NON-FERROUS EXTRACTIVE METALLURGY

(BTCMTPCC503, Core Paper)

(4L – 0TU – 0PR)
(IA : 30, TH : 70)

Prof Projjal Basu

Syllabus
• Module 1: Basic principles of extractive metallurgy - Thermodynamics
& kinetics of extraction processes (6h)
• Module 2: Thermodynamic basis of metal extraction: Ellingham
diagrams, predominance area diagrams, Pourbaix diagrams, concept of
activity and activity scales (10h)
• Module 3: Slags & mattes and their physico-chemical properties (6h)
• Module 4: Kinetics of extraction process: kinetic theory, reaction rate
theory, reaction across interfaces (10h)
• Module 5: Sustainable Chemical Metallurgy, Recycling and Recovery
from waste (6h)
• Module 6: Hydrometallurgy, electro metallurgy, pyrometallurgy, Ores,
mineral processing and beneficiation (8h)
• Module 7: Extractive metallurgy of Al, Cu, Zn, Ti, and Mg (10h)
Projjal Basu
Source of Metals
Metals in the earth’s crust (major source : ore deposits)
Element % Element % Element % Element %
O 46.7 Na 2.8 Zr 0.017 Zn 0.004
Si 27.5 K 2.6 V 0.014 Co 0.001
Al 8.1 Mg 2.1 Cr 0.01 Ag 0.000001
Fe 5.0 Ti 0.44 Cu 0.01 Au 0.0000001
Ca 3.6 Mn 0.10 Ni 0.008 Pt 0.0000001

Metals in ocean water (containing av 3.5% dissolved solids)

Element g/tonne Element g/tonne Element g/tonne Element g/tonne
Na 10500 Ca 400 Al 0.16-0.19 Ni 0.0001
Mg 1270 K 380 Li 0.10 Au 0.000005

Metals in Pacific ocean nodules

Element % nodule Element % nodule Element % nodule Element % nodule
Mn 23.86 Al 2.86 Ni 0.98 Cu 0.52
Fe 13.80 Mg 1.66 Ti 0.66 Zn 0.46
Projjal Basu
 Source of metals from earth crust
Element Abundance Element Abundance Element Abundance Element Abundance
(ppm) (ppm) (ppm) (ppm)
Oxygen 466,000 Phosphorus 1,050 Chromium 100 Scandium 22
(46.6%)
Silicon 277,000 Manganese 950 Rubidium 90 Lithium 20
Aluminium 81,300 Fluorine 625 Nickel 75 Niobium 20
Iron 50,000 Barium 425 Zinc 70 Nitrogen 20
Calcium 36,300 Strontium 375 Cerium 60 Gallium 15
Sodium 28,300 Sulphur 260 Copper 55 Lead 13
Potassium 25,900 Carbon 200 Yttrium 33 Radium 13
Magnesium 20,900 Zirconium 165 Lanthanum 30 Boron 10
Titanium 4,400 Vanadium 135 Neodymium 28 Krypton 9.8
Hydrogen 1,400 Chlorine 130 Cobalt 25 Thorium 7.2

Projjal Basu
 Mineral-bearing Resources in India
• Adequate to abundant : Fe, Al, Cr, Mn, Mg, Ti, Zr, Th, Pb, Zn, La, Ce, etc.
• Inadequate : Cu, Au, V, Ni, Cd, U
• Poor or so far not known : Sb, Bi, Co, Hg, Mo, Nb, Ta, Sr, Se, Te, Sn, Ag, W,
Pt)
• Non-ferrous : metals other than iron
• Mineral : naturally occurring inorganic compounds of one or more
metals in association with non-metals, such as, oxygen, sulphur,
halogens, etc., has well defined physical and chemical properties
• Ore : naturally occurring aggregate or a combination of minerals from
which one or more metals / minerals can be economically extracted

Projjal Basu
 Tonnage production of metals : Factors
• Accessibility of ore deposits (transport)
• Richness of metal/metals in ore deposits
• Location and magnitude of the ore deposits
• Nature of extraction and refining processes for the metal
• Physical and chemical properties of the metal
• Market demand of the metal
• Environmental regulations
Extractive Metallurgy : a process of separation
• Pyrometallurgy (high temperature)
• Hydrometallurgy (aqueous media)
• Electrometallurgy (using electricity) Projjal Basu
Inputs for quantitative process design in ext. met.
SCIENTIFIC FUNDAMENTALS
(Chemical Metallurgy)
A. Physico-chemical principles ENGINEERING FUNDAMENTALS
B. Structure of phases (including pore structure in porous solids) (Process Engineering Metallurgy)
C. Properties of phases, equilibrium properties, kinetic properties A. Momentum transfer
D. Reaction stoichiometry B. Mass transfer
E. Heterogeneous equilibria and surface properties C. Mathematical and computer techniques

RATIONAL PROCESS ANALYSIS

(Material and heat balances, reaction and phase equilibria,
reaction rates, rates of heat and mass transfer)

Plant data, Process knowledge RATIONAL PROCESS DESIGN Optimization techniques

Cost parameters Social / Environmental constraints

Projjal Basu
Minerals of common metals
Metal Mineral Chemical formula Metal Mineral Chemical formula Difference
between
Fe Hematite Fe2O3 Pb Galena PbS mineral and ore?
Magnetite Fe3O4 Cerussite PbCO3
Limonite Fe2O3.3H2O Anglesite PbSO4
Siderite FeCO3 Zn Sphalerite ZnS Minerals as
Gemstones
Cu Native copper Cu Zincite ZnO
Chalcocite Cu2S Franklinite (Fe,Zn,Mn)O
Covelite CuS Mg Magnesite MgO
Chalcopyrite CuFeS2 Dolomite MgCO3.CaCO3
Cuprite Cu2O Sn Cassiterite SnO2
Al Diaspore Al2O3.H2O Stannite (Cu2S.FeS.SnS2)
Gibbsite Al2O3.3H2O Mn Pyrolusite MnO2
Kaolinite Al2O3.2SiO2.2H2O Rhodochrosite MnCO3
Ti Ilmenite FeO.TiO2 Rhodonite MnSiO3
Rutile TiO2 Cr Chromite FeCr2O4

Projjal Basu
Minerals of common metals Minerals as
Metal Mineral Chemical formula Metal Mineral Chemical formula
Gemstones
V Patronite V2O5 Cd Native cadmium Cd

Carnotite K2O.2UO3.V2O5.3H2O Greenockite CdS

Vanadinite Pb3(VO4)2PbCl2 Sb Stibnite Sb2S3

Mo Molybdenite MoS2 Co Cobaltite CoAsS

Molybdite MoO3 Ag Native silver Ag

W Wolframite FeWO4 Argentite Ag2S

Scheelite CaWO4 Cerargyrite AgCl

Zr Baddeleyite ZrO2 Au Native gold Au

Zircon ZrSiO4 Calaverite AuTe2

Sylvanite (AuAg)Te2

Projjal Basu
Minerals as Gemstones

Projjal Basu
 Minerals of common metals
• Accessibility of ore deposits
• Port / Rail, near a city Factors to
consider for
• Richness of metal/metals in ore deposits deciding a
• Nature of extraction and refining processes for the metal mineral as an
ore
• Physical and chemical properties of the metal
• Market demand of the metal
• Including strategic demand (e.g. during war)
• Environmental regulations
• Import / Eport Policies, International Sanctions

Projjal Basu
 Early developments in extractive metallurgy
• 8000 BC : use of native copper (western Asia), also use of Au, Ag
• 4000 BC : Egyptians extracted Cu from ore, Chinese used flame
techniques to produce bronze and Fe
• 2000-1000 BC : Indians extracted Cu from ore and made bronze,
• 1300 BC : first smelting of ore (with charcoal and air blast)
• 300 BC : Aristotle described winning Ag from ores
• 79 BC : Pliny described Pb extraction
• Bronze age : making of bronze (harder than copper with lower melting
point) from mixture of copper ore and tin ore
• 700-800 AD : Cu precipitated from acid solution by Fe in Europe
• 1100-1300 AD : Alchemists developed acid treatment to treat ore, As
and Sb discovered
Projjal Basu
 Early developments in extractive metallurgy
• 1550 AD : Handbook on metallurgy appeared
• 1700-1800 AD : Co, Pt, Zn, Ni, Bi, Mn, Mo, Te, W, U, Zr, Ti, Y, Be, Cr
discovered
• 1800-1900 AD : Ta, Ir, Os, Pa, Rh, K, Na, B, Ba, Ca, Mg, Sr, Ce, Li, Cd, Se,
Si, Al, Th, V, La, Ru, Rb, In, Ga, Rare earths, Ra, Ac, Po discovered
• Till 1500 AD : known metals were Au, Ag, Hg, Cu, Sn, Pb, Zn, Fe

Projjal Basu
Major landmarks related to extractive metallurgy
Dudley (1620) Introduces coke to replace charcoal in England
Lavoisier (1772) Shows that oxides are compounds of metals and oxygen
Wohler, Berzelius, Bergman (1783) Demonstrated reduction of WO3, used H2 as reducing gas
Oersted (1825) Discovers Al, shows that alumina is not an element
Nielson (1828) Hot blast to attain high temperature in a B.F.
Faraday (1831) Explains electrolysis, proposed Faraday’s kaw
Bessemer, Kelly (1856) Pneumatic steel
Woehler, Deville (1850) Reduction of Al-salts to metal
Galvani, Volta, Grothans, Faraday, Developed electrochemistry
Davy (1850)
Clausius (1857) Explains origin of ions in electrolytes
Cowper (1857) Stoves for regeneration of heat
Siemens, Martin (1868) Open hearth steelmaking
Projjal Basu
Major landmarks related to extractive metallurgy
Mendeleev (1869) Proposes Periodic Table
Castner (1886) Demonstrates electrolysis of NaOH
Hall, Heroult (1886) Production of Al by electrolysis of alumina dissolved in
cryolite
Bayer (1887) Bayer process for alkali leaching of alumina (beginning of
modern hydrometallurgy)
McArther, Forests (1887) Cyanidation process for gold extraction
Goldschmidt (1894) Aluminothermal reduction of metal oxides
Becquerel (1897) Discovers radioactivity
Hahn, Strassmann (1938) Demonstrates uranium fission

Projjal Basu
 Platinum
Major Ores

Gold Iron (Hematite)

Titanium (Ilmenite)

Copper (Sulphide Ore)

Projjal Basu
 Relative reactivities and modes of occurrence
1. Highly reactive metals
1. Characteristics : high electrode potential, high (-)ve free energy of formation
2. Present in nature as simple compounds
3. Alkali and alkaline earth metals present usually as chlorides, carbonates,
sulphates
4. Also present in minerals as aluminates and alumino-silicates
2. Medium reactive
1. Mainly found as silicates
2. Some (higher in the table) may form simple oxides
3. Lower in the table : sulphides
4. Very low in table : selenides, telurides, arsenides, etc.

Projjal Basu
 Relative reactivities and modes of occurrence
Metal Electrode potential Remarks
range (V)
Li, Rb, Cs, K, B, Sr, 3.01 to 2.38 Forms chlorides, carbonates, and sulphates; highly oxidized in air; very
Ca, Na, La, Mg stable oxides; reacts spontaneously with water; forms ionic compounds
Th, Ce, Ti, Be, Hf, 2.10 to 1.44 Forms mainly oxides, silicates, or complex oxides; oxidizes on heating;
Al, Zr, V stable oxides; attacked by steam; forms mainly ionic compounds
W, Mn, U, Se, Zn, 1.10 to 0.335 Forms simple or complex oxides or sulphides; oxidizes on strong
Cr, Ga, Fe, Cd, In heating; moderately stable oxides; oxides of less reactive metals are
easily reduced; attacked by steam
Co, Ni, Mo, Sn, Pb, 0.335 to – 0.799 Forms sone selenides, telurides, arsenides in addition to sulphides and
Sb, As, Bi, Cu, Te, complex oxides; relatively unstable oxides which may decompose at
Rh, Re, Hg, Ag high temperature; not attacked by steam; mostly shows complex
bonding in compounds
Sb, As, Bi, Cu, Te, - 0.10 to – 1.70 Occurs as sulphides, telurides, or in free state; less stable oxides, some
Rh, Re, Hg, Ag, Pd, unstable even at room temperature; not attacked by steam or common
Ir, Pt, Au acids, shows complex bonding in salts

Projjal Basu
 Kinetic Principles
• Thermodynamics indicates the “possibility” of a specific direction
to which a reaction can proceed
• Actual reaction rate : can be known from kinetic analysis
• Slow reaction rate in a process is UNACCEPTABLE even if it is
favorable thermodynamically
• Kinetics : helps to understand the factors that govern the rate →
we know how to increase the process efficiency
• Empirical kinetics : helpful in process control, effects of various
parameters

Projjal Basu
 Kinetic Principles
A + B = C (product)
• Rate of forward reaction ≈ Amount of “A” or “B” transformed / “C”
produced
aA + bB + cC + ……. = products
a, b, c, … = number of molecules of A, B, C, … that react to form products
• Rate of reaction = (- dCA/dt)
(- dCA/dt) = k . CAa . CBb . CDd . …..
(k = rate constant; CAa, CBb, … = concentrations at time “t”))
• Order of reaction = sum of the exponents in concentration terms = (a + b
+ C + …)

Projjal Basu
 Kinetic Principles
First Order reaction
A=B+C
• Rate of reaction = (- dCA/dt)
(- dCA/dt) = k . CA
(k = rate constant; CAa = concentration of C at time “t”))
• Reaction Rate α single concentration of a component = First Order
Second Order
A+B=C+D
• Rate of reaction = (- dCA/dt) = (- dCB/dt) = k . CA . CB

Projjal Basu
 Kinetic Principles
For a reaction FAR from equilibrium
• Free energy difference between the reactants and products is
NEGATIVE and LARGE
• Forward reaction is HIGHLY possible
• Backward reaction is LEAST possible and unimportant
Reactions at equilibrium
• Both forward and backward reaction rates are SAME
• Reactions CLOSE to equilibrium
• Overall rate of reaction depends on both the forward and
backward reactions

Projjal Basu
 Kinetic Principles : Reaction Rate
• For a reaction A = B close to equilibrium,
Vf = kf . CA and Vb = kb . CB
At equilibrium,
Vf = Vb, meaning, kf . CAe = Kb . CBe
Equilibrium constant K = (Kf / Kb) = (CBe / CAe)
• Overall rate at which “A” is consumed = Vf – Vb
(- dCA/dt) = Vf – Vb
= Kf . CA – Kb . CB
= Kf . (CA – CB/K)
• For a reaction A + B = C + D
• K = (Kf/Kb) = (CC . CD) / (CA . CB) …… (effect of concentration)
Projjal Basu