Industrial and scientific aspects of nonferrous metals production

H.S. Ray
Central Glass and Ceramic Research Institute, Kolkata – 700 032, India

This industrial categorisation of nonferrous metals encompasses a very wide variety of metals which
can be put in different subgroups on the basis of different criteria such as tonnage production,
properties, application, price, nature of occurrence etc. Such criteria seldom have scientific basis.
However, there are common scientific principles which form the basis of methods of ore processing,
extraction and refining of all metals. This article discusses some of these principles and also briefly
discusses some developments which are futuristic.
Key words: Nonferrous metals, industrial aspects, energy, environmental, extraction, thermodynamics
and kinetics, future scenario.

1. Introduction
The word ‘nonferrous’ metals implies all metals other than iron. This classification becomes too wide
and scientifically ill-defined. Within this group there can be many subgroups and, therefore, there are
many terminologies which are in common use. Names of some such subgroups, which often overlap,
are common metals, less common metals, noble metals, reactive metals, reactor or nuclear metals,
alkali metals, rare metals etc. Some of these can have further classification based on properties,
applications or other criteria. Table 1 shows, as an example, a classification of rare metals.
Some nonferrous metals 9 (e.g. Mn, Cr, V, Mo, Si, Ti etc.) are often produced as ferroalloys and
therefore, generally discussed in ferrous metallurgy. Metals can be classified on the basis of different
scientific criteria but these are not useful to the industry concerned with utility, abundance, price,
properties etc. Scientific principles, however, form a common basis, in processing of ores, extraction
and refining methods. In this sense even ferrous and nonferrous metallurgy have common features.
This article mainly discusses some scientific principles relevant in winning of nonferrous metals, in
general, and also discusses some newer developments possible in the future with advancement of
science and technology.

Table 1: Classification of rare metals

___________________________________________________________________
Classification Metals Properties Applications
______________________________________________________________________
Light rare metals Li, Rb, Cs, Be Low density, high reactivity, Nuclear energy,
Unique nuclear properties space technology

Refractory rare metals Ti, Zr, Hf, V, High melting point, high Nuclear energy,
Nb,Ta, Cr, Mo, tempr., strength, corrosion space technology,
W, Re resistance, unique nuclear electronics, che-
properties -mical technology,
metallurgy
Dispersed rare Ga, In, Ti, Ge, Unique electronic properties Electronics metals
Se, Te, Re
Rare earth metals Se, Y, Li, Ce, Nd, Unique optical, magnetic Metallurgy,
(R.E.) Pm, Sm, Eu, Gd, and nuclear properties, catalysis, optics,
Tb, Dy, Ho, Er high reactivity refractories
Tm, Yb, Lu
______________________________________________________________________

2. Resources in India
Available resources form the basis of indigenous commercial activity. If resources are abundant and
not strategic then they can be exported. Yet, processing for value addition is always a more
favourable option. Ongoing industrial activities and R & D create a knowledge base that generate
capabilities to set up plants based on imported resources and/ or to export know-how.
In India, mineral resources are often categorised into the following three kinds.
(a) Adequate to abundant (Al, Be, Cr, Fe, Mn, Mg, Ti, Zn, Th and R.E.)
 (b) Inadequate (Cu, Pb, Au, graphite, V, Ni, Cd, Sn) (Some consider these as adequate for
now)
(c) Poor to scarce (Sb, Bi, B, Co, Hg, Mo, Nb, Ta, P, Sr, Te, Ag, W, Pt, metals)
(may move up to ‘b’ as above in near future.)
Table 2 lists some important minerals and indicates their relative abundance in India.

Table 2.: Some nonferrous mineral resources

______________________________________________________________________
Abundance/ Surplus Self Sufficient Dificient
______________________________________________________________________
Bauxite Zinc ore Gold ore Tine ore
Granite Copper ore Diamond Ores of cobalt
Magnesite Chromite ore Nickel laterite Tungesten
Manganese ore Mineral sands Lead ore Potash
IImenite Baryte Rock phosphate Fluorite
______________________________________________________________________

Table 3 lists production figures for some important minerals and the share of public and private
sectors. From production point of view, there are two groups, namely, the developed (Cu, Pb, Zn and
Al) and the developing (Ni, Co, Ti, W, Cr, R.E.). India has a strong nuclear energy

Table 3.: Production of some important minerals (1993-94) – share of public and private
sectors [2]
______________________________________________________________________
Minerals Unit Public % Private % Total
sector share sector share
______________________________________________________________________
Bauxite Mt 3 51 2 49 5
Gypsum Mt 1 94 Neg 6 1
Manganese Mt 1 46 1 54 2
Limestone Mt 11 15 64 85 75
Chromite ‚000 t 345 32 743 68 10008
Gold-bullion kg 1723 100 - - 1723
Diamond Carats 17649 100 - - 17649
Barytes ‘000 t 226 54 194 46 420
Magnesite ‘000 t 311 52 284 48 595
Dolomite ‘000 t 643 22 2329 78 2972
______________________________________________________________________
Programme under which rate metals are produced to meet indigenous needs.[1] For all metals
production one or more of the following aspects need increasing attention improved characterisation
of available resources up gradation beneficiation of resources by modern scientific techniques,
increased productivity in plants through stricter control of operational parameters and use of up-to-
date technology, more stringent quality parameters for products, minimisation of energy consumption,
stricter environmental control and better waste recycline and / or management, and finally, exploration
for and exploration of newer resources.
Regarding newer resources one can make mention of multimetal sulphides available in several
locations in the country, various indigenous and imported secondary resources, polymetallic ocean
floor nodules etc. Trillions of tonnes of nodules are scattered across the ocean floor. These nodules
whose principal constituents are Mn, Ni, Fe, Cu, Co and siliceous ocean floor silt are collectively
termed as ‘manganese nodules’. They are also potential sources of Ni and Co. Table 4 shows
percentages of some major constituents and compares their availability in land and ocean floor, It
should be noted that the seas contain in dissolved state nearly all metals but generally metal
extraction is not economical except for magnesium.
 Table 4: Reserve of metals in Pacific Ocean nodule[3]
______________________________________________________________________
Elements Amount of element___ Ratio of Nodule reserves/
Weight 109 tonnes Land reserves
______________________________________________________________________
Co 0.35 5.20 5000
Mn 23.86 358.00 4000
Ni 0.98 14.70 1500
Zr 0.06 0.93 1000
Al 2.86 43.00 200
Cu 0.52 7.90 150
Zn 0.46 0.70 10
Fe 13.80 207.00 4
______________________________________________________________________
To understand a scientific basis, metals can be grouped in terms of reactivity based on some
thermodynamic criterion such as hydrogen electrode potential, Table 5 shows how chemical
properties can be under stood on this basis. It should be noted, however, that commercial activities
ultimately depend on economic and technological factors.

3. The Developed Metals Industry

In India, today, there is significant production of Zn, Cu, Pb and Al, although each sector faces stiff
global competition and numerous economic uncertainties. There is now modern technology and
experts examine the position

Table 5: Properties of metals in relation to their positions in electrochemical series[3]

______________________________________________________________________
Metals Electrode potential Remarks
range (volts)
______________________________________________________________________
Li, Rb, Cs, K, B, Sr, 3.01 to 2.38 Forms chlorides, carbonates and sulphates;
Ca, Na, La, Mg is easily oxidized in air and gives very stable
oxides; reacts spontaneously with water,
forms ionic compounds.
Th, Ce, Ti, Be, Hf 2.1 to 2.44 Forms mainly oxides, silicates, or complex
Al, Zr, V oxides; oxidizes on heating; gives stable
oxides; is attacked by steam.
W, Mn, U. Se, 1.1 to 0.335 Forms simple or complex oxides or sulphides;
Zn, Cr, Ga, Fe, oxidizes on strong heating; forms moderately
Cd, In, Ti stable oxides; oxides of less reactive metals are
easily reduced; is attacked by steam.
Ti, Co, Ni, Mo, 0.335 to -0.799 Forms some selenides, tellurides, and
Sn, Pb, Sb, As, arsenides in addition to sulphides and complex
Bi, Cu, Te, Rh, oxides; forms relatively unstable oxides, some
Re, Hg, Ag of which decompose at high temperature; is not
attacked by steam; in many cases shows complex
bonding n compounds.
Sb, As, Bi, Cu, -0.1 to -1.7
Occurs as sulphides, tellurides, or in free state;
Te, Rh, Re, Hg, gives less stable oxide, some unstable even at
Ag, Pd, Ir, Pt, Au room temperature (Pb-Au); is not attacked by steam
or ordinary acids; shows complex bonding in salts.
______________________________________________________________________
periodically to monitor progress and future requirements.[4] With about 0.6 mt/year of production, India
is self sufficient in Al. However, there are short falls in Zn (about 20% against a demand or about
250,000 t/ year) and Pb (about 40% against a demand of about 90,000 t/ year). The situation is worse
for copper where annual demand of about 250,000 t is met 75% by imports. The industry has latest
technology but search for newer processes and intermediate technologies must continue. There is
need for recycling and environmental control. Experts have identified the R & D needs as:
development of newer agents, application of bacterial leaching, use of newer hydrometallurgical
routes employing ion exchange and solvent extraction, extraction of trace, minor and precious metals,
development of newer alloys, use of mathematical models in processes, R & D on ocean floor
nodules, energy minimization, enhancement of productivity and recovery, simplification of flowsheets,
and treatment of secondaries.
Aluminium must play in increasingly important role in the Indian industry. The vitality of the industry
will only be sustained if plants become more efficient and cost competitive and more environment
friendly. Areas identified for particular R & D attention have been discussed elsewhere.[5,6] Both the
Bayer’s process and the Hall Heroult’s process need further improvements. Table 6 lists the future
alumina quality projections. Constant attempts to improve things are yielding better results. Table 7
lists some typical results, achieved by a plant.
Welch,[7] in a recent review, mentions that the energy

Table 6: Future alumina quality projections[5]

______________________________________________________________________
Parameters Typical value Range
______________________________________________________________________
Iron (Fe2 O3), Silica (SiO2) 0.012% 0.015%
Soda (Na2O)-short term 0.30% 0.35%
-long term 0.25%
Specific surface area 70 m2/g 60 m2/g
-45 micron 6% 10% max
-20 micron <1% 2% max
+150 micron 1% 5% max
Attrition index 15% 25% max
Gibbsite 0.10% 0.20% max
ESP dust content Nil Nil
______________________________________________________________________

Table 7: Performances of the HINDALCO Smelter in 1986 (before modernisation) and in 1992-
93 (after modernisation)
______________________________________________________________________
Parameters Value in 1986 Value in 1992-93
______________________________________________________________________
Cell content (kA) 57-58 61-65
Average cell voltage (V) 4.71 4.558
Current efficiency (%) 87.69 93.84
Power consumption (DC) (kWh/kg) 15.99 14.467
Net anode consumption (kg/kg Al) 0.447 0.442
Fluoride consumption (kg/kg Al) 0.1665 0.2472
Gross carbon consumption (kg/kg Al) 0.728 0.606
Average pot life (days) 765 1118
______________________________________________________________________
Consumption has been reduced in some plants to around 13 kWh/kg with current efficiency in excess
of 96%. Efforts are directed towards constructing wettable cathode surfaces which corrode less and
developing non-consumable anodes, better cell design and process optimization etc. Unfortunately,
alternative paths to aluminium, e.g. carbothermic reduction of Al2O3, carbochlorination, electrolysis of
AlCl3 in chloride bath etc have not yet been economically viable. The scientific aspects of
thermodynamics and kinetics associated with the aluminium electrolysis will be described later in
section 7. The industry enjoys much scope for diversification, for example, there is great need of
various special grade alumina alone for various applications.

4. Environmental Aspects : Life Cycle Assessment (LCA)

Process ingredients and systems which are major contributors to environmental degradation are now-
a-days
 Table 8: Some principal wastes of the aluminium industry and their use[2]

Waste Classification Toxic/Non Disposal/Recovery

toxic
I. Bauxite mining
(a) Laterite: Laterite contains gibbsite, Non toxic Partly consumed through blending,
hematite, anatase, kaolinite, quartz, etc. land fill, cement, refractory and oil,
refining industries
(b) Overburden: Blanket of earth of rock Mainly land fill
overlaying the bauxite deposits, mainly Non toxic
consists of hydrated silica or sand.
(c) Dust: Generated from mineral and soil Non toxic Nil
during blasting, excavation transportation
and subsequent handling
II. Bauxite refining
(a) Red mud: The bauxite residue left after the Partially used for bricks and
extraction of alumina by Bayer process Toxic corrugated sheets, dry disposal to
conserve land and possibly
recovery of Fe2O3 and TiO2 by HCl
route
(b) Vanadium sludge: The Bayer liquor on Toxic Soda is neutralized and V2O5 is
chilling precipitates a soft wet crystalline recovered for ferrovanadate
mud containing isomorphous complexes of production
vanadates and phosphates of Na3PO4.NaF,
19H2O and
Na3VO4.NaF,19H2O
III. Power and steam plant
Fly ash: The pulverized coal used in steam Non-toxic Disposal in slurry form is ash dyke
boilers generates non-volatile inorganic fine and used to make bricks and
residue after ignition. The quality of the fly cement
ash generate is proportional to the ash
content of the coal used.
IV Alumina smelter
(a) Cathode carbon: Crumbled and deformed Toxic Disposal in confined area and
spent cathode made up of anthracite as incineration for recovery of
well as metallurgical coke fractions bound fluorides salts
with pitch coke, becomes graphitised and is
impregnated with fluoride salt
(b) Refractories: The fire clay and insulating Non-toxic Disposal in confined are,
bricks housed around the cathode carbon separation of diatomic bricks for
are also excavated from the cathode shell use as filter acid and recycling of
properly excavated fire clay bricks
(c) Primary smelter gases: During electrolysis, Toxic Stack disposal of clean gas,
harmful elements such as oxides of carbon, recycled of regenerated cryolite in
sulphur, tar vapours, fluoride gases and cells and incineration of ESP dust
particular matter along with air, are carried to recover cryolite.
out to electrostatic precipitator and
subsequently to wet scrubbers
Identified by making use of LCA which also serves as a basis for cooperation between the technical
specialists and environmentalists of three components, viz. (i) life cycle inventory analysis which
considers inputs for production emissions and pollutants throughout life cycle, (ii) life cycle impact
analysis which can be qualitative or quantitative, and (iii) life cycle improvement analysis which aims
at minimizing the adverse effects. In this, quantitative evaluations are mode of the resources and
energy used and waste released to the environment during the entire life (cradle go grave) cycle of
the product, package or process. As an example, consider production of a 50 kW electric pump, which
would need about half a tonne of coal for electricity generation and half a tonne of metal. The CO2
emitted is about 2 tonnes. Assuming a life of 20 years, the pump would consume some 1000 tonne of
coal emitting 400 tonne of CO2 and consume 9000 MWh of electricity. Thus, the impact of the pump
on the environment in terms of CO2 emission above is 2000 times than required for its production.
Various aspects of impact of the nonferrous metals industry on the environment have been discussed
more in detail in the present monograph by other experts. It should be noted, however, there are
remedial measures now technologically feasible. Table 8 lists some principal wastes of the aluminium
industry and possible treatment methods.[2]

5. Metals for Secondary Sources: The Energy Aspect

Increasing quantities of scrap and now being processed for increased production of metals. In North
America and Japan, more than a third of the output now comes form scrap. There is great deal of
recycling in the case of other metals too for which the figures may be approximately as follows: Pb, -
40; Au,-40; Ni,-20; Cu,-20; ferrous,-15; stainless steel,-80; and Zn, -5. In addition to the environmental
protection such as recycling leads to substantial energy saving. Table 9 shows some figures for
energy requirement for production of metals from their concentrates in theory and practice.
As is seen, the process efficiencies as usually low. Although there are scientific and technological
reasons for such wide gaps between theory and practice, it is possible to effect substantial energy
savings by use of correct science and technology. Recovery from secondary sources plays an
important role because energy consumption is often substantial lowers as indicated in Table 10.
Metals and minerals industry is most energy intensive. In advanced countries, it may amount to only
10-15% of the total volume of manufactured output, but it consumes 50% or more of delivered energy,
the metal sector accounting for about two-third of this.

Table 9: Energy requirement for production of metals from their concentrates.[3]

Metal Process energy (106 Free energy 106 kCal/ Process efficiency
kCal/ tonne) tonne (%)
Titanium sponge 90.4 4.0 4.4
Magnesium ingot (sea- 85.4 5.1 5.9
water process)
Aluminium ingot 49.6 6.4 12.9
Ferrochrome low 31.5 2.2 7.0
carbon
Sodium metal 22.9 1.8 7.8
Nickel cathode 22.4 0.8 3.5
Ferrochrome high 13.9 2.2 15.8
carbon
Ferromanganese (arc 12.1 1.8 14.8
furnace)
Copper refined 12.1 0.45 3.7
Zinc (electrolyte) 12.1 1.1 9.0
Ferromanganese (blast 10.8 1.8 17.0
furnace)
Steel slab 5.5 1.4 26.0
Tin ingot 4.8 1.0 20.0
Lead ingot 4.5 0.2 4.4
 Table 10: Unit energies for production of primary and secondary metals[3]
Metal Primary from ore (106 Secondary (106 kCal/tonne)
kCal/tonne)
Magnesium 90.2 3.0
Aluminium 61.5 3.0
Nickel 36.3 3.8
Copper 28.2 4.5
Zinc 16.4 4.5
Steel 8.1 3.3
Lead 6.8 3.0

The energy intensive values of some important processes are intensive values of some important
processes are indicated in Table 11, which compares actual fuel consumption with theoretical
minimum values (approximate figures). The Table also indicates potential energy saving based on
today’s technology.
The energy requirement for a process is based and understood in terms of a parameter called
Process Fuel Equivalent (PFE).
Use of PFE eliminates many misconceptions. An aluminothermic process is not necessarily attractive
from energy point of view because of exothermic because

Table 11: Comparison of specific fuel consumption process with theoretical minimum[8]
Typical specific fuel Potential specific fuel Theoretical minimum
consumption consumption using specific fuel
(BTU/tonne) technology consumption based
(BTU/tonne) upon thermodynamics
availability analysis
(BTU/tonne)
Iron and steel 20x106 15x106 6.0x106
Petroleum refining 4x106 3x106 0.4x106
Paper 40x106 20x106 Negligible
Primary aluminium 17x106 140x106 25.2x106
production
Cement 7x106 4x106 0.8x106

Table 12: Energy requirements for metal production from concentrates (approxi-mate values)

Metal Process Product PFE(GJ/tm)

(a) Pyrometallurgy Steel ingot 22
Fe Blast furnace, oxygen
steelmaking
Cu Flash smelt (O2), Cu0 cathode 23
convert, electrofine
Pb Blast furnace, dross, Refined Pb0 21
fire-refine
(b) Hydro- and electrometallurgy
Cu Leach sulphide Cu0 cathode -100
concentrate, electrowin
Zn Roast, leach, Special high grade Zn0 55
electrowin
Al Bayer leach, Hall Al0 ingot 280
electrolysis
Aluminium itself consumes energy in its production. Similarly, in theory use of scrap metal also is not
necessarily attractive unless it is available as a zero energy source. Sponge iron produced as an
alternative to scrap iron cannot necessarily lead to overall energy economy during steelmaking.
Some people often have the misconception that because of the high temperature involved,
pyrometallurgy, in general, is more energy intensive. This is often not true because many high
temperature steps, such as roasting of sulphides generate exothermic heat and hot flue gases also
allow waste heat recovery. Moreover, handling of large volumes of liquors, drying, evaporation and
other units operations and, particularly, electrolytes and electrorefining require significant energy in
hydro- and electrometallurgy. Table 12 lists some energy requirement values typical of pyro- and
hydro and electrometallurgical operations.

6. Extraction as a separation process

Basically, all extraction processes involve separation of a desired phase from an input source. In
pyrometallurgy, this often achieved through a slag-metal reaction. At higher temperatures, there is
often closer approach to equilibrium and, therefore, it is often possible to apply thermodynamics
directly. We can compare an extraction step to some common methods of separation as summarized
in Table 13.
In metal extraction, there can be three basic approaches: (a) produce a bulk metal and then refine, (b)
produce and simultaneously purify, and (c) produce a pure compound to then produce a pure metal.
Common bulk metals are generally produced by (a) and (b) whereas

Table 13: Comparison of separation processes

Extraction
Addition of solvent
Removal of solvent
Two-phase liquid mixture
Selectivity
Change of temperature
Solvent mixture
Solvent separator
Solvent-rich solution saturated
with solvent
Solvent-rich solution with
more solvent than needed for
saturation
Solvent-lean solution
saturated with solvent liquid at
boiling point
Solvent-lean solution with less
solvent then needed to
saturate it
Distillation Slag-metal reaction
Addition of heat Addition of oxygen (S, Cl2 etc.)
Removal of heat Removal of oxygen by reduction
Mixture of liquid and Metal and slag phases
vapour
Relative volatility Relative stability of oxide
Change of pressure Change of temperature or slag
additions
Reboiler Furnace for oxidation of metal
Condenser Furnace for reduction of slag
Vapour at boiling point Slag in equilibrium with metal
Superheated vapour Slag more oxidized than for
equilibrium with metal
Liquid at boiling point Metal in equilibrium with slag
Liquid below boiling point Metal phase with less oxygen than
needed for saturation

for rare metals often adopt method (c). In pyrometallurgy, the usual steps are: drying, crushing,
grinding, beneficiation, agglomeration, roasting, reduction, smelting, refining etc. The usual steps in
hydro- and electrometallurgy are: leaching, solid/liquid separation, ion exchange, solvent extraction,
precipitation, electrolysis, electrorefining etc. There can be special techniques such as bioprocessing,
vapour transport processes, plasma processing, vacuum melting/ refining, sublimation, arc/beam
melting, zone refining etc. The final steps in any refining process become increasingly difficult
because the purified material tends to absorb impurities from the environment readily.
Thermodynamic considerations show that a metal is more stable when it is impure.[8] Therefore, often
one has to strike a balance between quantity and quality, and purification is based on carried out in
stages and in a selective manner eliminating impurities in order of priority, preferably.
Understanding of thermodynamic principles and kinetic theory can be of great advantage. It explains
results achieved by a great deal of trial and error. It can be used in guiding or altogether eliminating
trial and error. Many extraction methods, particularly those for rare metals, have been based on
theoretical and bench scale studies alone. The fundamental concept is described now. Essentially, in
all extraction and refining processes, a desired metallic value is transferred from one phase to
another. This is made possible by the presence of an activity or pressure gradient at metal/slag
separation, solid/gas separation, solid/liquid separation, liquid/liquid separation of whatever. Consider
some simple examples, ferroalloys are produced with relative ease because the alloying element
being at lower activity in solution allows easier reduction of its oxide. Consider extension of the idea to
beryl, BeO which is a very stable oxide. Beo is readily reduced by carbon when there is a large
excess of copper and Be is produced as Be-Cu.
BeO (s) + C (s) + Cu (I) = Be-Cu (s) + CO (g) (1)
The lower the Be content, lower is aBe and more feasible is the reaction to the right. It is another
matter that Be is often used as Be-Cu alloy just as Mn, Si, Ti, V, Ni etc are often used more as
ferroalloys a for deoxidation and/ or alloying rather than as pure metals.
Consider another simple example. One may want to have nickel impurities in the slag phase during
copper metallurgy so that nickel can be subsequently recovered from some treatment of slag. Many
years ago, the author reported some data[9] on activity and solubility of different oxides such as NiO,
FeO, CoO, Cu2O etc. in a standard silicate solvent (eutectic Na2O.SiO2 –K2O.SiO2). At all
temperatures NiO showed distinctive low solubility values. Assuming similar results in other slag
system, one can say that during copper smelting and converting, nickel will rather go to the copper
metal phase rather than the slag phase.
Techniques involved in rare metal extraction are different from conventional reduction, smelting and
refining processes familiarly adopted for common metals. Reasons for this which are discussed
elsewhere [10-12] make it imperative that they be produced first in the form of a pure compound in
which pure metal is extracted.
Many new developments which created initial excitement have not proved commercial viability
eventually. Mention may be made of the ALCOA process based on AlCl3 electrolysis (in chloride
solvent) using bipolar electrodes and continuous copper smelting (WORCRA process, NORANDA
Process). However, many of the ideas generated have found applications in other sectors.

7. Application of Thermodynamics and Kinetics-some examples

Even if science and technology so decide there cannot be a unique process for every metal because
an industry has to depend on diverse factors relating to local conditions such as availability and nature
of raw materials, labour and capital, traditions, market demands and other economic factors,
governmental regulations etc., aluminium is produced universally by electrolysis and lead by blast
furnace. But, for zinc and copper there are both the options of pyrometallurgy and hydro- and
electrometallurgy. There are greater options for rare metals where scientific research constantly
modify the processes of extraction and refining.
A great majority of extraction processes mainly depend on reduction of oxides or halides by carbon,
carbon monoxide or hydrogen provided the reduction temperatures is sufficiently high as governed by
thermodynamic criteria. However, at high temperatures required for reduction in may carbides and
nitrides tend to become stable. Thus, Al2O3 can be reduced by carbon but one will get aluminium
nitride or carbide only and not the metal. Similarly, one can reduce ilmenite (FeO.TiO2) by carbon in
plasma furnaces which allow easy attainment of high temperatures. However, one cannot produce the
metal or ferrotitanium because the thermodynamically stable phase is Fe-Ti-C.
Reduction reactions are controlled using mainly three factors: temperature, pressure and presence of
another phase which dissolves either the metal produced or the resultant gangue so as to reduce the
activity and drive the reaction thermodynamically. Consider some random examples which do not
require further explanation.

Reactions insensitive to pressure:

WO3 (s) + 3H2 (g) = W (s) + 3H2O (g) (2)
FeO (s) + CO (g) = Fe (s) + CO2 (g) (3)
Reactions sensitive to pressure – aided by vacuum (Pidgeon’s process);

2(MgO.CaO) (s) + Fe.Si (s) 2Mg (g) + Fe (s) + 2CaO.SiO2 (s) (4)

5CaO (s) + 2Al (I) 3Ca (g) + 2CaO.Al2O3 (s) (5)

The conditions required for such reactions are available in standard texts and, therefore, not
mentioned here. Under vacuum, it is also possible to reduce oxides of Pb, Zn, Mn, Bi with silicon. But
conventional methods are cheaper.
Aluminothermic reduction can produce many metals from their compounds as metals or ferroalloys,
Chlorides are also reduced metallothermically. The following are some examples.
TiCl4 (g) + 2Mg (I) = Ti (s) + 2MgCl2 (I) (6)
SiCl4 (g) + 2Zn (g) = Si (s) + 2ZnCl2 (I) (7)
BeF2 (I) + Mg (I) = Be (I) + MgF2 (I) (8)
ZrCl4 (I) + 2Mg (I) = Zr (s) + 2MgCl2 (I) (9)
ZrO2 (s) 2Ca (s) + Zr (s) + 2CaO (s) (10)
UO3 (s) + 3Ca (s) = 3CaO (s) + U (s) (11)
UF4 (s) 2Ca (s) = 2CaF2 (s) + U (s) (12)

Metallothermic reactions are exothermic, reduction by calcium often releasing the maximum heat
which can melt both the slag and the metal for a good clean solid/ liquid separation. Na and K are not
preferred as reducing agents because they volatilize. Consider reduction of ThF4 by Ca. If one adds
some ZnCl2 into the system, then the reactions is written as:
ThF4 + 0.3ZnCl2 + 2.6Ca = Th +2CaF2 + 0.3CaCl2 + 0.3Zn + 0.3Ca (13)
ZnCl2 reduction produces extra heat, acts as a booster and produces a Th-Zn alloy where lower
activity of Th drives the reaction more to the right. Sometimes, a flux may be added only to dissolve
the product compound to aid the reaction. Estimation of exothermic heat forms a critical factor in such
reactions. Such estimations are possible by calorimetry of differential thermal analysis. [13] The
importance of reaction heat may be illustrated by considering aluminothermic reduction of Mn ores.
Table 14 shows some data on heat balance for reduction of different oxides.
Table 14: Heat balance for aluminothermic reduction of manganese oxides[3]
Oxide Heat required (kCal) Heat available mole of Mn/Al ratio in reduction
Al2O3 (kCal) charge
MnO 157 124 1.5
Mn3O4 139 152 1.125
MnO2 121 214 0.75
Reduction of MnO2 by Al will generate excess heat which is sometimes controlled by adding cold iron
chips or by using coarse particles which retard reaction rate. On the other hand, when available heat
falls short of the required heat, including that of heat losses, the process may be made autogenous
either by preheating the charge or by adding boosters such as NaNO3 which provide extra heat. A
realatively fluid sag can be obtained by using alloys of Al with Ca and / or Si and also by using CaF2.
Similarly use of CaCl2 help the following reaction.
ThO2 + 2Ca +2.4CaCl2 = Th + 2CaO + 2.4CaCl2 (14)
It is difficult to accept that such a reaction really proceeds through collision of four atoms of Na and
one molecule of TiCl4 in gas phase because probability of this will be insignificant. It is possible to
write a large number of other reactions involving lower chlorides of TiCl3, TiCl2, TiCl, which are known
to be stable and which, together with NaCl form liquid phases. Presumably, reactions in this liquid
phases. Presumably, reactions in this liquid phase bring out the reduction. The mechanism is
electrochemical and titanium metal produced is crystalline. TiCl4 can be reduced by Mg also.
TiCl4 (I) + 2Mg (g) = 2MgCl2 + Ti (s) (15)
In this case, it is not possible to write stepwise reactions in terms of subchlorides and no
electrochemical mechanism is possible. That is why one does not get a crystalline product by
magnesium reduction, and vacuum melting of sponge becomes necessary. Haldies are common
starting materials in rare metal extraction and these can be produced through chlorination reaction,
consider the following reaction.
TiO2 (s) + 2Cl2 (g) = TiCl4 (g) + O2 (g) (16)
It is easily shown by thermodynamic calculations that there is little conversion even at temperatures
as high as 1000oC. If, however, carbon is present then the reaction, now called ‘indirect’ chlorination,
is highly feasible.
TiO2 (s) + 2C(s) + 2Cl (g) = TiCl4 (g) + 2CO(g) (17)
Carbon thus encourages removal of oxygen in association with Ti by forming stable CO. Chlorination
reactions can be selective and, therefore, exploited in chemical beneficiation. Thus, iron oxides in
ilmenite are easily chlorinated in presence of carbon by a variety of chlorinating agents.

8. R & D for the future

Unit operations, unit processes and flowsheets in nonferrous metallurgy will continue to be modified
with increasing applications of modern chemistry, physics, chemical engineering and technology and
general geosciences. With gradual depletion of rich ores, there will be greater need of
characterization of newer, complex and/ of lean ores. Rao et al.,[14] for example, has shown how
multimetal sulphides can be characterized using a variety of techniques simultaneously. Attempts will
continue to adopt totally new technologies (e.g. ALCOA) as well as introduce improvements in
process steps. For example, continuing R & D is making bioleaching of ores an increasingly attractive
option. Leaching reactions are being made more selective by better controlling of process parameters
and use of newer reagents, accelerated by unconventional techniques such as by application of
ultrasound.[15] Electrowinning may be drastically improved by better cell design, use of newer
materials for electrodes, control of fluid flow to aid diffusion steps, fluidized electrodes etc. In
pyrometallurgy too, advances continue. Flash roasting and fluidized bed roasting processes may
improve further. Unfortunately, interesting results of many R & D programmes take a long time to go
beyond the laboratory stage. Developments in some areas may not see any commercial applications.
One needs to reexamine use of hydrogen as reducing agent. Through a powerful agent, its use is
restricted because of its cost and potential danger in its use. For nearly two decades now hydrogen
has been used to reduce aqueous amines of copper, nickel and cobalt to produce these metals as
powders in presence of a catalyst. Several million tonnes of high purity powders have found
applications in powders in presence of a catalyst, dispersion, strengthening of metals and in plasma
spraying, SO2 and CO can also be used as reducing agents. The basic reaction may be written as
follows:
M2+ + Z/2 (H2) = M2+ + Z+H (18)
Reduction is made more feasible by increases in hydrogen pressure and pH (lower acidity). It is easily
seen that while noble metals and some metals placed slightly higher than hydrogen are reduced (Fe,
Ni, Co), the process cannot work for zinc or rare metals placed even higher. In these cases,
enormous pressures would be relieved even if the solution is highly alkaline. Fused salt electrolysis
will continue to play an important role for rare metals in particular and attempts will continue towards
energy minimization. Table 15 summarises the present features of electrowinning of some reactive
metals.
Another area which merits attention is that of vapour transport processes first introduce nearly a
hundred years ago. The so-called ‘iodide process’ applied for nickel refining is an example.
45oC
Ni (s) + 4CO (g) Ni(CO)4 (19)
240oC
A similar reaction for aluminium refining is written as follows:
1000oC
AlCl3 (g) + 2Al(I) (impure) 3AlCl (g) (20)

700oC
3AlCl (g) 2Al (pure) + AlCl3 (g) (21)
Such processes can be looked upon as ‘indirect’ distillation where a gaseous phase picks up metallic
values in one reactor under one condition of temperature and pressure to form an intermediate
gaseous species, which is made to decompose in another reactor under a different condition of
 temperature and pressure to release purified metal. The reagent gas is re-circulated. In theory, this
techniques is applicable for a wide variety of metals, the process being governed in theory by
magnitudes of enthalpy and entropy changes. It is anticipated that the greatest development of vapour
transport processes will occur in connection with direct treatment of ores. As most of the chemical
reactions are carried out in sealed reactors and many of the reactants allow re-circulation, this type of
processes will be environment friendly. Advancement of technology social pressures may well induce
greater attention to these processes which are yet to find large scale commerciali-zation.
A priority area for India is titanium because there are large ilmenite deposits. Only a small beginning
has been made by pilot plant scale production of small quantities of the metal by the Kroll’s process
where TiCl4 is reduced by magnesium. This makes it imperative that magnesium is also produced
indigenously. Shortage of electric power stands in the way of application of the well known Sorel
Process or its variations. In this process, ilmenite is smelted by carbon to produce pig iron and a
titanium containing slag from which titanium can be recovered as a volatile chloride and then reduced.
Energy consumption may be minimized by first producing synthetic rutile, TiO2 through rotary kiln
reduction of ilmenite and subsequent removal of iron by the process of ‘rusting’, titanium can then be
recovered by different methods. Finally, there is

Table 15: Some features of fused salt electro winning of reactive metals

Current Cell Energy

Tempr.
Metal Bath composition efficiency voltage required
(oC)
(%) (volts) (kWh/kg)
Aluminium Cryolite Al2O3
950-980 85-90 4.5-5.3 17.6
(liquid)
Magnesium MgCl2-NaCl-CaCl2
700-790 80-90 6.5-7.5 18.7
(liquid)
Misch metal ReCl3 (alkali or alkaline
800-900 45 14 16
(liquid) earth chlorides)
Sodium (liquid) CaCl2-NaCl 590 80 6.9 10.5
Tantalum K2TaF7 (alkali metal
800-950 - - -
(dendrite) chloride)
Titanium K2TaF6-NaCl TiCl4 in 740-760 - 4.5 -
(dendrite)

LiCl-NaCl-KCl 500 90 6-8 -

Zirconium K2ZrF6-NCl
800-850 - 4.5 -
(dendrite)
Beryllium BeCl2-NaCl-KCl
350 - 6-9 -
(flakes)
(Energy densities range from 0.5-1.2 A/cm2)
a scope for recovery of vanadium form vanadiferrous iron ores and also from red mud. No concrete
steps have been taken in this direction although some R & D has been done.

9. Nonferrous Metallurgy at Regional Research Laboratory, Bhubaneswar

This Laboratory has done some notable theoretical and applied work in the sector of nonferrous
minerals and metals. These relate to areas of geology, environment, characterization, beneficiation,
agglomeration, roasting and processing of ores, minerals and secondaries using hydrometallurgy,
pyrometallurgy and plasma processing techniques. Two important programmes are briefly mentioned.

9.1 Processing of Ocean Nodules

This Laboratory has developed a hydro and electrometallurgical, flowsheet based on which a
demonstration plant (500 kg/day) is being set up at Hindustan Zinc Limited (HZL), Udaipur after
successful pilot plant trials. The metallic values of Cu, Ni and Co are solubilised in this process as
ammine complexes. The steps involved are ammonia leaching (with SO2 reduction), coextraction of
Cu, Ni and Co using solvents, selective striping of Ni followed by Cu and final electrowinning of
metals. This process does not have any pyrometallurgical step and has flexibility to produce metals
as compounds if so preferred, e.g. Co and Ni as sulphides.

9.2 Processing of Chromite Overburden

Millions of tones of chromite overburden (COB) stockpiled at Sukinda valley of Orissa poses an
environmental problem. Containing 0.7-0.8% Ni and approximately 0.1% Co, it is also a valuable
source of nickel. Every year the same 6-7 mt of COB is stockpiled and this contains more than the
country’s annual requirements (-30,000 tonne nickel), A consortium of several national Institutions and
Laboratories with Regional Research Laboratory, Bhubaneswar as the nodal agency has now
developed a process for recovering Ni and Co from this COB and a demonstration plant to treat 10
tpd COB to produce Ni of 10 tonne capacity per annum is being established. It is hoped that this will
lead to eventual establishment of a full-fledged industry to produce around 10,000 tpa on Ni which is
now imported to the extent of about 30,000 tpa. The major steps in the processes are reduction
roasting, ammoniacal leaching, solvent extraction followed by electrowinning of Ni or precipitation of
basic nickel carbonate followed by its dissolution in nickel spent electrolyte and electrowinning.

10. Concluding Remarks

The minerals and metallurgical industry enjoys much scope for diversification. Ongoing industrial
activities and R & D create a knowledge base that generate capabilities to set up plants based on
indigenous/ imported resources and / or to export know-how.
To understand a scientific basis, metals can be grouped in terms of reactivity based on some
thermodynamic criterion such as hydrogen electrode potential. Understanding of thermodynamic
principles and kinetic theory can be of great advantage and the applications can be used in guiding or
altogether eliminating trial and error.
Although there are scientific and technological reasons for such wide gaps between theory and
practice, it is possible to effect substantial energy savings by use of correct science and technology.
(edited text of paper published in the Proceedings of International Seminar on Nonferrous Minerals &
Metals, Nonferrous Meet ’99 on February 18-19, 1999 at Bhubaneswar)

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Reference Book:
Minerals Processing & Engineering
Mr. V. N. Mishra, Mr. G. D. Yadav, Mr. K. S. Rao