Principles of Extractive Metallurgy

Lecture 02:
a. Occurrence/Source of Metals
b. Metal Extraction Process Overview

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Concepts:
• Metals containing raw materials
• Crustal abundance of Metals
• Minerals, Ores and Gangue
• Common Metallic Ores
• Concentration Factors, Reserve and Resources
• Association of common impurity/valuable metals in major ores
• Major minerals production in India
• Extractive Metallurgy: Pyrometallurgy, Hydrometallurgy, Electrometallurgy
• Steps for Metal Extraction
• Chemical Concept on Metal Extraction
• Thermodynamics Concepts on Metal Extraction
• Metal Extraction Flowchart
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 Keywords:
• Crustal abundance • Pyrometallurgy
• Sea-nodules • Hydrometallurgy
• Minerals • Electrometallurgy
• Ores • Pretreatment
• Gangue • Metal Separation
• Concentration Factor • Refining
• Impurity/Byproduct in ores • Metal Activity Series
• Rank and self-sufficiency • Standard Affinity

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Occurrence of Metals
• Chemically active elements always occur in the combined state i.e. in the
form of stable compounds (minerals) containing that element.
• Less reactive metal, like platinum, gold occur in free (native) state.
• Metals that occur in the combined form exist as their oxides, sulphides,
carbonates, phosphates and silicates etc.
• Deposits in Earth’s crust is the most important source of metal bearing
minerals.
• Sea water (and deep sea-nodule) is a vast source of a large number of
elements.
• Scrap metals (reclaimed and recycled) can also be another source of metals.

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Relative Abundance of Elements on Earth’s Crust
Abundacy Element (wt%)
1-10% Al(8.3), Fe(5.6), Ca(4.1), Na(2.4), Mg(2.3), K(2.1) Metals in Sea Nodules
Element Wt% Reserve (Nodule/Land)
0.1-1% C, H, Ti (0.44), Mn (0.1), P (109 ton) Reserve
0.01-0.1% Ba, Cl, Cr, F, Rb, S, Sr, V, Zr
Mn 23.9 358 4000
0.001- .01% Cu (.01), Ce, Co, Ga, La, Li, Nb, Ni, Pb, Sn, Th, Zn, Yt
Fe 13.8 207 4
1-10 ppm As, B, Br, Cs, Ge, Hf, Mo, Sb, Ta, U, W, Rare earths*
0.1-1 ppm Bi, Cd, I, In, Tl Ni 0.98 14.7 1500
.01-0.1 ppm Ag, Pd, Se Co 0.35 5.2 5000
.001-.01ppm Au, Ir, Os, Pt, Re, Rh, Ru Cu 0.52 7.9 150
Zn 0.46 0.7 10
Mo 0.05 0.77 60

Average Content in Sea Water

Element Concentration
(kg/ton)
Na 10.5
Mg 1.27
Ca 0.4
K 0.38
*Rare Earths Metals: Sc, Y, Lanthanides
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 Minerals and Ores
• Minerals: Naturally occurring inorganic solid (having distinctive physical
properties and crystal structure crystalline) compound of definite composition
consisting of one or more metals in association with nonmetals.
• Ores: Aggregate of minerals from which one or more metals or minerals may
be extracted economically (with profit or hope of profit). An ore may have
wide variation in composition and in physical and chemical properties.
• All ores are minerals but all minerals may not be considered as
ores (on economic criteria).
• Gangue: Some minerals (nonmetallic materials, pyrites, usually worthless)
associated with a deposit in ore are not useful from the point of view of metal
extraction; these are known as gangue.

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 Common Metallic Ores
Metal Mineral (Formula)
Iron (Fe) Magnetite (Fe3O4), Hematite (Fe2O3), Siderite (FeCO3), Limonite
(2Fe2O3-3H2O)
Copper (Cu) Native Copper (Cu), Chalcopyrite (CuFeS2), Chalcocite (Cu2S),
Covellite (CuS), Cuprite (Cu2O)
Aluminum (Al) Diaspore (Al2O3-H2O), Gibbsite (Al2O3-3H2O), Kaolinite (Al2O3-
2SiO2-2H2O)
Lead (Pb) Galena (PbS), Cerussite (PbCO3), Anglesite (PbSO4)
Zinc (Zn) Sphalerite (ZnS-zinc blende), Zincite (ZnO), Franklinite ([Fe, Zn,
Mn]O)
Magnesium Magnesite (MgO), Dolomite (MgCO3-CaCO3)
Tin (Sn) Cassiterite (SnO2), Stannite (Cu2S-FeS-SnS2)
Chromium (Cr) Chromite (FeCr2O4)
Cobalt (Co) Cobaltite (CoAsS)
Cadmium (Cd) Greenockite (CdS) 7
 Common metallic
Nickel (Ni) ores/sources
Millerite (NiS), Garnierite (Hydsrosilicate of Ni and Mg),
Pentlandite ([Fe,Ni]S)
Manganese (Mn) Pyrolusite (MnO2), Rhodochrosite (MnCO3), Rhodonite (MnSiO2)
Titanium (Ti) Ilmenite (FeO-TiO2), Rutile (TiO2)
Zirconium (Zr) Baddeleyite (ZrO2), Zircon (ZrSiO4)
Vanadium (V) Patronite(V2S5+S), Carnotite(K2O-2UO2-V2O5-3H2O), Vanadinite
(3Pb3[VO4]2PbCl2
Molybdenum Molybdenite (MoS2), Molybdite (MoO3)
Tungsten (W) Wolframite (FeWO4), Scheelite (CaWO4)
Silver (Ag) Native Ag, Argentite (Ag2S), Cerargyrite (AgCl)
Gold (Au) Au, calaverite (AuTe2), Sylvanite (AuAg)Te2
Beryllium (Be) Beryl (3BeO-Al2O3-6SiO2)
Mercury (Hg) Cinnabar (HgS)
Uranium (U) Pitchblende (complex oxide)
Antimony (Sb) Stibnite (Sb2S3) 8
Common Types of Ores

chalcopyrite

Pentlandi
te

Hematite

Cassiterit Bauxites
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 Abundant compound forms of
metal

No metal can be economically extracted from a source in which its concentration

is the same as its crustal abundance.
Fortunately, geochemical processes have resulted in significant selective
concentration of the elements in certain portions of the Earth’s crust. 10
Factors Affecting Commercial Production of Metals
• Accessibility of the deposits
• Richness and type of ore deposits
• Nature of extraction and refining processes of the metals
• Physical and Chemical Properties of the metals
• Demands and future developments of the metals
• Production cost and economy
In metallic ores, %metal is often quoted as grade.

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 Concentration Factors of Common Metals

Deposit having average minimum exploitable grade so that

economic processing is possible with profit are called reserves.
Deposit having less than average minimum exploitable grade but
expected to be profitable for metal extraction in near future are
called resources.
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 Common Metals Association with Major Ores

Most ores contain more than one recoverable metal (present as different minerals, or metal
solid solution within the ore mineral of another).
Silver is frequently found dissolved in lead and copper minerals (principal source of Ag is as a
by-product from refining lead). 13
Linkages of metals as found in natural resources

Ref: M.A. Reuter et.al., XXII International Mineral Processing Congress, 2003,
14 p128.
Contribution, Rank, Demand, Self Sufficiency of India in
Production (MT) of Principal Minerals 2020
Minerals World India % India’s Domestic % Self
Production Production Contribution Rank Demand Sufficiency
Bauxite 368.6 20.37 5.6 6th 23.16 88
Chromite 31 2.87 9.3 4th 3.02 95
Ironore 3016 204 6.8 4th 148 100
Manganese ore 49.6 2.69 5.4 5th 6.66 40
Magnesite 28.3 0.08 0.3 17th 0.4 20
Phosphates 221 1.46 0.7 15th 9.24 16

Share (%) of States in Values

of Mineral Production 2021-
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 Extractive Metallurgy: Overview
 Primary extractive/chemical metallurgy is the science and engineering of
extracting and refining of metals from ores.
 Closely related to this technology is mineral beneficiation whereby ores are
treated by mechanical, physical, and physico-chemical means to remove
gangue and prepare concentrates either for metal production or to be used
for the chemical and other industries as industrial minerals.

Mineral Chemistry
Chemistry
Mineral Extractive Minerology
Pyro
Ore Beneficiation Metallurgy Metal
(Chemical)

tro
Hy
(Physical)

Elec
dro
Mineral Chemical
Engineering Engineering
Industrial Minerals
Engineering

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Extractive Metallurgy: 3 Divisions
• Pyrometallurgy: The use of high temperature for recovering metals (most
suitable for treating high grade ores).
• Hydrometallurgy: The use of aqueous solutions to dissolve and recover
value metal (suitable for low grade ores).
• Electrometallurgy: The use of electric current to effect a chemical reaction
like electrowinning, fused salt electrolysis, electrorefining and electric
heating (suitable for extracting reactive metal from their pure compounds,)

In Greek ‘pyr’ means ‘more at fire’ and ‘hydor’ means ‘more at water’. 17
 Metal Extraction Processes
• The actual process of extraction of a metal from its ore depends upon the
nature of the ore and the metal.
• There is no universally operational method for the extraction of metals.
Certain common steps however, are involved in all metallurgical processes.
Main steps are:
1. Mineral Beneficiation {Ore  Concentrate; Removal of gangue particles
from value mineral particles}
2. Ore/Concentrate Pretreatment {Modification of chemical nature for
convenient reduction to recover metal}
3. Metal Separation {Reduction smelting/conversion /Electrochemical:
Removal of nonmetallic part from the metal bearing compound}
4. Refining {Bulk - Refined metal; Physical and Chemical}
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 Chemical aspects of metal production
• Three main steps:
1. Preliminary treatment
• Thermal (ores of Li, Bi, Be, Sb, Mg); Roasting (ores of Pb, Zn, Cu)
• Halide Formation (ores of Ti, Zr, Hf, U)
• Leaching (ores of Al, Ti)
• Matte Smelting (ores of Cu, Ni)
2. Metal separation
• Reduction [chemical, electrolytic] (Fe, Zn, Pb, U, Th, Nb, Al)
• Conversion (Cu, Ni)
• Thermal decomposition (Pt, Pd)
3. Refining
• Chemical [selective oxidation of impurities] (Fe, Cu, Pb, Ni)
• Chemical transport [carbonyl, iodide process] (Ni, Zr, Ti)
• Physio-chemical [precipitation of impurities] (Pb)
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• Physical [distillation, vacuum melting, zone refining] (Cd, Zn, Hg, Fe)
Principles of Extraction: Metal Activity Series

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 Ellingham Diagram
Stability of Metal Bearing Compound
at Standard Condition (∆G0 vs. T)
AFFINITY OF ELEMENTS FOR OXYGEN (Shown here)
AFFINITY OF ELEMENTS FOR OTHER NON-METAL (S,
C, N, Cl, F)

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 The affinities of Cu & Fe for S
have similar values, but the
affinity of Fe for O is much
greater than the affinity of Cu
for O2.
C can be used only for the
reduction of oxides because
its affinity for S, Cl & F is
lower than that of the metals.

Standard potentials of metals

Standard affinity for
compound formation
between metals and the
principal nonmetals at
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1000-1200 K
Schematic of Metal Separation

Halide

Halogenation
Red
ucti
on

Reduction
Oxide Metal
Oxidation

rs i o n
o n ve
C
Sulfides
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General flowsheet outline for extraction of metal

Ore resource
Comminution

Beneficiation

Preparatory treatment
(roasting/smelting)

Hydrometallurgy Pyrometallurgy
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 Hydrometallurgy Pyrometallurgy

Leaching

S/L separation Preparatory General flowsheet outline for extraction of metal

cont…
operation

Leach Liquor

Adsorption Solvent Ion

on charcoal extraction exchange

Purified Solution
Precipitation Compound intermediate

Electrolytic reduction Chemical Reduction 26

 Electrolytic reduction Chemical Reduction

Fused salt Aqueous Metallothermic Nonmetal

processes processes reduction Reduction

Classical furnace
processes

Vacuum metallurgy
Reduction under (reduction)
open conditions General flowsheet
outline for extraction
of metal cont…
Virgin metal

Electrlytic processes Vacuum metallurgy Chemical processes

Refined metal 27
 Cu ore (1-2% Cu) Cu matte (30-70% Cu)
Fluxes
Crushing, grinding Slag Air
Blowing in
Bessemer converter
Tailing (0.1-0.2% Cu) Flotation
Blister copper (98+% Cu)
Cu concentrate
Slag Fire refining
(20-30% Cu)
Air
SO2 to H2SO4 plant
Partial roast Waste electrolyte Anodes (99.5% Cu)
(Ni Recovery etc.)
Fluxes Electrolytic refining
Slag to waste Matte smelting Cu cathodes Anode mud
(0.3-1% Cu) (99.9% Cu) for recovery
Usually remelted of noble metals)

Typical flowsheet for the production of copper from a low-grade sulfide ore

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References
1.Chemical Metallurgy: Principles and Practice, Chiranjib Kumar Gupta,
2003, WILEY-VCH.
2.Handbook of Extractive Metallurgy, Volume 1, Edited by Fathi Habashi,
1997, WILEY-VCH.
3.Extraction of Nonferrous Metals, 2018, H.S. Ray, R. Sridhar, K. P. Abraham,
EWP Pvt. Ltd., Delhi.
4.https://mines.gov.in/ (Web portal of Ministry of Mines, GoI)

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