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LECTURE NOTES

MetE 208
Chemical Principles of Materials Production
Prof.Dr. Yavuz A. TOPKAYA

1. INTRODUCTION
1.1 Sources of Metals
1.2 Mineral Dressing
1.3 Preliminary Treatment
1.4 Extraction Processes
1.5 Fuels and Refractories
1.6 Ironmaking
Flowsheet
Blast Furnace Charges and Operation
1.7 Steelmaking
Flowsheet
Steelmaking Processes
1.8 Non-ferrous Metals
1.8.1 Copper Production (As flowsheets)
1.8.2 Zinc Production (As a flowsheet)
1.8.3 Lead Production (As a flowsheet)
1.8.4 Aluminum Production (As a flowsheet)

2. MATERIAL BALANCES (STOICHIOMETRY)
2.1 Stoichiometric Principles
2.1.1. Conservation of Mass
2.1.2. Mass Relations in Metallurgical Reactions
2.1.3. Volume Relations in Metallurgical Reactions
2.1.4. The gram-atom, kg-atom, gram-mole, kg-mole
2.1.5. Gas Laws
2.1.6. Excess of Reactants
2.2 Analyses of Materials
2.3 Charge Calculations

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2.4 Examples
2.4.1. Combustion
2.4.2. Excess Reactants
2.4.3. Roasting
2.4.4. Gas Treatment
2.4.5. Problem Hours on Material Balances

3. HEAT BALANCE
3.1 Kinds of Energy and Conservation of Energy
3.2 Heat Balance
3.3 Procedure in Calculating a Heat Balance
3.4 Choice of Reactions
3.5 Examples of Heat Balance

4. REFERENCES
4.1 SCHUHMANN R., Metallurgical Engineering Vol I, Engineering
Principles, Addison Wesley, 1952
4.2 ROSENQVIST T., Principles of Extractive Metallurgy, McGraw-Hill,
1973
4.3 GILCHRIST J. D., Extractive Metallurgy Pergamon, 1980
4.4 NEWTON J., Extractive Metallurgy, John Wiley, 1967
4.5 PEHLKE R.D., Unit Processes of Extractive Metallurgy, Elsevier, 1973
4.6 FINE H.A. and GEIGER G.H., Handbook of Material and Energy
Balance Calculations in Metallurgical Engineering, AIME, 1979
4.7 SCHLESINGER M.E., Mass and Energy Balance in Materials
Engineering, Prentice-Hall, 1996

5. MARKING
1st Mid-Term 25 %
2nd Mid-Term 25 %
Final 40 %
Homeworks 10 %

6. COURSE ASSISTANT: PINAR BURCU KAYIN


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CHAPTER 1

1.1. THE SOURCES OF METALS

Metallurgy is the science and art of extracting metals from their ores, refining them
and preparing them for use.
Ores are naturally occurring deposits in the Earths crust. The ores are mined and
treated by various unit operations (mechanical processes) and unit processes (chemical
metallurgical processes) to extract metals, and to convert them into the metallic (chemically
uncombined) form.
Earths crust refers to the outer siliceous shell of the Earth which is about 35 km thick.
Metallic ores and other mineral products are produced from this crust. Therefore, the original
source of all metals is the Earths crust.
Average analysis of the Earths crust is given in Table 1. As it can be seen from the
table that oxygen, silicon, aluminum and iron are the four most abundant elements.
Since engineering metals Al, Fe, Mg and Ti are far more abundant than the other
metals. There is never likely shortage of these due to exhaustion of the ore deposits.
The commonly known metals, e.g. Au, Pb, Sn are so small in quantities in the Earths
crust that their commercial recovery is impossible. But, by natural events, those are
concentrated in certain parts of the Earths crust resulting in their economical recovery.
Ore deposits are metal-bearing veins, beds, placer deposits and solutions, which are
used to extract, metal commercially. Geological processes result in the concentration of
metals in ore deposits.

Table 1
Composition of the Earths Crust
Element % Element % Element %
O 46.66 Ti 0.44 Zn 0.0080
Si 27.72 H 0.13 W 0.0069
Al 8.13 Mn 0.10 Li 0.0065
Fe 5.00 P 0.08 Ce 0.0046
Ca 3.63 F 0.08 Sn 0.0040
Na 2.89 S 0.052 Y 0.0028
K 2.59 Cl 0.048 Nb 0.0024
Mg 2.09 C 0.032 Nd 0.0024
- - Rb 0.031 Co 0.0023
- - Ba 0.025 La 0.0018
- - Zr 0.022 Pb 0.0016
- - Cr 0.020 Cf 0.0015
- - Sr 0.015 Th 0.0011
- - V 0.015 - -
- - Ni 0.010 - -
- - Cu 0.010 - -
TOTAL 98.65 TOTAL 1.110 TOTAL 0.0459

Less than 0.001 % (Cs, Ge, Be, As, U, Mo, Ta, Sb, etc.)
Less than 0.0001 % (Hg, Tl, Bi, Cd, Ag, In, Se, Pd, Pt, Au, etc)
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1.1.1. Further Definitions

Ore is naturally occurring aggregate of minerals from which a metal or metals may be
extracted at a profit.
Mineral is a naturally occurring homogeneous inorganic substance of definite
chemical composition and with certain characteristic physical properties; e.g. galena PbS,
chalcopyrite CuFeS
2
.
Ore minerals are those minerals that contain the valuable metals in an ore; e.g. PbS,
CuFeS
2
, ZnSetc.
Sulfide ores are ores that contain sulfides, e.g. non-ferrous ore minerals such as PbS,
CuFeS
2
, and ZnSetc.
Oxide or Oxidized ores contain oxide, carbonate, sulfate, hydroxide or silicate ore
minerals; e.g. Fe
2
O
3
, PbCO
3
, FeCO
3
, PbSO
4
, Zn
2
(OH)
2
.SiO
3
etc.
Gangue minerals are the valueless minerals found in ores, e.g. waste wall rock broken
with ore. In a typical Pb Zn ore, we have: galena (PbS-ore mineral), sphalerite (ZnS-ore
mineral) and quartz (SiO
2
-gangue mineral).
Tenor (grade) of an ore is the amount of valuable metal in the ore. This is given in
percentage of metal or metallic oxide, except in precious metal ores; e.g. Au, Ag and Pt where
the analysis is reported in gms / metric ton or troy ounces / short ton. (1 troy ounce = 31
grams, 1 short ton = 2000 lbs or 907 kg)
Placer or placer deposits are ore deposits formed by the erosion of rocks by the action
of wind and water. Rocks are broken down both chemically and mechanically, and the action
of water tends to concentrate some of the minerals, e.g. native Au, Pt and cassiterite (SnO
2
)
Ferrous and non-ferrous ore: Ferrous ores are ores used in ferrous metallurgy; the
metallurgy of iron and steel. Non-ferrous ores are used in the technologies of all metals other
than iron.
Alloys: An alloy is a substance, with metallic properties, that contains more than one
element, e.g. brass is an alloy of copper and zinc; steel is an alloy of iron and carbon (C 2%).

1.1.2. Minerals and Ores of Common and Precious Metals

Iron ores
Ore minerals of iron are hematite (Fe
2
O
3
), magnetite (Fe
3
O
4
), limonite (Fe
2
O
3
.xH
2
O)
and siderite (FeCO
3
). Magnetite is a magnetic mineral. Hematite is the most important ore
mineral of iron and it is weakly magnetic. Since siderite and limonite are ore minerals lower
in grade than others, they are not so desirable in iron ores. Pyrite (FeS
2
) may be used after
roasting as pyrite cinder (iron oxide ash) for the production of iron.
Ores: Most iron ores contain large amounts of the iron ore mineral and relatively small
amounts of gangue. Most of the direct-smelting ores contain about 50 % Fe, although ores
with as low as 25-30 % Fe are smelted after concentration.

Aluminum ores
Ore minerals of aluminum are gibbsite (Al
2
O
3
.3H
2
O), diaspore (Al
2
O
3
.H
2
O), boehmite
(Al
2
O
3
.H
2
O), corundum (Al
2
O
3
), kaolinite (Al
2
O
3
.2.SiO
2
.2H
2
O), etc.
Ores: The only commercial ore of aluminum is bauxite. Bauxite is a rock containing
the hydrated oxides of aluminum; gibbsite, diaspore and boehmite (Al
2
O
3
.xH
2
O). Bauxites
contain 55 61 % Al
2
O
3
, 10 30 % combined water, 1 25 % Fe
2
O
3
, 1 3 TiO
2
and 1 12
% SiO
2
. Bauxites with low SiO
2
are desirable.


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Copper ores
Most important ore minerals of copper are chalcopyrite (CuFeS
2
), bornite (Cu
5
FeS
4
),
chalcocite (Cu
2
S), covellite (CuS), enargite (CuAsS
4
), malachite (CuCO
3
.Cu(OH)
2
), cuprite
(Cu
2
O) and chrysocolla (CuSiO
3
.2H
2
O).
Ores: The primary ore mineral in copper ores is chalcopyrite. Others are secondary
minerals formed by the alteration of primary chalcopyrite and chalcocite. Sulfide ores in
nature are usually associated with pyrite (FeS
2
) or pyrrhotite (Fe
1-x
S) and other base metal
sulfides such as ZnS, PbS, NiS, etc. The ore minerals are usually associated with siliceous and
other gangue minerals. Therefore, the grade of ore is reduced to 1 2 % Cu.

Lead ores
The only important lead ore mineral is galena (PbS). Anglesite (PbSO
4
) and cerussite
(PbCO
3
) are found in the upper portions of some lead ore deposits but they are not important
commercially.
Most lead ores are found as veins, so are not suited to bulk mining methods. As a
result, the average grade of lead ore mined is higher than that of copper ore; in the range 3.0
to 8.0 % Pb and associated with zinc and silver.

Zinc ores
Sphalerite (ZnS) is the only important zinc mineral and usually associated with PbS or
CuFeS
2
and cadmium. Smithsonite (ZnCO
3
) and calamine (Zn
2
(OH)
2
.SiO
3
) often occur in the
oxidized portions of sphalerite ore bodies. Grade of zinc sulfide ores: 2 12 % Zn.

The precious metal ores
Gold, silver and platinum metals most commonly occur as native metals. They are in
the metallic state but they are usually alloys rather than pure metals. In a few cases, gold
occurs as calaverite (AuTe
2
). Besides native silver, other important ore minerals of silver are
argentite (Ag
2
S), pyrargyrite (Ag
3
SbS
3
), etc.
Gold, silver and platinum are usually associated with base-metal sulfides and pyrite.

Chromium ores
The economical mineral in chromium ore is chromite (FeO.Cr
2
O
3
). Commercial
chromium ores usually contain 40 % Cr
2
O
3
or more.

















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1.2. MINERAL DRESSING

The first process most ores undergo after they leave the mine is mineral dressing
(processing), also called ore preparation, milling, and ore dressing or ore beneficiation. Ore
dressing is a process of mechanically separating the grains of ore minerals from the gangue
minerals, to produce a concentrate (enriched portion) containing most of the ore minerals and
a tailing (discard) containing the bulk of the gangue minerals.

Since most ore minerals are usually finely disseminated and intimately associated with
gangue minerals, the various minerals must be broken apart (freed) or liberated before they
can be collected in separate products. Therefore, the first part in any ore dressing process will
involve the crushing and grinding (which is also known by a common name called
comminution) of the ore to a point where each mineral grain is practically free.

1.2.1. Comminution

Crushing and grinding are usually carried out in a sequence of operations by which the
lump size is reduced step by step. There are 3 stages of crushing and 2 stages of grinding.

i. Primary Crushing (coarse crushing): In primary crushing, ore or run-of-mine
ore (up to 1 m in size) is crushed down to about 10 cm and it is done in a jaw
or gyratory crusher.
ii. Secondary Crushing (intermediate crushing): In this case, ore is crushed from
10 cm to less than 1 2 cm size; for this purpose jaw, cone or roll crushers are
used. These secondary crushers consume more power than primary crushers.
iii. Tertiary Crushing (fine crushing): By tertiary crushers ore is crushed from
1 2 cm to less than 0.5 cm. Short head cone crushers, roll crushers, hammer
mills can be used for this purpose.

The two stages of grinding are:
i. Coarse Grinding: Rod mills are generally used as coarse grinding machines.
They are capable of taking feed as large as 50 mm and making a product as
fine as 300 microns.
ii. Fine Grinding: Fine grinding, which is the final stage of comminution, is
performed in ball mills using steel balls as the grinding medium. The ball mill,
after feeding 0.5 mm material may give a product that is less than 100 microns.
Grinding is usually done wet.

The principle purposes of grinding are:
i. To obtain the correct degree of liberation in mineral processing.
ii. To increase the specific surface area of the valuable minerals for
hydrometallurgical treatment; i.e. leaching.

Mineral processing combines a series of distinct unit operations. The flowsheet shows
diagrammatically the sequence of unit operations in the plant.





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A simple flowsheet of a mineral processing plant

Ore


Crushers
(+) Oversize

Screens
(-) Undersize

Grinding
(+) Oversize

Classification
(-) Undersize

Concentration

Concentrate Tailing

Comminution and concentration are two primary operations in mineral processing as it
can be seen from the above flowsheet, but many other important steps are involved.
e.g. Sizing by screens and classifiers.
Dewatering by thickeners, filters and driers, etc.
Auxiliary operations conveying, sampling, etc.

1.2.2. Sizing Methods

There are two methods of industrial sizing.
i. Screening
ii. Classification

Screening is generally carried out on relatively coarse material, as the efficiency
decreases rapidly with fineness. Screening is generally limited to materials above about 250
microns in size, finer sizing normally being undertaken by classification.

Industrial sizing is used in closed circuit with a crusher or a ball mill. For the large
lump sizes coarse grizzlies made of rails or trommel (revolving) screens made of punched
plate may be used. For finer material, screens are usually made of woven metal wire.
The material that passes through the openings (apertures) of a particular screen is
known as the undersize and material that remains on the screen is the oversize.

Laboratory screening: The other use of screening is as a measuring technique with the
purpose of determining the relative amounts of various particle sizes in a given material. The
particle size distribution of crushed or ground ore is determined by means of a screen
analysis. For this purpose standardized screening scales are developed. Most common is the
American Tyler Screen Scale (Tyler Standard Series) where the screen number(mesh number)
is given as the number of meshes (openings) or wires per linear inch (1 inch=2.54 cm): the
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diagonal of each screen opening is equal to the edge of the previous screen. So, the linear
dimension of each opening differs by a constant factor of 2 = 1.414.
Tyler screen scale starts with 1.05 inch (26.67 mm), for smaller particle sizes the
dimensions are usually given in microns (1 micron = 10
-3
mm). Thus, 200 mesh (#) is equal to
74 microns in the Tyler Screen Series, Table 2.
The result of a screen analysis is given as the fraction of the sample which passes
through one screen but which is stopped by the subsequent screen so we can say that a certain
percentage is + 26.67 mm (coarser than the coarsest screen), another percentage is 20 mesh
+ 28 mesh (dimensions between 0.833 mm and 0.589 mm) and finally that a certain
percentage is 200 mesh (finer than 0.074 mm or 74 microns). The mesh number does not
directly indicate the size of the aperture, and the aperture can be calculated from the mesh
number if the wire diameter is known.
1 inch (25.4 mm) = Number of wires * Wire diameter + Number of apertures * Aperture size

Table 2
The Tyler Standard Series for Screen Analysis
Aperture Size Tyler Mesh #
Millimeters Microns
26.67 - -
18.85 - -
13.33 - -
9.423 - -
6.680 - 3
4.699 - 4
3.327 - 6
2.362 - 8
1.651 - 10
1.168 - 14
0.833 833 20
0.589 589 28
0.417 417 35
0.295 295 48
0.208 208 65
0.147 147 100
0.104 104 150
0.074 74 200
0.052 52 270


2




s
e
r
i
e
s

0.037 37 400


Classification: Classification is defined as a method of separating mixtures of mineral
particles into two or more products according to their settling velocities in water, in air or in
other fluids as given in below figure. Industrial classification may be carried out in different
types of classifiers and these classifiers are; hydraulic classifiers, mechanical classifiers and
cyclones. Basically they all work according to the principle that the particles are suspended in
water which has a slight upward movement relative to the particles. Particles below a certain
size and density are carried away with the water-flow, whereas the coarser and heavier
particles will settle.
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In classification mostly we use wet cyclones (hydrocyclones) in which rapid spinning
of the pulp centrifuges the solid particles.


Feed
Overflow (particles with
terminal velocities < V)








Fluid Velocity, V

Spigot Product
(particles with terminal velocities > V)

1.2.3. Concentration

The second fundamental (main) operation in mineral processing, after the release, or
liberation, of the valuable minerals from the gangue minerals, is the separation of these values
from the gangue, i.e. concentration.
Concentration is usually accomplished by utilizing some specific difference in
physical (or chemical) properties of the metal and gangue compound in the ore.
In concentration the following terms are used:
Head is the feed to a concentrating system.
Concentrate is defined as the valuable mineral(s) separated from ore undergoing a
specific treatment.
Tailing is the fraction of ore rejected in a separating process. It is usually the valueless
portion, i.e. discard or waste.
Middlings are the particles of locked valuable mineral and gangue, i.e. liberation has
not been attained. Further liberation can be achieved by further comminution.
Recovery is the percentage of the total metal, contained in the ore that is recovered in
the concentrate.

Physical Concentration Methods

1. Separation dependent on optical and radioactive properties of minerals, i.e.
hand pickling, optical sorting, radioactive sorting, etc.
2. Separation dependent on specific gravity (density) difference of minerals, i.e.
heavy-media separation, gravity concentration by use of tables, jigs, cones, etc.
3. Separation utilizing the different surface properties (i.e. surface chemistry) of
the minerals, i.e. froth flotation, etc.
4. Separation dependent on magnetic properties of the minerals, i.e. low and high,
dry and wet magnetic separation, etc.
5. Separation dependent on electrical conductivity properties of the minerals, i.e.
electrostatic separation, etc.

So mineral processing is concerned mainly with the physical methods of separation of
minerals. Pyrometallurgy and hydrometallurgy may also deal with raw materials but those
processes change the character of some or all of the constituents of the raw materials.
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1.3. PRETREATMENT PROCESSES

Minerals recovered from ores are not always in the optimum chemical or physical
state for conversion to metals. Oxides are more conveniently reduced to metals than sulfides,
or the metal might be more readily leached from the ore if it were present as a sulfate, a
chloride, or an oxide. Chemical conversion to the desired species often is an integral segment
of the extractive process. Sulfide ores or concentrates, for example, usually are heated in an
oxidized atmosphere (roasted) to convert them to an oxide or sulfate.
The physical state of an ore may be too fine for charging to a process. Fine ores often
are agglomerated by sintering prior to charging to a blast furnace, the principal smelting unit
for lead and iron. In the case of iron ore, pelletizing is another very important agglomeration
process that has achieved commercial adaptation in the iron and steel industry.
In the sections below, the following pretreatment processes will be explained:
i. Drying
ii. Calcination
iii. Roasting
iv. Agglomeration

1.3.1. Drying
Drying usually means the removal of mechanically held water or moisture from
concentrate, or other solid materials by evaporation, i.e. expensive operation, usually done in
a drying furnace (fixed or fluidized bed, or kiln) and usually accomplished by passing hot
combustion gases through or above the substance.
Drying may be accomplished either at atmospheric pressure by heating the substance
above the normal boiling point of water, or, under reduced pressure where the atmospheric
pressure is brought below the vapor pressure of water at the temperature in question.

H
2
O
(l)
H
2
O
(g)
H
298
o
K
= +10.5 Kcal / gram-mole (Endothermic process)

Therefore, in addition to the heat needed to bring the substance to the drying
temperature, the heat of evaporation must be supplied at that temperature.

Moisture Determination
Take a grab sample weighing 100 to 1000 grams or more (It should include
representative portions from the top, bottom and center of the car of ore or concentrate)

Sample

Weigh the Sample

Put into Drying Oven

Dry @ 105C

Weigh again

Determine the Loss in Weight

Calculate % Moisture
% Moisture = {(wet weight - dry weight) / wet weight} * 100
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1.3.2. Calcination
Calcination is the thermal treatment of an ore or a concentrate to effect its
decomposition and the elimination of a volatile product, usually CO
2
, water vapor, or other
gases.
Therefore, by contrast with drying, calcination involves the removal of H
2
O, CO
2
, etc.,
which are chemically bound as e.g. hydrates or carbonates.

Lost Lost


Material Free water Chemically bound H
2
O,CO
2
Completely dehydrated
and calcined material

Drying Calcination

Increasing Temperature

T
calcination
>> T
drying

Temperature necessary for the decomposition pressure to reach 1 atm varies.
e.g. FeCO
3
and Mg(OH)
2
; T 200C
MnCO
3
, MgCO
3
; T 400C
CaCO
3
; T 900C
BaCO
3
and Na
2
CO
3
; T 1000C

Examples of calcination reactions:
i. CaCO
3
CaO + CO
2
H
298
o
K
= +42.5 kcal/gram-mole T 900
o
C

This calcination reaction is endothermic. It is more endothermic than drying.

ii. MgCO
3
MgO + CO
2
@ about 1700 1800C

MgO produced is called periclase. It is a stable crystalline structure
(with no hydration or shrinkage), used as a refractory

iii. 2Al(OH)
3
Al
2
O
3
+ 3H
2
O @ about 1000C chemically combined water is driven
off.
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1.3.2.1.Calcination Furnaces
Shaft furnace For the calcination of coarse limestone
Rotary kiln For the calcination of materials with mixed particle size or lumps which
disintegrate during the process
Fluidized bed For materials of uniform, small particle size
Fuels used in calcination furnaces are gas, oil, coke, pulverized coal, etc.


Temperature of gas and solids during calcination of limestone in a coke-fired shaft furnace,
i.e. temperature profiles

1.3.3. Roasting
General Definition: Roasting is the oxidation of metal sulfides to give metal oxides
and sulfur dioxide.
Typical examples are:
2ZnS + 3O
2
= 2ZnO + 2SO
2
, H
298
o
K
= -220 Kcal/gm-mole Strongly Exothermic
2FeS
2
+ 11/2O
2
= Fe
2
O
3
+ 4SO
2
, H
298
o
K
= -410 Kcal/gm-mole Reactions


Product ( calcine )

In addition other reactions may take place:
SO
2
+ O
2
= SO
3
Formation of SO
3
2PbS + 4O
2
= 2PbSO
4
Formation of metal sulfates
or
2PbO + 2SO
2
+ O
2
= 2PbSO
4
Formation of metal sulfates
ZnO + Fe
2
O
3
= ZnFe
2
O
4
Formation of ferrites (complex oxides)
Typical ores or concentrates, which are roasted, are the sulfides of Cu, Zn and Pb. In
these cases, the main purpose is to convert the metal sulfides, partly or completely, into
oxides for subsequent treatment. SO
2
is then a by-product. But for pyrite roasting;
2FeS
2
+ 11/2O
2
= Fe
2
O
3
(pyrite cinder) + 4SO
2

Fe
2
O
3
is the by-product while SO
2
gas is the main product.
12
1.3.3.1.Temperature of Roasting
T
roast
> 500 - 600C: in order for the reactions to occur with sufficient velocity.
T
roast
< 1000C: roasting is usually carried out below the melting points of the
sulfides and oxides involved and to avoid ferrite formation.

Dead roast or sweet roast: Roasting to completion with the elimination of most of the
sulfur by overall reaction.

Partial roasting: Removal of some of the sulfur by roasting.
e.g. partial roasting of copper concentrates
CuFeS
2
+ 4O
2
= CuSO
4
+ FeSO
4
2CuS + 7/2O
2
= CuO.CuSO
4
+ SO
2

1.3.3.2.Types of Roasting
1. Oxidizing roast
2. Volatilizing roast
3. Chloridizing roast
4. Sulfating roast
5. Magnetizing roast
6. Carburizing roast
7. Sinter or Blast roasting

1.3.3.3.Types of Furnaces for Roasting
Development sequence:
Stationary heaps - old days
Hand rabbled furnaces - later development
Multiple hearth furnaces - long time used for roasting
Flash or Suspension roasting furnaces
Fluidized bed roasting furnaces
Others:
Blast roasting or sinter roasting, roasting in a rotary kiln, etc.
Fluidized bed roasting became the dominant technique for roasting FeS
2
(pyrite),
sulfides of Cu, Zn, Co, Ni, etc. in recent years. It is very efficient and close control is
possible.

1.3.4. Agglomeration
When the particle size of an ore or concentrate is too small for use in a later stage of
treatment, i.e. in the blast furnace, it must be reformed into lumps of appropriate size and
strength that is agglomerated. Agglomeration is used particularly if the ore is to be smelted in
a shaft furnace where fine-grained material would plug up the gas passage, i.e. decrease gas
permeability.

Types of agglomeration
i. Sintering
ii. Pelletizing
iii. Briquetting
iv. Nodulizing

Below sintering and pelletizing of iron ores or concentrates are explained.

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1.3.4.1. Sintering
Sintering may be defined as a process in which relatively coarse materials, e.g. for
iron ore concentrate 8mm + 0.15mm (100 mesh), are converted into coarse agglomerates by
partial melting and fusion. The sinter product has a porous structure.
Sintering is generally done by the use of a Dwight Lloyd sintering machine.
Sectional-view of a Dwight Lloyd sintering machine is given below.

1.3.4.2. Pelletizing
Pellets are made by rolling critically moist finely divided material around in a drum or
in a rotating inclined disc. Below pelletizing of iron ore concentrate is explained.


i.e. Iron ore concentrate: Particle size 70 % - 325 mesh (44 microns) with
specific surface area, i.e. Blaine Number 1600 2200 cm
2
/gram
Bentonite (i.e. clay): Binder
Flux : Calcium oxide powder (to control basicity)
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After the production of green pellets, they are dried and fired at 1200 - 1375C,
i.e. induration, in order to obtain fired pellets of sufficient strength.
For hardening of green pellets, the following pellet firing processes or furnaces are
available:
i. Shaft furnace
ii. Grate-Kiln machine
iii. Travelling grate (similar to Dwight-Lloyd)
iv. Grate-rotary hearth-shaft furnace
Pelletizing is well suited for very fine grained concentrates which are not easily
sintered on the grate. Pelletizing of chromium concentrates, copper concentrates, etc, are also
being done.

15
1.4. METAL EXTRACTION PROCESSES

Following the mining, mineral processing and pretreatment of minerals, their
extraction is accomplished by application of chemical metallurgy in one of the three areas of
extractive metallurgy: Pyrometallurgy, hydrometallurgy or electrometallurgy.

1.4.1.Pyrometallurgical Extraction Processes
Pyrometallurgy deals with chemical reactions at high temperatures. These are
reactions that take place at temperatures from 100C up to 3000C or more. Pyrometallurgy
or fire metallurgy is the most important of the extraction processes and it is the oldest division
of metallurgy. Practically all iron and steel, lead, and tin, most copper, and a small proportion
of zinc, etc. are won from their ores and concentrates by pyrometallurgical methods.
Pyrometallurgical reactions involve a number of different solids, liquids and gases
and, take place in a variety of furnaces, converters, roasters and other devices. The most
important pyrometallurgical extraction processes are as follows:
i. Roasting agglomeration calcination and drying (these are pretreatment
processes that are pyrometallurgical in nature.)
ii. Smelting - Matte smelting (Cu and Ni, etc.)
- Smelting for metal (Fe, Pb, etc.)
iii. Converting (Cu, Ni, etc.)
iv. Reduction of oxides, etc. (Direct reduction of iron ore, zinc ore, etc.)
v. Refining (Cu, Pb, etc.)
vi. Distillation (Zn, Hg, etc.)
vii. Halide metallurgy

1.4.1.1. Smelting
Smelting is mainly a process of melting and separation of the charge into two
immiscible liquid layers, i.e. a liquid slag and a liquid matte or a liquid metal. There are two
types of smelting: Smelting for matte and smelting for metal.
Under Neutral or Reducing Conditions

Slag e.g. SiO
2
, CaO, Al
2
O
3
, etc
Metal sulphides Matte Smelting
e.g. Cu concentrate Matte e.g. Cu
2
S, FeS, etc
20-30% Cu 30-55% Cu
Matte can be defined as molten mixture of sulphides of heavy metals. Liquid slag is
the siliceous or oxidized part of the concentrate.
Matte smelting is done in one of the following furnaces: (Diagrams given below)
- Reverberatory furnace (for fine concentrates)
- Flash furnace (for fine concentrates)
- Blast furnace (for lumpy ore or agglomerated concentrates)
- Electric furnace (for fine concentrates)
Matte smelting is therefore a pyrometallurgical concentrating stage in the overall
extraction of a metal from its sulphides.
Fluxes (Under Reducing Conditions)

Liquid slag e.g. SiO
2
, CaO, Al
2
O
3
Metal oxides Smelting for Metal etc
(ore or concentrates) Liquid metal e.g. Pig iron
e.g. Fe
2
O
3
, Fe
3
O
4
Reducing agent (coal, coke, etc.) Fe+4%C+1%Si, etc
16





17

Liquid slag contains the gangue minerals and fluxes. It removes the impurities. Liquid
metal, such as pig iron, is an alloy of iron containing C, Si, Mn, etc. Smelting for metal is
done in blast, reverberatory and electric furnaces. Metal oxide smelting is an important
extraction process producing an impure metal which must be subsequently (fire) refined.

T
matte smelting
< T
metal oxide smelting

1.4.1.2. Converting
Flux Horizontal converter, e.g. Pierce-Smith
Converter
Matte air and/or oxygen Liquid matte
Converting blowing (sulphide matte) e.g. Cu
2
S - FeS

Preferential oxidation of the more reactive impurity metal sulphides, e.g. FeS
FeO. Air blowing is controlled to convert the remaining more noble metal sulphide to the
required metal, e.g. Cu
2
S Cu (blister copper)
Cu
2
S + 3/2O
2
Cu
2
O + SO
2
i. 2MeS + 3O
2
2MeO + 2SO
2
FeS + Cu
2
O FeO + Cu
2
S
FeS + 3/2O
2
FeO + SO
2

Cu
2
S + 3/2O
2
Cu
2
O + SO
2
ii. MS + 2MO 3M + SO
2
Cu
2
S + 2Cu
2
O 6Cu + SO
2
Cu
2
S + O
2
2Cu + SO
2
Cutaway view of a horizontal side-blown Pierce-Smith converter is given below.


18


1.4.1.3. Reduction of Metal Oxides
Metal oxides Reduction Metal

Reduction is by C, CO, H
2
or other metals (metallothermic reduction)
e.g. 3MO + 2Al 3M + Al
2
O
3
2MO + Si 2M + SiO
2
G - T diagram can be used to assess the various reducing agents:
2MO
(s)
+ C
(s)
2M
(s)
+ CO
2(g)
below 650C
MO
(s)
+ C
(s)
M
(s)
+ CO
(g)
above 650C
e.g. Fe, Mn, Cr, Sn, Pb and Zn are the main metal oxides reduced with carbon.

If T
reduction
>1800C cost of reduction increases substantially due to;
- Refractory problems
- Reactivity of the produced metal with its environment.

1.4.1.4. Refining
Fire Refining
Air and/or O
2(g)
blowing
+
Poling (Introduction of hydrocarbons CH
4
, woodetc)

Impure metal from Fire refining slag
sulphide matte smelting preferential oxidation of
and converting impurity elements SO
2(g)
e.g blister copper
Fire refined metal
(98.5 % Cu, 0.02 0.1 % S) e.g. fire refined copper
0.5 0.8 % O (99.5 % Cu, 0.001 0.003 % S)
0.05 0.2 % O

Steelmaking is also a typical refining process; impurities in pig iron are lowered to
acceptable levels.
Flux Air and/or oxygen
blowing
Impure metal from
metal oxide smelting Steelmaking Slag
e.g. pig iron
(Fe, 4%C, 1%Si, 1% Mn, etc.) Steel (Fe, 0.3%C, 0.001%Si, 0.3% Mn )

19
1.4.1.5. Distillation

Low boiling point (Bpt) metals can be separated and refined from higher boiling point
metals by distillation, i.e. evaporation and subsequent condensation to the pure metal due to
their difference in vapour pressures.

M
(l)
M
(g)
The metals that may be refined by distillation are mainly limited to those with boiling
point less than 1000C. Use of vacuum distillation extends the range of metals that can be
refined.
Separate recovery of vapour
Liquid mixture Distillation
Residue

Partial Vaporization

e.g. Extractive metallurgy of zinc and mercury (Hg
bpt
: 357C)
Removal of As (arsenic) from (iron ores) liquid iron (fractional distillation)
Vacuum dezincing (Zn
bpt
: 907C) of desilverized lead bullion (Pb
bpt
:1740C)

1.4.1.6. Halide Metallurgy

By using halogens (Cl, Br, F, I) metal halides (chlorides, iodides, fluorides, bromides)
are formed.

Zircon Chloridizing ZrCl
2
Reduced with Mg Zirconium
ZrSiO
4
roasting (Kroll Process @ 800 - 1000C) metal

or some volatile metal halides are produced, e.g. SnCl
4
, TiCl
4
, AlCl
3
some metal halides have low decomposition temp. ZrI
4
Zr + 2I
2
, @ 1400C
Therefore, it is possible to separate certain metal halides and to purify by distillation.


1.4.2. Hydrometallurgy (Water Metallurgy)

1
st
definiton: Hydrometallurgy is concerned with the leaching of ores, concentrates
and calcines with aqueous solutions to dissolve and recover the valuable metals.

2
nd
definiton: The separation of a soluble substance from an insoluble by means of a
solvent. The solvent is either water or an aqueous solution.

Essential steps i. Leaching or lixivation (dissolving of metal)
ii. Recovery of metal from pregnant leach solution

Auxiliary step Separation of pregnant solution from the leach residue.

1.4.2.1. Advantages

- High extraction of the value metal
- Requires very little fuel
20
- Equipment needed is relatively simple and inexpensive
Principle expense is the cost of the necessary chemical reagents. In some
processes the solvent is regenerated
- Suited to the treatment of low-grade ores as well as concentrates
e.g. gold ores, zinc concentrates, Al
2
O
3
extraction by the Bayer process, etc.
- Less environmental problems.
BUT
- Many materials will not respond to treatment by leaching methods.

Water & Solvents


Crushing Sands (coarse) Percolation leaching Separation Metal
Ore & -6mm of solution recovery
Grinding Slimes (v.fine) Agitation leach and residue from
solution


Preliminary Treatment

- Sometimes unnecessary i.e. direct leaching
- Sometimes concentration and roasting

1.4.2.2. Solvents
Requirements
i. It must dissolve the ore minerals rapidly enough to make commercial
extraction possible, and it should not attack the gangue minerals.
ii. It must be cheap and readily available in large quantities.
iii. If possible, it should be regenerated.

Some solvents
i. Water e.g. CuSO
4
, ZnSO
4
leaching (most sulfates are water soluble)
ii. Acids e.g. Dilute H
2
SO
4
for oxidized Cu and Zn ore CuSO
4
, ZnSO
4

ZnO + H
2
SO
4
ZnSO
4
+ H
2
O
iii. Bases e.g. NH
4
OH+oxygen, or NH
4
CO
3
+NH
4
OH for leaching CuCO
3
NaOH for leaching bauxite Al
2
O
3
+ 2NaOH 2NaAlO
2
+ H
2
O
iv. Salts e.g. NaCN or KCN dissolves Au and Ag
4Au (or Ag) + 8NaCN + O
2
+ 2H
2
O 4NaAu(CN)
2
+ 4NaOH
v. Bacterial (Thio Bacillus Thiooxidans or Thio Bacillus Ferrooxidans)
leaching e.g. FeSO
4
Fe
2
(SO
4
)
3
(using Thio Bacillus Ferrooxidans)
FeS
2
+ Fe
2
(SO
4
)
3
3FeSO
4
+ 2S

1.4.2.3. Leaching Methods (Continuous, batch) (Referring to diagrams below)

i. In place (in situ) e.g. mine water for leaching CuSO
4

ii. Heap leaching (-8 inch or 20cm ore), Dump leaching
iii. Sand (Percolation) leaching (-1/4 inch or -6mm ore) in large vats or tanks
iv. Agitative (Slime) leaching is done by agitation of fine solids in steel tanks or
Pachuca tanks (either mechanically or with compressed air)
v. Pressure leaching in autoclaves
21





22
1.4.2.4. Solid-Liquid Separation

Separation of pregnant leach solution and leach residue (S/L) is by decantation or
thickening followed by filtration. A continuous method of leaching and separation of the
enriched solution from the gangue is by continuous countercurrent decantation (CCD) where
several thickeners are often used. CCD as used after cyanidation of gold and silver ores is
shown in below flowsheet. With the use of CCD, the pregnant leach solution (L) is separated
from the leach residue (S), at the same time the leach residue is washed with wash water so
that no pregnant leach solution is lost with the leach residue.


1.4.2.5. Recovery of Metal from Solution

Recovery of metals from pregnant leach solution is done by precipitation (Ppt),
electrowinning (EW), solvent extraction (SX), ion exchange (IX), cementation, gaseous
reduction, etc.

Cementation: Cu
++
+ Fe Cu + Fe
++
Cu is displaced from aqueous solution by
metallic iron

scrap iron sponge type finely

divided cement copper

Cd
++
+ Zn Cd + Zn
++
Cadmium cementation.

Cadmium sponge

Electrochemical Series (25C, 1 N solution) volts
Li / Li
+
+ 3.095 Cr +0.744 Pb +0.126
K +2.925 Fe/Fe
2+
+0.440 H
2
/H
+
0.000
Na +2.714 Cd +0.403 Cu / Cu
2+
- 0.337
Mg +2.363 Co +0.277 Hg -0.788
Al +1.662 Ni +0.250 Ag -0.799
Zn +0.763 Sn +0.136 Au - 1.680
The metal with the more positive
(oxidation) potential will pass
into the solution and displace a
metal with a less positive
potential.
23
v
Gaseous Reduction:
alency=n
M
n+
+ n/2 H
2
M
o
+ nH
+
@ elevated T over 100C and P.
(Ni + H
2
Ni + 2H )
recipitation

(or CO, SO
2
, H
2
S,etc.)
++ +
e.g. Co, Ni, etc.

P : Zn
(zinc dust)
+ 2NaAu(CN)
2
Na
2
Zn(CN)
4
+ 2Au
(without reduction)

aAlO
2
Al(OH)
3
Solvent Extraction (SX):
precipitate
N
2
+ 2H O + NaOH (Hydrolysis reaction)

Liquid liquid extraction (liquid ion exchange) LIX

ixing

e in leac capable arat
xtract n in v rious phosphoricacid
contact with leach solution containing uranium
1g/l U
3
O
8

ranium Cr hing Leaching CD rganic
A
idue
rganic
ted organic
DU)
(For solution concentration or purification purposes)
Aqueous solution + organic m for SX
(pregnant solution)
(insolubl hing solution, of sep ing
from leach solution, must be highly selective)
E io a organic Di(2-ethylhexyl)
(DEHPA)+kerosene
types of mixing units
(stirred tanks, columns, etc.)


U us C pregnant solution o
ore & grinding with H
2
SO
4
DEHP
Leach res mixer settler raffinate

(SX)
6 g/l U
3
O
8
loaded o
HCl stripping regenera
100g/l U
3
O
8
(after stripping)
NH
3
ppt

(NH
4
)
2
U
2
O
7
(A


Ion Exchange (IX): Generally used for low grade uranium ore processing, water
e.g. Water Softening
ater inate-silicate) removes Ca/Mg from water softened water
.g. IX of Uranium
synthetic resin IX
. Amberlite IRA 425, Dowex 11, etc.)
softening, processing of rare-earth metals, etc.


W Zeolite (sodium alum
IX resin by exchange with Na

e
pregnant solution +
(with uranium) (organic polymers, e.g
24

Reaction: Anionic exchange
R
4
(UO)
2
(SO
4
)
3
+ 4X
-
eg ive ion
Elution
UO
2
(SO4)
3
-4

+ 4 RX
(complex anion)

resin n at

with
t NaCl, HCl eluen
H
2
SO
Uranium CCD ed
4

crushing leaching IX columns load solution metal
ore grinding resin (eluate) recovery
leach effluent
residue to waste rege nerated resin
gy

1.4.3. Electrometallur
Electrometallurgy deals with metallurgical processes that require electric current for
chemic
Electrolytic refining (e.g. Cu, Fe, Co, Pb, Zn, etc)
Fused salt electrolysis (e.g. Al
2
O
3
, MgCl
2
etc)

ii. Electrowinning Recovery of metals from pregnant leach solution
elow electrowinning of copper, electrolytic refining of copper and fused salt

al reduction.

i. Electrolysis
( production of Na, Zr, Ti, K, Ca, etc )

(e.g. Cu, Au, Zn, Sb, etc)

B
electrolysis of alumina to obtain aluminum metal are explained as examples.




25




26
SUMMARY

General Classification of Ores for Leaching
Pregnant
Barren solution leach liquor
(Solvent)












Dissolution Communition and Sizing Mineral Dressing


Pretreatment (optional)

Separation
Dissolution Concentrate
Dump, Heap, Vat
Leaching
Pretreatment
(optional)
Separation Dissolution

e.g. Production of
Direct Leaching
Ore
In-Place Leaching

Mineral Deposit

Transported for Leaching
High Grade Ore
Suitable for
Beneficiation
Low Grade Ore
Not suitable for
Beneficiation
e.g. Cu dump leaching Uranium, Vanadium Separation
Leaching of waste products Gold, Silver
not economic to subject them Aluminum
to additional treatment. Nickel e.g. Production of
e.g. fine grinding, Beryllium Zn, Cu, Ni, Co, W
concentration, etc. Titanium Pt, Ti, Mn, Mo
Cobalt
27

Recovery of Metal from Solution
(Separation of metal)


Leach solution
(Solvent)




Cementation Hydrogen
Gold, copper Ni, Co, Cu
Cu
2+
+ Fe Cu + Fe
2+
M
2+
+ H
2
M + 2H
+









Uranium, copper As salts, sulfides
-Uranium (Na
2
U
2
O
7
)
Precipitation by
contact reduction
Ore or
concentrate
Precipitation
by reduction
Dilute process
stream
Concentrated
liquor
Solvent Extraction
Ion Exchange
Precipitation
without reduction
(as yellow cake)
Cu, Zn -Fe, Co, Cu, Ni
Electrowinning
as hydroxides
-Aluminum as Al(OH)
3
-Ppt of Mg, Be, etc.











28
1.5. FUELS and REFRACTORIES

Cost of energy is usually a high proportion of the total cost of the metal production;
therefore, energy should be used efficiently.
coal
natural gas
fuels (solid, liquid, gas) oil
Energy electricity (generated by fossil fuels, water or nuclear power)
For Smelting solar energy, etc
Reduction
Handling
Comminution Ore Metallurgical Metal(s)
Separation etc Processing


Refractories

1.5.1. Fuels
1.5.1.1. Definitions
A fuel is any substance (it may even be a metal) that may be burned rapidly enough so
that the heat resulting from the oxidation is capable of being applied to industrial operations.
Combustion is the term applied to the burning of fuel.
Incomplete combustion is a term applied to combustion in which not all the fuel is
burned (leaving unburned carbon in ashes for example).
Imperfect combustion means that not all the fuel is oxidized to its highest degree (if
CO is formed, for example instead of CO
2
).
Ignition temperature of fuel is the temperature at which combustion starts. This is not
definite and it depends upon the physical condition of the fuel and atmospheric pressure.
Ashes and cinders are the residue left after the fuel has burned.

1.5.1.2. Heat Producing Elements:
These are given by the order of importance as:

C, H, S, Si, Mn, Al, and P.

C is used in the elemental form (charcoal, coke), combined form (hydrocarbons) and
partly free, partly combined form (lignite and bituminous coals).
H occurs in its free state in some gaseous fuels, or combined as in hydrocarbons.
S is important in roasting and in matte converting as the fuel but is undesirable as an
impurity in the finished metals (for example in steel).
Fe
2
O
3
+SO
2
e.g. Used for
Sulphide Concentrate Roasting Heat Evolved steam production
e.g. FeS
2
(exothermic)
Sometimes enough heat evolved to sustain the process.
e.g. Autogenous roasting of FeS
2
, sintering of PbS, etc.
i.e. No carbonaceous fuel added.





29
1.5.1.3. Classification of Fuels
I-Solid Fuels
a. Natural
1. Wood
2. Peat (accumulation of compacted and partially devolatilized vegetable matter)
3. Lignite Coal
4. Bituminous Coal
5. Anthracite Coal
b. Prepared (Artificial)
1. Pulverized Coal
2. Briquetted (Compressed) Fuels
3. Carbonized (Distilled) Fuels
a) Charcoal
b) Coke

II-Liquid Fuels
a. Natural
Petroleum of Crude Oil
b. Prepared
1. Distilled Oils
2. Coal Tar
3. Residual Oils (Fuel Oil)

III-Gaseous Fuels
a. Natural
Natural Gas (CH
4
, C
2
H
6
, C
3
H
8
, ...)
b. Prepared
1. Coal (Coke-oven) Gas (H
2
, CH
4
, ....)
2. Oils Gas (H
2
, CH
4
, CO, ...)
3. Blast Furnace Gas (N
2
, CO, H
2
, CO
2
, ...)
4. Producer Gas
a) Water Gas (50%H
2
, 50%CO)
b) Air Gas (30%CO, remainder N
2
)
c) Mixture of the two

1.5.1.4. Choice of Fuels
Factors to be considered when selecting the right kind of fuel are:
1. Cost: Cheapest of suitable fuels will be used for the purpose.
2. Availability: The metallurgical plant must be at a location with an access to fuel
sources (coal mines or oil fields).
3. Suitibility for the process: For blast furnace for example only metallurgical coke
can be used. It has sufficient strenght, porosity, calorific value and it is low in ash,
S, etc. In hearth or reverberatory furnaces only pulverized coal, fuel oil or gas, all
yielding long flames will be required.
4. Purity: This refers to ash content, P and S in the fuel which all are undesirable.
Ash is non-combustible, decreases the calorific value and since its melting point is
high, to make it fluid during smelting, it has to be fluxed along with the impurities
in the ore or concentrate.
5. Calorific Value: Depends upon the carbon, hydrogen and ash contents of the fuel.
6. Calorific Intensity: This is the intensity attained by the combustion of the fuel.
30
1.5.2. Refractories

1.5.2.1. Definitions
Refractory materials or refractories are those materials that can withstand high
temperatures, corrosion from liquids and abrasion of hot gases laden with dust.
Acid refractory or acid oxide is one which will absorb oxygen ions when dissolved in
a basic melt:
SiO
2
+2O
2-
= SiO
4
4-
Basic refractory or basic oxide is one which will provide oxygen ions when dissolved
in a melt:
MgO= Mg
2+
+O
2-
Neutral refractory is a material that is attacked by neither acidic nor basic oxides and
is used to replace basic refractories where the corrosive action is strong.

1.5.2.2. Refractory Materials
The commercial refractories are based on either of the following substances:
1. Silica (SiO
2
)
2. Alumina (Al
2
O
3
)
3. Aluminosilicate (xAl
2
O
3
.ySiO
2
)
4. Lime (CaO)
5. Magnesia (MgO)
6. Forsterite(2MgO.SiO
2
)
7. Dolomite ( MgO.CaO)
8. Hematite (Fe
2
O
3
) or Magnetite (Fe
3
O
4
)
9. Chromite (FeO.Cr
2
O
3
)
10. Carbon (Graphite)
11. Metals (Water-cooled)
12. Carbides (Silicon carbide and others)

1.5.2.3. Melting Point of Refractories
Silica 1724C
Kaolin 1740 C (High Al
2
O
3
clay)
Bauxite Brick 1600-1820 C (High in Al
2
O
3
)
Alumina 2050 C (corundum)
Magnesia Brick 2165 C
Chromite 2050-2200

C
Silicon Carbide (beyond 2700

C)
Carbon solid at 3600

C
The softening points of refractories, not their melting points should be considered
when selecting a refractory for the lining of a furnace.

Temperatures Attained in some Metallurgical Process
Copper Smelting 1000- 1100

C
Zinc Retorts 1400- 1600 C
Bessemer Converter 1600

C
Oxygen Converter 1850

C
Tuyeres in Fe Blast Furnaces 1900

C
Electric Arc Temperature 3600

C
Electric Arc Furnace for Steelmaking 1800

C max
31
1.5.2.4. Classification of Refractories

I-Acid Refractories
a. Siliceous Materials
Consist of SiO
2
and are low in metallic oxides and alkalies (Na
2
O, K
2
O)
1. Natural Rock (Sandstone, Quartzite)
2. Quartzite Sand (Ganister)
3. Silica Brick

b. Aluminosilicates (xAl
2
O
3
.ySiO
2
)
All silica should be in a chemically combined form with alumina. Since any free silica
would lower the melting point.
1. Natural Rock
2. Prepared Mass (Fireclay)
3. Burned Brick (Firebrick)

II- Basic Refractories
a. Aluminum Oxides
1. Bauxite or Bauxite Brick
2. Alundum (Electrically fused bauxite)

b. Calcium and Magnesium Oxide
1. Magnesia
2. Lime
3. Dolomite

III- Neutral Refractories
Aluminosilicates are sometimes classified as neutral refractories, but they exhibit an
acid reaction when contact with basic slags.
A. Carbonaceous Refractories (Graphite, carbon bricks)
B. Chromite (chrome-magnesite)
C. Artificial Refractories (Zirconium carbide ZrC, silicon carbide SiC)
D. Metals (Fe, Cu, Mo, Ni, Pt, Os, Ta, Ti, W, V and Zr)
E. Others (Forsterite, concrete, serpentine,etc)

IV- Rarer Refractories: ThO
2
, TiO
2
, ZrO
2
, Y
2
O
3
, Ta
2
O
3
, CeO
2
, etc.

1.5.2.5. Some Properties of Refractories
Thermal Conductivity: Must be low to minimize heat losses from furnace walls.
Coefficient of Thermal Expansion: Must be low, since the refractories will expand
when heated up to operating temperature. Allowance must be given to this during the
construction of the furnace.
Thermal Shock Resistance: Means the ability of a refractory to withstand repeated
heating and cooling. The expansion and contraction, which accompanies heating and cooling,
may cause the refractory to break or spall. To avoid this, all refractories are, in general heated
and cooled very slowly.
Porosity: Since most refractories are made by firing mixtures of solids, the formation
of pores between the solid grains can not be prevented. The porosity should be kept at a
minimum, since all the refractory properties (e.g. strength, thermal shock resistance) of the
brick improve when the porosity is decreased, except in the case of insulating refractories.
32
Resistance to Chemical Attack: Most of the oxide or silicate refractories are already
fully oxidized so that they will not be affected by oxygen. However, graphite and silicon
carbide will oxidize at high temperature and actually will burn.
Chemical attack usually results from the contact of acid and basic refractories, through
slag or dust. With acid slag (i.e. slag high in silica) acidic refractories and with basic slag (i.e.
high in CaO, MgO) basic refractories should be in contact. The product of the chemical
reaction has a very low melting point (forms a eutectic). For the same reason acid and basic
refractories should not be laid side by side in the heated portions of the furnace. Bricks may
have to withstand abrasive damage or erosion by fast moving, dust-laden gases.
Softening Point: It is the temperature at which, the refractory is plastically deformed
under load. The selection of the refractory for a given service temperature should take the
softening point into consideration not the melting point of the refractory.
Ability to Stand High Temperatures: Refractories should stand high temperatures.

33
1.6. PRODUCTION of PIG IRON in an IRON BLAST FURNACE


Continuous Pyrometallurgical Smelting Operation

Blast Furnace Gas
(gaseous fuel (by-product))
CO 22-27%
CO
2
11-16%
H
2
O 3-5%
N
2
56-57%

Slag
CaO 35-45%
SiO
2
30-35%
Al
2
O
3
10-15%
MgO 2-10%
Pig Iron
Main product of blast furnace
C 3.5 4.25 %
Mn 0.5 2.5 %
Si 1.0 3.0 %
S, P, etc. 0.025%
Fe Rest

For 1 ton of Pig Iron Production
1.50 tons of iron ore or
sinter or pellets
0.50 ton of coke
0.25 ton of limestone
2.00 tons of air
Total 4.25 tons
Raw Materials
1. Coke: Fuel+Reducing agent
( -7.5 cm + 1.5 cm)
2. Limestone: For slag formation
+ Removal of impurities
(-7.5 cm +2.5 cm)
3. Source of Iron
Iron ore Fe>51%
-75mm +8mm
and/or
Sinter -50mm +8 mm
and/or
Pellets 10-12 mm
34
1.7. STEELMAKING

Steelmaking is an intermittent process.
Steel is an alloy of iron and C (max 2%C)
Most steels contain< 0.6% C
Steel Making Processes
1. Bessemer Process(Acidic)- Thomas Process (Basic)
2. Open-hearth Steelmaking (Siemens-Martin Furnaces)
3. Oxygen Steelmaking- L.D., LD-AC, Kaldo, Rotor, etc. (Ereli, skenderun,
Karabk)
4. Electric Steelmaking (ukurova, Asil elik, Kroman, emta, etc.)

Mpt BF Flux: Lime (CaO)
Acid Steelmaking
1250-1450
o
C Pig Iron e.g. 4%C Steelmaking (S,P-cant be removed)
1%Mn (Pyrometallurgical
1%Si Refining Process)
P,S vary Basic Steelmaking
(S,P can be removed)

Steel (Mpt: 1500-1600
o
C)
(Lower impurity contents)
e.g. C : 0.04-0.80%
Mn: 0.06-0.30%
P : 0.01-0.05%
S : 0.01-0.05%
Si : Negligible
During Steelmaking:
Si oxidized to SiO
2
- goes to slag
Mn oxidized to MnO - goes to slag
C oxidized to CO(g) burns at the mouth of converter or collected
P oxidized to P
2
O
5
- goes to slag
S reacts with CaO CaS in slag (CaO+S=CaS+CO)


Example: Oxygen Steelmaking: L-D (Linz-Donawitz) Process
BOF (Basic Oxygen Furnace)

Refractories
Steel Shell
Magnesite Brick

Magnesite or Dolomite
(Working Lining)


At exothermic reactions, usually excess
heat is produced; in order to cool it, scrap is
added. So L-D steelmaking is autogenous.
35
1.8. EXTRACTIVE METALLURGY of NONFERROUS METALS

1.8.1. Extractive Metallurgy of Copper

Copper Ores Sulphide Ores Pyrometallurgical Extraction
Oxidized Ores Hydrometallurgical Extraction

1.8.1.1. Sulphide Ores of Copper
e.g.
CuFeS
2
containing ore (0.5-2.0%Cu)

Comminution

Flotation Tailing

Cu Concentrate (20-30%Cu)


or or or or or or
Drying Roasting Green Conc. Drying Sintering Continuous
or Process
Electric Ergani Murgul KBI Pelletizing
Furnace
Reverberatory Flash Cu Blast
Furnace Furnace Furnace




Matte (30-55% Cu) xCu
2
S.yFeS


Converting


Blister Cu (98.5% Cu)


Fire Refining (S, O removed)


Anodes (99.5% Cu)


Electrolytic Refining


Electrolytic Cu
or (99.99 %Cu)
Cathode Cu
36
1.8.1.2. Oxidized Ores of Copper

e.g. (oxides, carbonates, hydroxides, silicates, sulphates, etc. of copper)

CuCO
3
.Cu(OH)
2
Malahite, CuSiO
3
.2H
2
O Chrysocolla, Cu
2
O Cuprite, etc.



Lean Ore Rich Ore Oxide Concentrate
(Cu<1.0%) (1-2 %Cu) or
Roasted Sulphide
(20-30 %Cu)


Heap Leaching Vat Leaching Agitation
with H
2
SO
4
with H
2
SO
4
Leaching



Pregnant Leach Electrolyte Electrolyte
Solution (5 kg Cu/m
3
) (35 kg Cu/m
3
) (40 kg Cu/m
3
)




Cementation SX
by scrap


Cement Cu Electrolyte
(40 kg Cu/m
3
)


Electrowinning



Cathode Copper (99.94% Cu)












37
1.8.2. Extraction of Lead

Lead Sulphide Ore

Comminution and Concentration

Lead Concentrate (40-70% Pb)
e.g. PbS Concentrate (S acts as fuel)



Fluxes Roasting and Sintering Moisture (8-10%)
-6 mm CaCO
3
(Done together on a Dwight-Lloyd)
sintering machine
CaCO
3
CaO+CO
2
- Heat At 1100 C Dust Laden Gases
containing SO
2

Sinter SO
2
Dust
Coke (fuel)
Air H
2
SO
4
Scrap Lead Blast Furnace BF gas
(For slag formation) 1400
o
C


Slag (SiO
2
, FeO, Lead Bullion (96-99%Pb)
ZnO, CaO etc.)

Refining
Waste

Commercial Pb Ag, Sb, Zn, Cu, Sn. etc.
Reduction in Blast Furnace:
PbO + CPb + CO
PbO + CO Pb + CO
2

38
1.8.3. Extraction of Zinc

Zinc Sulphide Ore

Comminution and Concentration

Pyrometallurgical Route Hydrometallurgical Route

ZnS Concentrate Roasting
(50%Zn) (ZnS+3/2O
2
ZnO+SO
2
+heat), T:900C

Roasting Pressure Leaching
under O
2
Leaching with H
2
SO
4
at 80
o
C
Sintering, Briquetting, etc. ZnO+H
2
SO
4
ZnSO
4
+H
2
O

Horizontal Retort Furnace Solid/Liquid
Solid
Separation
(Leach Residue)
or Liquid
Vertical Retort Furnace Solution Purification
or Cd,Cu,Co,Ni,etc
Blast Furnace 1300
o
C separated
or Electrolysis
Other Furnaces 2ZnSO +2H O+2e
4 2 2 4 2
Cathodes: Al
-
2Zn
0
+ 2H SO +O Anodes: Pb or Pb-Ag
Slab Zn

Reduction Reaction:
ZnO + C Zn +CO Electrolytic Zinc
ZnO + CO Zn +CO
2
99.99% Zn

39
1.8.4. Extraction of Aluminum

Hydrometallurgical Production of Al
2
O
3
(alumina) by the Bayer Process

Bauxite (e.g. 55% Al
2
O
3
) Al
2
O
3
.xH
2
O

Raw Material Preparation (Crushing, Grinding, etc.)
NaOH Regenerated


Leaching with NaOH Al
2
O
3
+2NaOH
2NaAlO
2
+H
2
O
T up to 300
o
C
P up to 40 atm.

Liquid/Solid Separation Leach Residue
(Red Mud) Hydrometallurgy
Fe
2
O
3
, SiO
2
,TiO
2
,
etc.

Precipitation of Al(OH)
3
NaAlO
2
+2H
2
O
Al(OH)
3
+NaOH
Seeds
Al(OH)
3

Separation of Al(OH)
3



Calcination of Al(OH)
3
At 1100
O
C
2 Al(OH)
3
Al
2
O
3
+3H
2
O

Al
2
O
3
(99.6%)
3NaF.AlF
3
(cryolite)
Electrometallurgy
Fused Salt Electrolysis


Aluminum Metal
>99.5% Al

At the Cathode: At the Anode:
Al
2
O
3
2Al + 3/2O
2
C + O
2
CO
2
C + O
2
CO

40