulfide concentrate contains 50 percent Zn, 13 percent
Fe, 32 percent S, and 5 percent Si02. When 100 kg is roasted with air,
85 kg of calcine with 54.5 percent Zn, 14.1 percent Fe, 2.7 percent S, and
5.4 percent Si02 is obtained. The remaining percentages are assumed to be
oxygen. The flue dust is assumed to have the same composition as the
calcine. The roast gas contains 8 volume percent S02' Calculate (a) the
weight of the flue dust and its content of the various components, as well as
(b) the volume (in Nm3) and (c) the composition of the roast gas, and (d) the
volume of air used. Air may be regarded as containing 21 volume percent of
O2 and 79 volume percent of N2.

SOLUTION (a) For the concentrate and solid products we get the following
material distribution (basis 100 kg of concentrate).
Concen-
trate Calcine Flue dust
Zn: 50 kg 0.544 x 85 = 46.2 kg 3.8 kg = 54.5 percent
Fe: 13 kg 0.141 x 85 = 12.0 kg 0.99 kg = 14.1 percent
S: 32 kg 0.027 x 85 = 2.3 kg 0.19 kg = 2.7 percent
Si02: 5 kg 0.054 x 85 = 4.6 kg 0.38 kg = 5.4 percent
O2: balance = 19.9 kg 1.64 kg = 23.4 percent
Total 100 kg 85.0 kg 7.00 kg = 100 Eercent

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 INTRODUCTION 17

Here the weight of the flue dust (7.00 kg) is estimated from the difference
between the zinc content of the concentrate (50 kg) and that of the calcine
(46.2 kg) and from its assumed zinc percentage (54.4), zinc being the major
component. From the weight of dust and its assumed composition the con-
tents of the remaining components are calculated.
(b) The sulfur content of the gas is now obtained as the difference between that
of the concentrate and that of the calcine plus flue dust, and amounts to
32.0 - 2.5 = 29.5 kg = 0.92 kmol ofS, which in the roast gas is present as
0.92 kmol of S02' This gives the total amount of roast gas equal to
0.92/0.08 = 11.50 kmol or 258 Nm 3.
(c) The composition of the roast gas is obtained from the following reason-
ing: the oxygen in the calcine and flue dust amounts to 19.9 + 1.64 =
21.54 kg = 0.67 krnol of O2, which together with 0.92 kmol in S02
gives a total of 1.59 kmol of O2, all derived from air. This amount is
associated with (1.59 x 79)/21 = 6.0 kmol of N2, which must also be
present in the roast gas. The remaining part of the roast gas, 11.50-
(0.92 + 6.0) = 4.58 kmol represents a surplus of air. This surplus contains
4.58 x 0.21 = 0.96 kmol of O2 and 3.62 kmol of N2• Thus we have the
total composition of the roast gas:
S02 - 0.92 kmol = 8.0 volume percent
N2 = 6.0 + 3.62 = 9.62 kmol = 83.7 volume percent
O2 - 0.96 kmol = 8.3 volume percent
Total 11.50 kmol = 100 volume percent
(d) The amount of air used is then:
N 2 = 9.62 kmol
O2 = 2.55 kmol
Total
--~~~~--------~
12.17 kmol = 273 Nm3

PROBLEMS
I-I Express in mole (atomic) percents the composition of a stainless steel with 18 wt o/Q chromium,
8 wt "10 nickel, and the balance iron.
1-2 Air contains 21 volume percent 01, 78 volume percent N2, and J volume percent Ar (argon).
Express its composition in weight percents.
1-3 Pyrite (FeS1) is roasted with an excess of air lO give Fe20J and S02. The roast gas contains
6.3 percent S02' the balance being Oland N 2' Calculate per metric ton of pyrite: (a) theoretical
air requirement (in NmJ), (b) actual air requirement, (0) composition of roast gas in volume per-
cents, (d) volume of roast gas at 500°C.
14 A blast furnace burden contains 160 kg FeZ03, 54 kg SiOz, 20 kg AI20). 100 kg CaCO) , and
18 kg C. For the smelling of the above burden 266 Nm3 of air is used. The hot metal produced
contains 4 percent C and J percent Si, the balance being iron, and it is assumed that all the iron in
the burden enters the hot metal. The remaining oxides form a slag, whereas CO2 from the lime-
stone is expelled and mixes with the furnace gas. Carbon in the gas is present partly as CO2 and
partly as CO and there is no free oxygen. (a) Calculate the weight of the hot metal, as well as the
weight and composition of the slag; (b) calculate the volume and composition of the furnace gas. all
for the above basis.

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U'IBLIOGRAPHY

Bray, J. L.: ..Non Ferrous Production Metallurgy 0, and" Ferrous Process MetaJlurgy," John Wiley
and Sons Inc., New York, 1947 and 1954.
Dennis, W. H.: .. Metallurgy of the Non-Ferrous Metals" and" Metallurgy of the Ferrous Metals,"
Sir Isaac Pitman and SOilS Ltd, London, 1961 and 1963.
Gilchrist, J. D.: "Extraction Metallurgy," 2d ed. Pergamon Press, London, 1980.
Gill, C. 8.: "Non-Ferrous Extractive Metallurgy," John Wiley and Sons Inc., New York, 1980,
Habashi, F.: .. Principles of Extractive Metallurgy," Vol. I, Gordon and Breach, New York, 1969.
Liddell, D, M.: "Handbook of Non-Ferrous Metallurgy," McGraw-Hill Book Co. Inc., New York,
1945.
Newton, J.: .. Extractive Metallurgy," John Wiley and Sons Inc., New York, )959
Schuhmann, R, Jr.: .. Metallurgical Engineering," vOl: I, Addison-Wesley Publ. Co. Inc., Reading.
Mass., 1952.

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