EXTRACTIVE METALLURGY (FMC304) 3-0-0

Unit
Topics to be Covered
No.
Typical ore to metal flow sheet; brief introduction to pyro/hydro-metallurgy, criteria for selecting
1
pyrometallurgy/ hydrometallurgy route for metal extraction
Drying. Gas-solid reactions; shrinking core model; calcination, roasting, agglomeration, reduction
2
reactions
Smelting; matte smelting; flash smelting; converting; vacuum/inert-gas degassing; zone refining;
3
fractional distillation; blast furnace, different zones in blast furnace, blast furnace profile
Leaching; types of leaching, Eh-pH diagrams and their usefulness, chemical precipitation;
4 cementation, solvent extraction; ion exchange; aqueous and molten salt electro-winning; electro-
refining; gaseous reduction of metals
5 Typical flowsheets for extraction of metals such as copper, aluminium, magnesium

1. Process selection in extractive metallurgy by P. Hayes

2. Extraction of nonferrous metals by H. S. Ray, R. Sridhar, K. P. Abraham
3. A first course in iron and steelmaking by Deepak Mazumdar
4. Principle of Extractive Metallurgy by H. S. Ray and A. Ghosh
 Extractive Metallurgy is a science of separating metals from their ores chemically and subsequently refine
them to recover the metal in a pure form.
A ore may be defined as a naturally Run of mines
Mineral Dressing occurring aggregate of minerals from which ore
metal can be extracted economically.
Mineral
C A mineral may be defined as a naturally dressing
Comminution: Crushing, grinding
occurring homogeneous substance of
definite chemical composition and with a Extraction
certain characteristic physical properties. process
C
Sizing: Sorting, screening, classification

Impure metal
Concentration: Gravity conc., Heavy media Dewatering: Sedimentation
separation, Jigging, C Tabling, Magnetic C
thickening, Coagulation, Filtration,
separation, Electrostatic separation, flotation Drying Refining
process
“Mineral dressing is the processing of raw materials to yield
marketable products and waste by means that do not C
Agglomeration: Pelletization, Sintering Pure metal
destroy the physical and chemical identity of the minerals”..
M. A. Gaudin (1951)
Extraction of metal
 Unit Operations in Mineral Processing
Process Description Properties of mineral exploited
Comminution: Crushing, Subdivision of mineral lumps and particles into Brittleness
grinding smaller sizes
Sizing: Sorting, screening Separation according to size Size difference among particles

Hydraulic classification Settling in fluid Relative diff. in size and density

among mineral particles
Concentration:
Gravity concentration
Heavy media separation Settling in liquid Relative differences in density
among particles
Jigging Settling in liquid -do-

Tabling Friction movement along wet vibrating solid
surface
Magnetic separation Separation due to magnetic field in dry and wet
condition
Electrostatic separation Charging and charge loss of particles and their
deflections in electrostatic field
Flotation Attachment of gab bubbles to mineral in aqueous
pulp containing surfactant and frothers.
Density, size, shape and
coefficient of friction
Magnetic permeability and mag.
susceptibility of particles
Conductivity and charge
retention characteristic
Surface properties, affinity for
specific surface active reagents
Process Description Properties of mineral exploited
Dewatering:
Sedimentation thickening Settling of particles Nonspecific
Coagulation Neutralization of charge or repulsion forces Adsorption properties of minerals may
lead to beneficiation
Filtration Solid liquid separation Nonspecific
Drying Removal of moisture from moist solid Nonspecific

Agglomeration:
Pelletization, Nodulizing, Obtaining bigger lumps from smaller Solid-solid reaction at interfaces of
Sintering particles through adhesion or incipient particles
fusion of particles
 TYPICAL ORE TO METAL FLOW SHEET/FLOW DIAGRAM
Ore from mines

Comminution Fire refining

Flotation Casting (anodes)

Concentrate
Tailing
Electrolytic refining
Roasting Air
Flux Gases to waste
Fire refining
Matte smelting

Slag to waste Casting

Matte
99.99% copper
Air
Flux Converting Gases to waste

Slag Blister copper

99% Cu
Flow diagram for extraction of copper from low grade ore
 Extraction Processes
• Pyrometallurgy: Pyrometallurgical processes (pyro means ‘heat’ in Greek) are carried out at high temperature.
• Hydrometallurgy: Hydrometallurgy (Hyro means ‘water’ in Greek) is carried out in aqueous media at room temperature.
• Electrometallurgy: Electrometallurgy employs electrolysis for separation at room temperature as well as at high
temperature.

Pyrometallurgy: Pyrometallurgical methods of metal production are usually cheaper and suited for large scale productions.
1. Reaction rate are greatly accelerated at high temperatures. Small units can, therefore, achieve high production rates.
2. Some reactions which are not thermodynamically possible at low temperatures become so at higher temperatures.
3. There is greater ease physical separation of the product metal from gangue, if the products can be melted or vaporized at
high temperatures.

 Large amount of heat energy is required to generate high temperature: high fuel consumption
 Due to high temperature erosion of refractory by molten metal and molten slag, is rather more on the furnace lining
 Oxidation of Sulphur/carbon, during the process, generate Sulphur dioxide/carbon dioxide gas leading to pollution
Calcination: Calcination is the thermal treatment of an ore that brings about its decomposition and eliminates
the volatile product- usually carbon dioxide or water. The temperature required for calcination can be calculated
from the free energy temperature relationship for the reaction under consideration.
CaCO3 (c)= CaO (c) + CO2 (g), ∆G0T (cal) = 42300 – 37.7T

When the CO2 pressure is 1 at, ∆G0T becomes equal to 1 and T equal to 1123K or 850oC.

Roasting: The roasting of an ore or a concentrate is a process which precedes smelting in Pyrometallurgy and
leaching in hydrometallurgy. An oxide is more easily reduced to the metal than a sulphide, and leaching
becomes easier if the metal is present as a sulphate, chloride or oxide.
Therefore, the mineral constituent of an ore must be converted into another chemical form. Such a conversion
is known as roasting.
OXIDING ROASTING: It is the most important roasting process, burns out the Sulphur from a sulphide ore and replace it by an
oxide.
MS (c) + 3/2 O2 MO (c) + SO2 (g)
ZnS (c) + 3/2 O2 ZnO (c) + SO2 (g)
When a sulphide ore is roasted to a point where almost the entire Sulphur content is eliminated, the residue is called dead
roasting
A catalytic agent often speeds up the roasting process. Quartz and other gangue materials often act as catalysts during roasting.
Roasting deepens on factor such as time, temperature the availability of oxygen or air, the physical condition of ore and the
nature of mechanical devices used.

Volatizing Roasting: Volatizing roasting eliminates volatile oxides such as As2O3, Sb2O3 and ZnO from an ore. In volatizing
roasting, the inflow of oxygen should be carefully controlled, as excessive oxidation may lead to the formation of non-volatile
higher oxides.
Chloridizing Roasting: Chloridizing roasting is carried out to convert certain metal compounds to chlorides under oxidizing or
reducing conditions. Many metals e.g. uranium, beryllium, niobium, zirconium and titanium are extracted from their chlorides.
2NaCl + MS + O2 = Na2SO4 + MCl2,
4NaCl + 2MO + S2 + 3O2 = 2Na2SO4 + 2MCl2

Other Kind of Roasting

• Sulphating Roasting converts certain sulphide ores to sulphates, usually prior to leaching.
• Magnetizing roasting is the controlled reduction of hematite (Fe2O3) to magnetite (Fe3O4).
• Reduction roasting is the partial reduction of an oxide ore prior to actual reduction smelting.
• Blast roasting or sinter roasting not only modifies the physical condition of an ore but also helps in its partial oxidation.
ROASTING PRACTICE

Required Physical condition of product: Coarse or fine particles

Required Chemical condition of product: Chemical composition of minerals/ores

INDUSTRIAL ROASTING UNITS

Multiple Hearth Roasting: Designed by McDougall in England (Late 19

Century)
Basic principle: Counter current flow of solid ore and oxidizing gases
Shell dia: 25 ft and No of hearth: 6-12
Charging method: Top charging
Ore movement: continuous shifting of charge by revolving mechanical rabble
attached to the arm
Oxidizing gas movement: Ascending
Drawback:
• Slow roasting
Flash Roasting:
• Preheated ore particles are made to fall through body of hot air
• Instantaneous oxidation or flash of combustible constituents of the ore, Sulphur
• Ore should be fine size
• Temperature of combustible zone = 900 – 9500C

Fluidized Bed Roasting:

• Principle- Ore particles roasted while it is suspended in an upward stream gases
• Gas passes through a bed of solid particles, size range: 0.005-0.05 mm
• The behaviour of the bed depends on the velocity of the gas
1. When the gas flow rate is very slow the gas permeates the bed without disturbing the ore particle.
The pressure drop across the bed is proportional the gas flow
2. When the gas velocity increases, the bed expands upward due to the drag forces exerted by the gas
The pressure drop across the bed depends on the gas velocity
3. When the gas velocity is further increases, a stage is reached when the pressure
drop across the bed is equal to the weight of the particles per unit area of he bed. The
particles now remain suspended.
4. Further increasing the gas velocity leads to the continued expansion of the bed and
results in an increase in the inter particle distance.
5. A stage reaches when the expansion of the bed becomes independent of the gas
velocity . A major portion of the gas stream appears in the form of bubbles bursting
on the surface of the bed, like a well-stirred boiling liquid. This is called fluidized bed.

Sinter Roasting/Blast Roasting:

Sinter roasting is the treatment of a sulphide ore in a sintering
machine where roasting and agglomeration take place simultaneously.
It is carried out in a Dwight-Lloyed Sintering machine.
SMELTING
Smelting is a heating process for the production of a metal or matte
The process is one of reduction of the oxide of the metal with carbon/Sulphur
A flux is added to form a slag that is easily fusible to gangue materials
Mineral + Gangue + Reducing agent + Flux = Metal/Matte + Slag + Gas
The General characteristics:
 The materials to smelted are charged in the solid state
 The products of the smelting are in the liquid state
 The heat required for smelting is supplied by external sources
Types of smelting
1. Reduction smelting: Carried out in blast furnace, the ore is reduced by carbon in the presence of flus, molten metal and
slag produced
2. Flash smelting/ Matte smelting: Carried out in reverberatory furnace or flash smelter, reducing agent is not used, sulphide
acts as a reducing agent, product is molten matte and molten slag.
FLUXES
• A flux is used to lower both the liquidus temperature and the viscosity of the slag
• Flux can be classified according to the chemical and it is selected keeping in view as the chemical nature of
gangue and properties desired in the slag
• For siliceous gangue- a basic oxide like lime is used as a flux, for a basic gange- an acidic oxide like silica is
used
• Oxidizing flux: Na2O2, NaNO3 and KNO3, reducing flux: NaCN and neutral flux: CaF2 or Na2SO4

SLAG
Function of slag:

 To collect the unreacted gangue minerals

 To provide a medium in which the impurities in a metal can collect

A must possess the following properties:
1. The difference between the specific gravities of the slag and the metal should be high
2. The slag must be fluid enough to permit its easy separation from metal
3. The slag must have a chemical composition which ensures that the activities of the impurities

Reduction Melting using carbon

Carbon is element as a reducing agent:
 Easily available
 Inexpensive
The reduction of a metal oxide by carbon can be represented as:
MO + C = CO + M
MO + C = 2M + CO2
The above reaction can be represented more accurately as:
MO + CO = M + CO2
CO2 + C = 2CO
Combining both reaction: MO + C = CO + M
Metallothermic reduction of oxide
An oxide is reduced by a metal that forms stable oxide

It is carried out in an open or a close container

A metal that forms a stable oxide would replace metals from less stable oxides

Fe2O3 + 2Al = Al2O3 + 2Fe

TiO2 + 2Ca = 2CaO + Ti

Formation of slag
• The reduction of a metal oxide by a metal results in a more stable oxide
• Carbon reduction releases siliceous materials or other gangue materials to form a refractory oxide phase
• The formation of liquid slag is felicitated by addition fluxing agents such as quartz and lime
• All silicate melts are viscous, it can be decrease by addition of a suitable basic oxides

Structure of silicate slags

• The structure of pure crystalline silicate is tree dimensional network
consisting of silicon and oxygen atoms possessing both long range and
short range order
• In molten silica, some Si-O-Si bonds rupture due to the effect of thermal
energy and some depolymerization takes place.
• When basic metal oxide MO (Cao, MgO) is added to molten silica, the
three dimensional network starts breaking.
• The silica accepts an oxygen iron and MO donates an oxygen ion
• Depolymerization reaction shows as the quantity of metal oxide addition
increases

Metal losses in Slags

 A complication could arise during smelting when reactant and product oxides themselves form compounds
 Sometime advantageous in case of slag with low melting point and a part of the reactant raw materials would be lost
due to dissolution in the slag
 Metal recovery would be low
 Ex. During smelting of lead ore in B/F, PbO may combine with silica to enter the slag as silicate.
 The PbO loss can be minimize by addition of scrap iron to the charge
 The scrap iron reduce the PbO and also helps in recovery lead from the silicate
PbO + Fe = FeO + Pb
PbO.SiO2 + Fe = FeO.SiO2 + Pb
Classification of Slags
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑐𝑖𝑑𝑖𝑐 𝑜𝑥𝑦𝑔𝑒𝑛 𝑓𝑟𝑜𝑚 𝑆𝑖𝑂2
𝑆𝑖𝑙𝑖𝑐𝑎𝑡𝑒 𝑑𝑒𝑔𝑟𝑒𝑒 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑏𝑎𝑠𝑖𝑐 𝑜𝑥𝑦𝑔𝑒𝑛 𝑓𝑟𝑜𝑚 𝐶𝑎𝑂, 𝑀𝑔𝑂, 𝐹𝑒𝑂, … .

Basic slags: A basic slag has a silicate degree < 1. The principal anions in a molten basic slag are O2- and SiO44-
Neutral slags: A neutral slag has a silicate degree = 1. The principal anions in a molten neutral slag is SiO44-
Acid slag: A acid has a silicate degree >1. The principal anions in a molten acid slag are the chain silicate anions Si2O76-,
Si3O108-, the ring silicate anions Si4O128- and other globular anions
 SMELTING FURNACES
• The blast furnace is the most popular furnace for reduction smelting
• Smelting of iron ore is the best example of blast furnace operation
• Lead is also produced in the blast furnace
• The imperial smelting has developed for the simultaneous production of lead and zinc
in the blast furnace
• Lead is tapped and zinc is recovered by dissolving the out coming zinc vapours in a
steam of molten lead
• Zinc separates from lead on cooling
• The blast furnace operates in a strongly reducing atmosphere than a reverberatory
furnace
Blast furnace
• An electric arc smelting is employed when very high temperature is required for reduction
• A temperature around 2000oC can easily attained
• Ferroalloys requires high temperature for reduction are smelted in electric arc furnace
• No special furnace is required for the Metallothermic reduction of an oxide
• The need of heat is maintained by exothermic reactions of oxides

Electric Arc Furnace Unit for Metallothermic reduction

• The flash smelting is one of most interesting
development for the smelting of nickel
sulphide and copper sulphide concentrates
• It is a combined process of flash roasting and
smelting operations
• The objective is to burn the concentrate with
oxygen or preheated air blown
• Sufficient heat is generated to form a matte
and a slag
• Oxygen enriched preheated air or pure oxygen
is used instead of air to increase the
combustion rate and to maintain autogenous Flash Smelter
smelting
• The off gases are rich in SO2 and can be used
for H2SO4 production