Extractive

Metallurgy
Prof. Dr. Eng.
Mohamed Sayed Ahmed
 Definition of extractive metallurgy
The extraction of metals from their
ores or from the naturally occurring
aggregates of minerals by various
mechanical and chemical methods.
 Metals
A solid material which is typically
hard, shiny, malleable, fusible, and
ductile, with good electrical and
thermal conductivity (e.g., iron, gold,
silver, and aluminum, and alloys
such as steel).
 Commercial Classification of Metals
Ferrous Metals Non-ferrous Metals
Iron and Steel Alloys 1. Heavy metals (e.g., Cu, Ni, Pb, Zn, Sn) - sp. gr. “7-11
gm/cm3
2. Light metals (e.g., Al, Mg, Ca, Na, K) - sp. gr. < 4 gm/cm3
3. Noble (Precious) metals (e.g., Au, Ag, Pt)
4. Minor (Secondary) metals (e.g., As, Sb, Bi, Cd, Hg, Co)
5. Refractory metals (e.g., W, Mo, Ta, Ti, Zr, V) - m.p. > 1650
0C (alloying elements)

6. Scattered metals (e.g., Ge, In, Ga, Tl, Hf) - they have no
ores of their own (they are distributed in extremely
minute quantities in the earth’s crust)
7. Radioactive metals (e.g., Ra, Th, U)
8. Rare-earth metals (e.g., Y, La, Ge)
9. Ferroalloys metals (e.g., Cr, Mn) - mainly used as
alloying elements in cast iron and steels
 Sources of Metals

Primary Sources Secondary Sources

(from ores) (from scrap)
Metals are mainly obtained
from bodies of materials
occurring in the earth’s
crust and called “Ores”.
Ore may be defined as a metal-
bearing mineral or an aggregate of
such minerals containing a large
enough proportion of the metal
which can be profitable extracted.
The earth’s crust to a depth of about
16 km. contains an average of:
- 46.59 % Oxygen
- 27.72 % Silicon
- 25.69 % all other elements
 Metallurgical extraction methods
1) Pyro metallurgy: 2) Hydrometallurgy:
(temp. > 500 C) (temp. < 300 C)

- Calcination - Leaching
- Roasting - Thickening
- Sintering - Precipitation
- Smelting - Electrolytic deposition
- Distillation
Roasting Operations
 Oxidizing roasting
Oxidizing roasting involves heating the ore in excess
of air or oxygen, to burn out or replace the impurity
element (e.g., S) partly or completely by oxygen.

Sulfide roasting, the general reaction can be given by:

2MS (s) + 3O2 (g) = 2MO (s) + 2SO2 (g)
Roasting the sulfide ore, until almost complete removal
of the sulfur from the ore, results in a dead roast.
 Volatilizing roasting
Volatilizing roasting, involves careful oxidation at
elevated temperatures of the ores, to eliminate
impurity elements in the form of their volatile
oxides. Examples of such volatile oxides include
As2O3, Sb2O3, ZnO and sulfur oxides.
Careful control of the oxygen content in the roaster
is necessary, as excessive oxidation forms non
volatile oxides.
 Chloridizing roasting
Chloridizing roasting transforms certain metal compounds to
chlorides, through oxidation or reduction. Some metals such as
Uranium, Titanium, Beryllium, and some Rare earths are
processed in their chloride form.

Certain forms of chloridizing roasting may be represented by

the overall reactions:
2NaCl + MS + 2O2 = Na2SO4 + MCl,
4NaCl + 2MO + S2 + 3O2 = 2Na2SO4 + 2MCl2
The first reaction represents the chlorination of a sulfide ore
involving an exothermic reaction. The second reaction
involving an oxide ore is facilitated by addition of elemental
sulfur. Carbonate ores react in a similar manner as the oxide
ore, after decomposing to their oxide form at high temperature.
 Sulfating roasting

Sulfating roasting oxidizes certain

sulfide ores to sulfates in a controlled
supply of air to enable leaching of the
sulfate for further processing.
Sulfating: 2MS (s) + 4O2 (g) = 2MSO4 (s)
Oxidizing: 2MS (s) + 3O2 (g) = 2MO (s) + 2SO2 (g)
 Magnetic roasting
Magnetic roasting involves controlled roasting
of the ore to convert it into a magnetic form,
thus enabling easy separation and processing
in subsequent steps. For example, controlled
reduction of Hematite (non magnetic Fe2O3) to
Magnetite (magnetic Fe3O4).
3 Fe2O3(s) + CO = 2 Fe3O4(s) + CO2
 Reduction roasting
Reduction roasting partially reduces an
oxide ore before the actual smelting process.
An example is the reduction roasting of a hematite containing
material to produce magnetite that can be magnetically
separated.
3 Fe2O3(s) + CO = 2 Fe3O4(s) + CO2

A second example comes from the Waelz process, where zinc

oxide in steel mill waste is reduced to a metallic zinc and
volatilized for recovery in the off-gas system.
2 ZnO(s) + 2 CO → 2 Zn(g) + 2 CO2
 Sinter roasting
Sinter roasting involves heating the fine ores at high
temperatures, where simultaneous oxidation and
agglomeration of the ores take place.
An example is the sinter roasting of lead sulfide ores
in a continuous process after froth flotation to convert
the fine ores to workable agglomerates for further
smelting operations.
A second example is the sinter roasting of iron ores
fines in a sinter machine, to create a product that can
be used in a blast furnace.
Production of Volatile Metals

Metal m.p., 0C b.p., 0C Density, gm/cm3

Hg -38.4 356.6 13.55
Cd 321 765 8.64
Zn 419.5 907 7.14
Pb 327.4 1740 11.34
Cu 1083 2360 8.64
Fe 1536 ̴ 3000 7.87
Zn Extractive Metallurgy
Physical and Chemical Characteristics of Zn

Atomic number 30
Atomic mass 65.409
Melting point, 0C 419.53
Boiling point, 0C 907
Density, gm/cm3 7.135
Crystal structure HCP

• Zn is a coarse grain metal.

• Zn is brittle at normal temperature.
• Zn can be easily rolled into sheets and drawn into wire at 100-150 0C.
• Pure Zn is highly resistant to attack by dry air at temp. < 200 0C, due
to the film of basic carbonates formed on its surface (a dense film).
• Pure Zn is quite useful for galvanizing and brass making processes.
 Zn-ore is defined as an aggregate of such minerals
containing a large enough proportion of Zn-metal which
can be profitable extracted.
Zn-ores generally contains “2 – 7.5 %” Zn-metal.

 Zn-minerals mostly are:

Zn-mineral Chemical composition % Zn
Sphalerite (Zn,FeS) 67
Smithsonite (ZnCO3) 52
Willemite (Zn2SiO4) 59
Hemimorphite (Zn4Si2O7(OH)2 H2O) 54

The main Zn-mineral is Sphalerite (Zn,FeS), which contains up to 67% Zn

 How is zinc extracted from its ore?
Zinc metal is produced using extractive metallurgy. After grinding
the ore, froth flotation, which selectively separates minerals from
gangue by taking advantage of differences in their hydrophobicity, is
used to get an ore concentrate. A final concentration of zinc of about
50% is reached by this process with the remainder of the
concentrate being sulphur (32%), iron (13%), and SiO2 (5%).
Roasting converts the zinc sulfide concentrate produced during
processing to zinc oxide:
2 ZnS + 3 O2 → 2 ZnO + 2 SO2
The sulfur dioxide is used for the production of sulfuric acid, which
is necessary for the leaching process.
The oxide is further processed using either of two basic methods:
Pyrometallurgy or Hydrometallurgy.
Pyrometallurgy processing reduces zinc oxide with
carbon or carbon monoxide at 950 °C into the metal,
which is distilled as zinc vapor. The zinc vapor is
collected in a condenser. The following equations
demonstrate this process:
2 ZnO (s) + C → 2 Zn (g) + CO2
2 ZnO (s) + 2 CO → 2 Zn (g) + 2 CO2
Hydrometallurgy processing leaches zinc from the
ore concentrate by sulfuric acid (Electrowinning):
ZnO (s) + H2SO4 (aq. soln.) → ZnSO4 (aq. soln.) + H2O
After this step electrolysis is used to produce zinc metal.
The Metallurgy of Zinc
(Pyrometallurgy Processing)
The Metallurgy of Zinc
(Hydrometallurgy Processing)
Thermodynamic of ZnO Reduction by C
 Thermodynamic of ZnO Reduction by C
About ½ of the world’s production of Zn is made by reduction of
sinter-roasted Zn-ore with C
The relation between the standard thermodynamic potentials (ΔG)
of formation of oxides and temperature (Fig.) shows that ZnOs can
be reduced by C to Znvap. At temp. > 920 oC, according to the
following reaction:
ZnOs + Cs = Znvap. + CO
Reduction of ZnOs by C will take place according to the following
steps:
1) 2 C + O2 = 2 CO
2) 2 ZnOs + 2 CO = 2 Znvap. + 2 CO2
3) 2 CO2 + C = 2 CO

Reduction of ZnO by C will take place at temp. above the

intersection of the two lines of ZnO and CO, at temp. > 920 oC and
1 atmosphere.
The relation between the standard thermodynamic potentials (ΔG) of formation of oxides and temp.

Δ G, kcal / mole O2

920 oC

Temperature, oC
Kinetic of ZnO Reduction by C
 Kinetic of ZnO Reduction by C
Reduction of ZnO by C/CO begins at about 920 oC

according to the following reactions:

ZnOs + CO = Znvap. + CO2
CO2 + C = 2 CO

Overall reaction: ZnOs + C = Znvap. + C

Znvap.

CO
ZnO C
CO2
O2
at temp. > 920 oC
The reduction of ZnO with C consists of:
1. Reduction with CO on the ZnO surface ( ZnO + CO = Zn + CO2)
2. The Boudouard reaction on C surface (C + CO2 = 2 CO)
3. Diffusion of the gases between the two surfaces (Diffusion)

The three steps are coupled in series, and the slowest step will be rate
controlling. Measurements showed that the diffusion of gases between
the two surfaces (ZnO and C) is rate controlling.
Therefore, it is possible to increase the reaction rate of the overall
reaction “ZnO (s) + C = Zn (vap.) + C“ by:
 Increasing the gas velocity (by blowing CO through a fixed or fluidized
bed of ZnO and C mixture).
 Increasing the surface area and decrease the distance between the
two surfaces (good mixing of finely crushed oxide sinter and coke).
 Overheating is necessary to get an acceptable reduction rate
(overheating to 1000 or 1100 oC ).
 Using excess of coke to increase CO and decrease CO2 content in the
gas (by using 2-3 times the stoichiometric amount of C).
Reoxidation and Condensation of Zn
 Reoxidation and Condensation of Zn
What happens to the “Znvap.- CO - CO2” gas mixture when this is cooled from the
reaction temperature?
If complete chemical equilibrium is established at all temps of reactions:
1) ZnOs + CO = Znvap. + CO2
2) CO2 + C = 2 CO
On cooling, reactions 1) and 2) would reverse to give ZnO and C, i.e., we would
back where we started .
Fortunately, reversion of reaction 2) is very slow, and the amount of soot formed
on cooling of the gas is usually small. However, reversion of reaction 1) is much
faster, and unless special precautions are taken most of CO2 in the reaction gas
will on cooling react with equivalent amount of Znvap.. Thus if the gas had
contained about 50% each of Zn and CO and 1% of CO2, then;
2 Znvap. + CO2 = 2 ZnOs + C
i.e., 2% of its Zn content would reoxidize on cooling. If by means of excess C and
high temp., the CO2 conc. is lowered to 0.1%, only 0.2% of Znvap. would reoxidize.
Even though the amount of ZnO formed is small, it may have an adverse effect on
the process in so far as it acts as nuclei for the condensation of Zn vapor, the
droplets formed will be covered with thin layer of ZnO and this will prevent Zn
droplets from coalescing.
Industrial Zn Processes
Horizontal Retort Process
(similar to coking and Hoganas sponge iron)
Horizontal Retort Process:
 Made of fireclay
 Cylindrical shape
 Diameter ≈ 0.3 m
 Length ≈ 1.5 m
 Fuel (hot combustion gases)
 Small cross sectional is necessary for heat flow into the
retort within a reasonable time. (production of 100 tons
Zn / day requires over 3000 retorts)
 Zn vapor condenses in air cooled condensers and CO
gas burns to waste at the mouth of the condensers.
 Charging and emptying the retorts and draining of the
condensers are manual.
 Thus with present high costs of labor and fuel the
process is becoming uneconomical.
The basic disadvantages of Horizontal Retort:

 intermittent nature
 cumbersome furnaces
 difficulty of mechanization
 high cost (labor and fuel)
 CO burns to waste
 low production
 Vertical Retort
(developed by the New Jersey Zn Co.)
Vertical Retort: (New Jersey Furnace)
 made of SiC (m.p. above 2700 oC)
 the shape of a rectangular shaft
 "10-15" m high & 2 m long & ̴ 0.3 m width
 fuel producer gas
 A battery consists of a number of retorts separated
by combustion chambers (the retorts are heated
from outside) in the same way as in cooling plant.
Charge of Vertical retort:
Briquettes prepared from a mixture of:
1)roasted Zn concentrate
2)coal
3)suitable binder, e.g., coal tar
 After through mixing, the batch (mix) is passed
through a briquetting press, and the briquettes
are heated to 700-800 oC.
 Thus, the briquettes attain a strong and porous
structure.
 The retorts are charged with briquettes (700-800 oC).
 Carbothermic reduction takes place above 900 oC.
 By the time the briquettes have reached the bottom
of the retort (virtually all Zn is expelled).
 In the bottom of the retort a small amount of spent
combustion gases is introduced in order to prevent
Znvap. from condensing in the lower part of the retort
and to sweep it upwards.
 The spent briquettes are discharged through a water
lock.
 Blast Furnace
(developed by developed by Imperial Smelting Corporation, England)

Blast furnace for smelting of mixed Zn & Pb sinter.

Refluxing units