Lectures1 3
Lectures1 3
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 Earth’s 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.
Earth’s 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 Earth’s crust.
Average analysis of the Earth’s 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 Earth’s
crust that their commercial recovery is impossible. But, by natural events, those are
concentrated in certain parts of the Earth’s 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 Earth’s Crust
Element % Element % Element %
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)
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 CuFeS2.
Ore minerals are those minerals that contain the valuable metals in an ore; e.g. PbS,
CuFeS2 , ZnS…etc.
Sulfide ores are ores that contain sulfides, e.g. non-ferrous ore minerals such as PbS,
CuFeS2, and ZnS…etc.
Oxide or Oxidized ores contain oxide, carbonate, sulfate, hydroxide or silicate ore
minerals; e.g. Fe2O3, PbCO3, FeCO3, PbSO4, Zn2(OH)2.SiO3…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 (SiO2-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%).
Iron ores
Ore minerals of iron are hematite (Fe2O3), magnetite (Fe3O4), limonite (Fe2O3.xH2O)
and siderite (FeCO3). 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 (FeS2) 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 (Al2O3.3H2O), diaspore (Al2O3.H2O), boehmite
(Al2O3.H2O), corundum (Al2O3), kaolinite (Al2O3.2.SiO2.2H2O), 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 2O3.xH2O). Bauxites
contain 55 – 61 % Al2O3, 10 – 30 % combined water, 1 – 25 % Fe2O3, 1 – 3 TiO2 and 1 – 12
% SiO2. Bauxites with low SiO2 are desirable.
Copper ores
Most important ore minerals of copper are chalcopyrite (CuFeS2), bornite (Cu5FeS4),
chalcocite (Cu2S), covellite (CuS), enargite (CuAsS4), malachite (CuCO3.Cu(OH)2), cuprite
(Cu2O) and chrysocolla (CuSiO3.2H2O).
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 (Fe1-xS) 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 (PbSO4) and cerussite
(PbCO3) 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
CuFeS2 and cadmium. Smithsonite (ZnCO3) and calamine (Zn2(OH)2.SiO3) often occur in the
oxidized portions of sphalerite ore bodies. Grade of zinc sulfide ores: 2 – 12 % Zn.
Chromium ores
The economical mineral in chromium ore is chromite (FeO.Cr2O3). Commercial
chromium ores usually contain 40 % Cr2O3 or more.
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.
Mineral processing combines a series of distinct unit operations. The flowsheet shows
diagrammatically the sequence of unit operations in the plant.
A simple flowsheet of a mineral processing plant
Ore
Crushers
(+) Oversize
Screens
(-) Undersize
Grinding
(+) Oversize
Classification
(-) Undersize
Concentration
Concentrate Tailing
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
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
-3
dimensions are usually given in microns (1 micron = 10 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
←√2series
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
0.037 37 400
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.
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.
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
Dry @ 105C
Weigh again
Calculate % Moisture
% Moisture = {(wet weight - dry weight) / wet weight} * 100
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 H2O, CO2, etc.,
which are chemically bound as e.g. hydrates or carbonates.
Lost Lost
Drying Calcination
Increasing Temperature
iii. 2Al(OH)3 ↔ Al2O3 + 3H2O @ about 1000C chemically combined water is driven
off.
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:
o
2ZnS + 3O2 = 2ZnO + 2SO2, ∆H 298 K = -220 Kcal/gm-mole Strongly Exothermic
o
2FeS2 + 11/2O2 = Fe2O3 + 4SO2, ∆H 298 K = -410 Kcal/gm-mole Reactions
Product ( calcine )
Dead roast or sweet roast: Roasting to completion with the elimination of most of the
sulfur by overall reaction.
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
1.3.4. 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
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
2
specific surface area, i.e. Blaine Number 1600 – 2200 cm /gram
Bentonite (i.e. clay): Binder
Flux : Calcium oxide powder (to control basicity)
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.
1.4. METAL EXTRACTION PROCESSES
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
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. Cu2S - 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. Cu2S → Cu (blister copper)
Cu2S + 3/2O2 → Cu2O + SO2
i. 2MeS + 3O2 → 2MeO + 2SO2 FeS + Cu2O → FeO + Cu2S
FeS + 3/2O2 → FeO + SO2
1.4.1.4. Refining
Fire Refining
Air and/or O2(g) blowing
+
Poling (Introduction of hydrocarbons CH4, wood…etc)
Impure metal from Fire refining → slag
sulphide matte smelting → preferential oxidation of
and converting impurity elements → SO2(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 )
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
or some volatile metal halides are produced, e.g. SnCl4, TiCl4, AlCl3
some metal halides have low decomposition temp. ZrI4 Zr + 2I2 , @
1400C Therefore, it is possible to separate certain metal halides and to purify by
distillation.