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, Nb,Ta, Cr, Mo, W, Re High melting point, high tempr., strength, corrosion resistance, unique nuclear properties Nuclear energy, space technology, electronics, che-mical technology, metallurgy Electronics metals

Dispersed rare Ga, In, Ti, Ge, Unique electronic properties 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) (c)

Inadequate (Cu, Pb, Au, graphite, V, Ni, Cd, Sn) (Some consider these as adequate for now) 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-todate 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 Al, Zr, V W, Mn, U. Se, Zn, Cr, Ga, Fe, Cd, In, Ti Ti, Co, Ni, Mo, Sn, Pb, Sb, As, Bi, Cu, Te, Rh, Re, Hg, Ag 2.1 to 2.44 Forms mainly oxides, silicates, or complex oxides; oxidizes on heating; gives stable oxides; is attacked by steam. Forms simple or complex oxides or sulphides; oxidizes on strong heating; forms moderately stable oxides; oxides of less reactive metals easily reduced; is attacked by steam.

1.1 to 0.335

are

0.335 to -0.799

Forms some selenides, tellurides, and arsenides in addition to sulphides and complex oxides; forms relatively unstable oxides, some of which decompose at high temperature; is not attacked by steam; in many cases shows complex bonding n compounds.

Sb, As, Bi, Cu, Te, Rh, Re, Hg, Ag, Pd, Ir, Pt, Au

Occurs as sulphides, tellurides, or in free state; gives less stable oxide, some unstable even at 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

-0.1 to -1.7

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 Bayers process and the Hall Heroults 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 ______________________________________________________________________ 0.012% 0.015% Iron (Fe2 O3), Silica (SiO2) 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 199293 (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 nowa-days

Table 8: Some principal wastes of the aluminium industry and their use[2] Waste Classification I. (a) Bauxite mining Laterite: Laterite contains gibbsite, hematite, anatase, kaolinite, quartz, etc. Overburden: Blanket of earth of rock overlaying the bauxite deposits, mainly consists of hydrated silica or sand. Dust: Generated from mineral and soil during blasting, excavation transportation and subsequent handling Bauxite refining Red mud: The bauxite residue left after the extraction of alumina by Bayer process Toxic Partially used for bricks and corrugated sheets, dry disposal to conserve land and possibly recovery of Fe2O3 and TiO2 by HCl route Soda is neutralized and V2O5 is recovered for ferrovanadate production Non toxic Partly consumed through blending, land fill, cement, refractory and oil, refining industries Mainly land fill Non toxic Non toxic Nil Toxic/Non toxic Disposal/Recovery

(b)

(c)

II. (a)

(b)

Vanadium sludge: The Bayer liquor on chilling precipitates a soft wet crystalline mud containing isomorphous complexes of vanadates and phosphates of Na3PO4.NaF, 19H2O and Na3VO4.NaF,19H2O Power and steam plant Fly ash: The pulverized coal used in steam boilers generates non-volatile inorganic fine residue after ignition. The quality of the fly ash generate is proportional to the ash content of the coal used.

Toxic

III.

Non-toxic

Disposal in slurry form is ash dyke and used to make bricks and cement

IV (a)

Alumina smelter Cathode carbon: Crumbled and deformed spent cathode made up of anthracite as well as metallurgical coke fractions bound with pitch coke, becomes graphitised and is impregnated with fluoride salt Refractories: The fire clay and insulating bricks housed around the cathode carbon are also excavated from the cathode shell Primary smelter gases: During electrolysis, harmful elements such as oxides of carbon, sulphur, tar vapours, fluoride gases and particular matter along with air, are carried out to electrostatic precipitator and subsequently to wet scrubbers Toxic Disposal in confined area and incineration for recovery of fluorides salts

(b)

Non-toxic

Disposal in confined are, separation of diatomic bricks for use as filter acid and recycling of properly excavated fire clay bricks Stack disposal of clean gas, recycled of regenerated cryolite in cells and incineration of ESP dust to recover cryolite.

(c)

Toxic

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 Titanium sponge Magnesium ingot (seawater process) Aluminium ingot Ferrochrome low carbon Sodium metal Nickel cathode Ferrochrome high carbon Ferromanganese (arc furnace) Copper refined Zinc (electrolyte) Ferromanganese (blast furnace) Steel slab Tin ingot Lead ingot Process energy (106 kCal/ tonne) 90.4 85.4 49.6 31.5 22.9 22.4 13.9 12.1 12.1 12.1 10.8 5.5 4.8 4.5 Free energy 106 kCal/ tonne 4.0 5.1 6.4 2.2 1.8 0.8 2.2 1.8 0.45 1.1 1.8 1.4 1.0 0.2 Process (%) 4.4 5.9 12.9 7.0 7.8 3.5 15.8 14.8 3.7 9.0 17.0 26.0 20.0 4.4 efficiency

Table 10: Unit energies for production of primary and secondary metals[3] Metal Magnesium Aluminium Nickel Copper Zinc Steel Lead Primary from kCal/tonne) 90.2 61.5 36.3 28.2 16.4 8.1 6.8 ore (106 Secondary (106 kCal/tonne) 3.0 3.0 3.8 4.5 4.5 3.3 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 todays 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 consumption (BTU/tonne) fuel Potential specific fuel consumption using technology (BTU/tonne) 15x106 3x106 20x106 140x106 4x106 Theoretical minimum specific fuel consumption based upon thermodynamics availability analysis (BTU/tonne) 6.0x106 0.4x106 Negligible 25.2x106 0.8x106

Iron and steel Petroleum refining Paper Primary aluminium production Cement

20x106 4x106 40x106 17x106 7x106

Table 12: Energy requirements for metal production from concentrates (approxi-mate values) Metal Fe Cu Pb Process Product (a) Pyrometallurgy Steel ingot 22 Blast furnace, oxygen steelmaking Flash smelt (O2), Cu0 cathode convert, electrofine Blast furnace, dross, Refined Pb0 fire-refine (b) Hydro- and electrometallurgy Leach sulphide Cu0 cathode concentrate, electrowin Roast, leach, Special high grade Zn0 electrowin Bayer leach, Hall Al0 ingot electrolysis PFE(GJ/tm)

23 21

Cu Zn Al

-100 55 280

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 Addition of heat Removal of heat Mixture vapour of liquid and Slag-metal reaction Addition of oxygen (S, Cl2 etc.) Removal of oxygen by reduction Metal and slag phases Relative stability of oxide Change of temperature or slag additions Furnace for oxidation of metal Furnace for reduction of slag Slag in equilibrium with metal Slag more oxidized equilibrium with metal than for

Relative volatility Change of pressure Reboiler Condenser Vapour at boiling point Superheated vapour

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) FeO (s) + CO (g) = Fe (s) + CO2 (g) (2) (3)

Reactions sensitive to pressure aided by vacuum (Pidgeons process); 2(MgO.CaO) (s) + Fe.Si (s) 5CaO (s) + 2Al (I) 2Mg (g) + Fe (s) + 2CaO.SiO2 (s) (4) (5)

3Ca (g) + 2CaO.Al2O3 (s)

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) SiCl4 (g) + 2Zn (g) = Si (s) + 2ZnCl2 (I) BeF2 (I) + Mg (I) = Be (I) + MgF2 (I) ZrCl4 (I) + 2Mg (I) = Zr (s) + 2MgCl2 (I) ZrO2 (s) 2Ca (s) + Zr (s) + 2CaO (s) UO3 (s) + 3Ca (s) = 3CaO (s) + U (s) UF4 (s) 2Ca (s) = 2CaF2 (s) + U (s) (6) (7) (8) (9) (10) (11) (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 MnO Mn3O4 MnO2 Heat required (kCal) 157 139 121 Heat available mole of Al2O3 (kCal) 124 152 214 Mn/Al ratio in reduction charge 1.5 1.125 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 Krolls 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 Metal Aluminium (liquid) Magnesium (liquid) Misch (liquid) Tantalum (dendrite) Titanium (dendrite) Bath composition Cryolite Al2O3 MgCl2-NaCl-CaCl2 alkaline Tempr. (oC) 950-980 700-790 800-900 590 (alkali metal 800-950 740-760 500 800-850 350 Current efficiency (%) 85-90 80-90 45 80 90 Cell voltage (volts) 4.5-5.3 6.5-7.5 14 6.9 4.5 6-8 4.5 6-9 Energy required (kWh/kg) 17.6 18.7 16 10.5 -

metal ReCl3 (alkali or earth chlorides) CaCl2-NaCl K2TaF7 chloride)

Sodium (liquid)

K2TaF6-NaCl TiCl4 in LiCl-NaCl-KCl

Zirconium (dendrite)

K2ZrF6-NCl

Beryllium BeCl2-NaCl-KCl (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 countrys 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) REFERENCES 1. 2. 3. 4. Gupta, C.K. and Bose, P.K., Bull. Mater. Sci., 1989, 12 (3-4), 381-405. Singh, B.P. and Ray, H.S., Recent advances in nonferrous metallurgy, In Proc. Multifacets on Metallurgy: Emerging Trends, ed. Amit Chatterjee, ATM-97, Jamshedpur, 1997, pp. 225-235. Ray, H.S., Sridhar, R. and Abraham, K.P., Extraction of nonferrous metals, affiliated EastWest Press Pvt. Ltd., New Delhi, 1985. Report of the Technology Advisory Group on Nonferrous Metals, Directorate General Technical Division, Ministry of Industry, Government of India, May 1993, A.C. Wadhawan, And overview of major nonferrous mineral and metals in India, Prof. N.P. Gandhi memorial Lecture, 1996, ATM, IIM, Bangalore, Nov. 14-17, 1998. Dixon, P.H. and Schenk, H.J., In Proc. Intl. Symp. on Aluminium Global Scenario, IIM, Calcutta, Nov. 1995. Ramachandran, T. R., In Proc. Intl. Symp. on Aluminium Global Scenario, IIM, Calcutta, Nov. 1995. Welch, B.J., Futuristic smelting technology for aluminium In Souvenir 6th Intl. Symp. Advances in Electrochemical Science and Technology. SAEST, Chennai, 26-28 Nov 1998, pp. 38-56. Ray H.S. and Panigrahy, S.C., Energy and the metallurgical industry Q.I.P. Notes, Department of metallurgical Engineering. Indian Institute of Technology Kharagpur, 1987. Alocock, C.B., Trans. IIM, 1974, 27(4), 183. Wills, G.M., Principles of refining by slag-metal reactions, In Proc. Intl. Symp. Advances in Extractive Metallurgy and Refining, ed. M.J. Jones, IIM, London, 4-5 Oct. 1991, pp. 162. Ray, H.S., Trans, Ind. Ceram. Soc., 1969, 27(3), pp. 82. Babu, R.S. and Sundaram, C.V., Indian Rare Metal Industry The Future Prospects, ATM, IIM, Calcutta, Nov. 1989, In souvenir Metallurgy of Some Rare and Rare Earth Metals in India, ed. P.R. Roy, Intl. Symp. on Nonferrous Metals, IIM, Calcutta, Nov. 1989. Sarangi, B., Ray, H.S., Tripathy, K.K. and Sarangi, A., J. Thermal Analysis, 1995, 44, 441 451.

5. 6. 7. 8. 9. 10. 11. 12. 13.

14. 15. 16.

Sarveswara Rao K., Das, R.P., Mukunda, P.G. and Ray. H.S., Met. Trans. B, 1993 24B, 937945. Sarvesware Rao, K., Muralidhar, J. and Ray, H.S., Metals Meterials and Processes, 1997, 9(1), 25-32. Swamy, K.M., Sarveswara Rao, K., Narayana, K.L., Murty, J.S. and Ray, H.S., Min. Proc. Ext. Met. Review, 1995, 14, 179-192.

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