Production of Magnesium

• Magnesium ores:
• The most important minerals of magnesium are dolomite (MgCO3.
CaCO3); magnesite (MgCO3); MgCl2 and MgSO4 present in sea water;
brucite [Mg(OH)2]; carnallite (MgCl2.KCl.6H2O), present in exposed
sea beds; olivine (Mg2SiO4); serpentine (Mg3Si2O7).
• India has a abundant reserves of the first three minerals. At present ,a
major portion of the worlds magnesium is produced from these three
minerals.
• The commercial minerals, namely dolomite and magnesite, and the
magnesium hydroxide derived from sea-water have a sufficiently high
magnesium content and do not require upgrading before being subjected
to subsequent metal extraction process.
• Two main types of production processes for the extraction of metallic
magnesium have emerged.
• (A) thermal reduction of oxide
• (B) electrolysis of the fused chloride
• As it is evident from Ellingham diagram, MgO is one of the most
stable oxides, and a temperature higher than 1800oC is required to
reduce it with carbon.
• The reduction temperature can be lowered by applying a vacuum
to distil off the magnesium and to drive the reduction reaction to
the right.
MgO + C = Mg (g) + CO(g)
• It is however, very difficult to prevent the backward reaction of
the Mg vapour with CO, and hence, carbon reduction has not
found commercial acceptance.
• Consequently, other reductants such as CaC2 (which provides Ca)
and Al have been successfully employed at 1200oC under vacuum
in order to reduce MgO. The reactions are
MgO + CaC2 = CaO + Mg (g) + 2C
3MgO + 2Al = Al2O3 + 3Mg (g)
• Although reduction by CaC2 and Al is feasible, it is not
commercially attractive. Pidgeon and Alexander (1944) developed
a process that is both economical and commercially acceptable to
reduce MgO.
• It is based on the reduction of MgO by ferrosilicon in the presence
of CaO, under vacuum.

• Pidgeon process ( thermal reduction method)

• On thermodynamic grounds, pure silicon cannot reduce MgO
when both the reactants and the products are in their standard
states. To over come this difficulty , pidgeon applied a reduced
pressure in order to remove the Mg vapour and to drive the
reduction reaction.
• In this process, calcined dolomite is briquetted with powdered
ferrosilicon (75 % Si), and the reduction is carried out under a
vacuum of 0.1 mm of mercury at 1100-1200oC in an externally
heated retort.
• The over all reaction is:
2MgO.CaO + FeSi = 2Mg (g) + 2CaOSiO2 + Fe
• Magnesium is the only gaseous product and is removed from the
retort to avoid the possibility of back reaction during cooling and
condensation.

• Equipment and Operation:

• In the pidgeon process, the retorts, each of which is nearly 25 cm in dia and 3 m
in length, and inserted horizontally in a single furnace.
• These retorts usually made of Nichrome steel ( Ni-15 %, Cr- 28 %, Mn- 1.25%,
Si- 1.5 %, C- 0.3 % and Fe balance) and last for about a year when continuously
employed for bath operation.
• The furnace is heated either by gas or electricity.
• The principal raw material is dolomite ore, which is mined and transported to
the magnesium plant. The ore is calcined in continuous rotary furnaces at
∼1300 ◦C. Energy for calcining is derived from the combustion of coal or gas.
The calcining process yields ‘dolime’, as given by the following reaction:
(CaCO3 · MgCO3)(s) + heat → (CaO · MgO)(s) + 2CO2(g) ↑
• Ferrosilicon is produced by the carbothermic reaction of quartzite in submerged
electric arc furnace at 1600oC.
• Calcined dolomite and ferrosilicon are mixed in the proportion of one silicon to
six calcine and the mixture is pelletized to make briquettes for reduction in the
reduction furnace. The total weight of the charge is approximately 100 kg.
• Initially, heating is carried out to vaporize the structurally combined water. The
temperature is then raised to about 1150oC and the application of 1-2 Pa
vacuum is commenced.
• At this stage the reduction of calcined dolomite by ferrosilicon produces
magnesium vapour and these vapours are condensed at the cool end. This
reaction can be represented by
2MgO.CaO + FeSi = 2Mg (g) + 2CaOSiO2 + Fe
• After 8-10 hrs, the application of vacuum is stopped, the seal is broken, and the
condensed magnesium removed.
• Thus, the reduction process yields magnesium in the form of crowns—one
crown per retort, with each crown typically weighing between 18 and 22 kg
depending upon the size of the charge and the process conditions.
• The extracted crowns are allowed to cool, and then taken for remelting, refining
(may be, alloying) and casting into magnesium (or magnesium alloy) ingots.
• The yield per retort is approximately 15kg. To achieve a daily production rate of
10 tons of magnesium, approximately 120 tons of dolomite and approx 12 tons
of ferrosilicon are required. The number of retorts required is about 300.

Mg
crown
Flow chart of Mg production by pidgeon process
Production of Mg from sea water by Dow process
• Sea water contains (MgCl2), seashells (CaCO3) decomposed
with heat to CaO and mixed with water and form Ca(OH)2.
MgCl2 + Ca(OH)2 = Mg(OH)2 + CaCl2
MgSO4 + Ca(OH)2 = Mg(OH)2 + CaSO4
• Mg(OH)2 (s) + 2HCl (aq) = MgCl2 (aq) + 2H2O (l)
• Evaporation
• Electrochemical reduction:
MgCl2 (aq) = Mg(l) + Cl2 (g) ( heating above 700◦C)
Flow chart of Mg production by Dow process
 Production of Copper
• Copper is extracted in two ways, one by Pyrometallurgy
technique and by hydrometallurgy technique.
• Sources of copper:
• Copper exists in nature mostly in the form of copper sulphide
with or with out other metallic sulphides.
• Common minerals of copper are chalcopyrite CuFeS2 (34.5),
chalcocite Cu2S (79.8), bronite Cu5FeS4 (55.5), covellite CuS
(66.5), enargite CuAsS4 (48.4), malachite CuCO3.Cu(OH)2 (57.3),
cuprite Cu2O (88.8) etc.
• Of the aforestated minerals, chalcopyrite is commercially the
most important ore.
• Steps involved in the extraction of copper by pyrometallurgical
process using conventional route consists of – concentration,
roasting, smelting, converting and refining.
• Concentration:
• A naturally occurring sulphide ore normally contains 0.5-2 %
copper.
• Initially this ore is subjected to crushing and grinding in order to
liberate the sulphide grains from the gangue. The average size of
the ore after grinding should be 40 µm.
• The grounded ore is subjected to froth flotation. During froth
flotation, the pH is controlled by the addition of CaO and a
xanthate reagent is used as a collector.
• The copper sulphide concentrate thus produced contains 15-35 %
Cu, 15-35 % Fe, 25-35 % S and 3-15 % gangue.

• Roasting:
• The purpose of roasting is to partially oxidize the iron sulphide
present in the copper sulhide.
• Roasting is carried out in multiple hearth roasters with the feed travelling from
one hearth to the other.
• The temperature of the each hearth is gradually increased by fuel firing so that
the charge gets heated up from the room temperature to about 550oC .
• During roasting several reactions take place simultaneously. The roasted calcine
consists of sulphides of copper and iron, oxides of iron and mixed sulphates of
copper and iron. Some of the typical reactions are:
2CuFeS2 + 6.5O2 = 2CuO + Fe2O3 + 4SO2
CuFeS2 + 4O2 = CuSO4 + FeSO4
2CuFeS2 + O2 = Cu2S + 2FeS + SO2
2CuFeS2 + 4.5O2 = Cu2S + Fe2O3 + 3SO2
2CuFeS2 + 7.5O2 = CuO. CuSO4 + 2FeSO4 + SO2
3CuFeS2 + 9.5O2 = 3CuO + Fe3O4 + 6SO2
6CuFeS2 + 13O2 = 3Cu2S + 2Fe3O4 + 9SO2

• The roasted calcine is transferred to the smelting furnace in the hot condition
itself so as to facilitate the separation and the subsequent recovery of copper.
• Smelting:
• Smelting seeks to separate the metal sulphide in an ore. Such a
separation can be achieved by smelting the charge with a suitable flux
at a temperature of about 1250oC.
• During smelting two layers of liquid are formed, namely , an upper slag
layer that consists of the gangue and the flux and a lower matte layer
that contains metallic sulphides.
• The specific gravity of the slag layer ranges from 2.8 gm/cm3 to 3.8
gm/cm3, whereas that of the matte layer ranges from 5 gm/cm3 to 5.5
gm/cm3. the difference in the specific gravities permits a clear-cut
separation of one phase from the other.
• During smelting, both the copper sulphide minerals and the slag melt.
In addition, exchange reaction takes place between the oxides and
sulphides of copper and the iron sulphide present in the furnace charge:
6CuO + 4FeS = 3Cu2S + 4FeO + SO2
2CuSO4 + 2FeS = Cu2S + 2FeO + 3SO2
Cu2O + FeS = Cu2S + FeO
• Conventionally, a smelting operation is carried out In
reverberatory furnaces fired with either coal or oil. A typical
reverberatory furnace is shown in figure. Smelting is carried out
in electric furnaces. A typical electric furnace is shown in figure.
• An electric furnace is more advantageous than a reverberatory furnace,
because the generation of a large volume of combustion gases is avoided.

• Converting:
• The purpose of converting is to remove iron, Sulphur and other impurities
from matte.
• For this, the molten matte produced as a result of smelting is charged into
a side blown converter which is a cylindrical vessel with a capacity of
100-200 tons of matte.
• A typical vessel is 4 m in dia and 9 m in length and is lined with a layer of
chrome-magnesite refractory.
• In the converter, the atmosphere is highly oxidizing compared with the
neutral or mildly oxidizing atmosphere during smelting.
• Air or oxygen enriched air is injected into the molten matte through
tuyers. Each tuyere is about 5 cm in dia and there are about 40 tuyers in a
converter. The total volume of gas flowing through these tuyers is about
600 m3/min.
• The products of the converter are slag and blister copper.
• Two distinct stages in copper converting, namely, the slagging stage
and the blister formation stage.
• Slagging stage:
• In the slagging stage, the iron sulphide present in the
matte is oxidized and the oxide is slagged out by the
addition of a siliceous flux.
• The reactions are:
2FeS + 3O2 = 2FeO + 2SO2
2FeO + SiO2 = 2FeO.SiO2 (fayalite)
• Slagging is carried out in stages, i.e., by adding freshly obtained furnace
matte to the converter and then blowing air. Next, the slag formed is
skimmed off by tilting the cylindrical converter. The molten slag and
matte phases are immiscible.
• During converting, the oxidation of the iron sulphide generates sufficient
heat to overcome the heat lost to the surroundings and to maintain the
matte and slag in a molten state in the converter.
• The slag obtained typically analyzes 2-9 % Cu, 40-50 % Fe, 20-30 %
SiO2 and 1-5 % (CaO+MgO).
• The iron oxide produced as a result of Fes oxidation is present in the slag
mostly as fayalite saturated with magnetite.
• The magnetite forms a coating on the chrome-magnesite refractory,
providing some protection from the refractory against attack by the slag.
• Conventionally, copper is recovered from the slag produced in the
converter by transferring the slag, in a molten state, to a smelting
furnace.
• Any matte particles present in the slag settle down at the bottom and the
slag can be discarded.
• In the modern practice, the metallic values are recovered by employing
either an electric furnace with a provision for cleaning the slag or by the
slow cooling of the slag followed by grinding and flotation.

• Blister formation stage:

• After slagging has been completed, the converter essentially contains
Cu2S which is called white metal because of its appearance.
• In the blister copper formation stage, Cu2S is oxidized to form copper by
a combination of the reactions
2Cu2S(l) + 3O2 (g) = 2Cu2O (l) + 2SO2 (g)
Cu2S (l) + 2Cu2O (l) = 6Cu (l) + SO2 (g)
The overall reaction is :
3Cu2S + 3O2 = 6Cu + 3SO2
• At this stage if an iron bar is dipped into the melt in the converter, a
solidifying copper shell on the iron bar can be noticed.
• The molten copper thus obtained may either directly sent for
refining or may be cast for shipment to a refinery.
• As the molten copper solidifies, a considerable quantity of gas
is given off. The gas bubbles break at the surface of the copper
and leave marks resembling those of broken blister. That is
why, the copper is known as blister copper.

• Refining:
• Blister copper is approximately 98.8 % pure. It contains
sulphur, iron and arsenic as the main impurities.
• Sulphur prevents making a usable casting; other impurities
reduce electric conductivity and affect malleability.
• Blister copper is refined by two process
– Fire refining
– Electrolytic refining
• Fire refining:
• The fire refining is similar to the process involved in smelting.
• Fire refining involves subjecting a liquid melt to slow, limited oxidation
so that the impurities are oxidized.
• A reverberatory furnace is used for fire refining purposes.
• The blister copper is melted down and then oxidized by blowing
compressed air through steel pipes inserted in the molten copper bath. A
certain amount of oxidation also occurs during melting.
• Some of the impurities are preferentially oxidized and rise out of the
copper to form a slag with the flux, generally silica or lime. The slag is
skimmed off at intervals.
• Oxidation is continued until the copper is considerably oxidized, up to
bout 0.9 % oxygen. When the oxidation is finished, the bath is skimmed.
• The metal is then vigorously stirred with large poles of green wood. The
wooden poles reduce remaining oxides by the reaction of the carbon in
the wooden poles, leaving a relatively pure copper product ( about 93.3
% pure).
• Electrolytic refining:
• Fire refined copper is suitable for many applications. For other,
especially in electrical work, it must be subjected to electrolytic refining,
which leaves it 99.95 % pure.
• Fire refining neither effectively removes impurities such as bismuth,
tellurium, selenium and nickel nor it recovers the precious metals.
Electrolytic refining is used to make good these deficiencies.
• Electrolytic refining is carried out in a tank made of concrete and lined
with antimonial lead. The fire refined copper, cast into a suitable shape
(anode) is suspended in a solution (electrolyte) composed of sulphuric
acid and copper sulphate. On the passage of current, pure copper from
anode passes into solution and is deposited on the cathode which is
usually a specially prepared copper sheet.
• The impurities associated with the fire refined copper do not deposit on
the cathode, but either go into solution or else are deposited on the
bottom of the tank.
• During electrolytic refining, since the electrolyte becomes contaminated
by the impurities, it is necessary to replace a portion of the same by fresh
solution to maintain its chemical composition within proper limits.
Flow chart of copper production
 Production of Aluminium
• Next to copper, aluminium is considered the most important nonferrous
metal.
• Aluminium is remarkable in many ways: it can be rolled, extruded, cast,
formed and machined.
• Its high strength to weight ratio is a distinct advantage in many structural
applications. Further, the metal exhibits excellent corrosion resistance,
electrical conductivity and thermal conductivity.
• Aluminium is good conductor of heat and electricity and is less
expensive than copper, aids in rendering Al as a replacement for Cu.
• The most common minerals are gibbsite (Al2O3.3H2O) and diaspore
(Al2O3.H2O). The % of Al2O3 in gibbsite is 65.4 and that in diaspore
85.4.
• Bauxite is a mixture of these two ores and contains varying amounts of
impurities such as Fe2O3, TiO2 and SiO2.
• The bauxite ores found in India normally contains between 58-67 %
alumina. These ores have a high content of TiO2 (5-10 %) and a low
content of silica i.e. 0.5-2%.
• The bauxite obtained from the mines is crushed and ground to a very fine
size in jaw crushers and hammer mills.
• Crushed ore is treated by the bayers process to produce pure
Al2O3.
• The ore is calcined to dry it and remove organic matter.
• It is then ground to about 100 mesh and leached in a hot solution
of caustic soda (NaOH) under the pressure of 3.5 to 4.75 kg/cm2 at
150-160oC.
Al2O3 + 2NaOH = 2NaAlO2 + H2O
• The Al2O3 is dissolved whereas other oxides mainly remain as an
insoluble red mud.
• After separation of the sodium aluminate solution from the mud, it
is diluted and slowly cooled and the aluminium is precipitated as
hydroxide.
NaAlO2 + 2H2O = Al(OH)3 + NaOH
• The hydroxide is separated, washed and dried at around 1000oC to
give almost pure aluminium oxide.
2Al(OH)3 = Al2O3 + 3H2O
• Al2O3 as obtained by bayers process is reduced electrolytically by
the Hall-Heroult process in order to produce metallic aluminium.
This is achieved by electrolysis of a solution of alumina in molten
cryolite.
• The hall-Heroult process is carried out in a rectangular steel shell,
with a lining of carbon that forms the cathode.

• Carbon anodes are suspended above the cell on bus bars. Each cell
can produce about 22 kgs of aluminium every day.
• The cell is operated at a voltage of 6-7.5 with a current density of 70-82
amperes/sq.metre of cathode. In practice, about 25kilowatt hours are
used in producing 1 kg aluminium.
• For operating the cell, cryolite is charged into it and fused by the heat
generated by passage of the electric current. As soon as the cryolite is
fused completely, the alumina added and reduction takes place
2Al2O3 = 4Al + 3O2
• During electrolysis, a crust (layer) of cryolite and alumina forms on the
top of the molten bath. From time to time Al2O3 is pre-heated on this
crust and fed into the bath by breaking a hole in the crust.
• The molten aluminium formed collects at the bottom of the cell and is
tapped off into ladles and cast into pigs.
• The entire process of electrolysis is continuous.
• The aluminium produced by hall-heroult process is pure enough, 99.5
%, for most purposes and may be cast directly or, after alloying, into
slabs or billets suitable for working.
• Newer processes for Aluminium production:
• The Hall-Heroult process has stood out as the only commercial process
for aluminium production. Of late, extensive research for alternative
method has been carried out, and, in all probability, the chloride process
being developed by ALCOA ( Aluminium company of America) could
become a viable alternative as far as energy efficiency is concerned.

• AlCOA process:
• In the ALCOA process, the alumina produced by the bayers process is
chlorinated under reducing conditions in the presence of carbon at 700-
900oC to produce a mixture containing AlCl3, CO, and CO2.
Al2O3 (c) + 2C (C) + 3Cl2 (g) = 2AlCl3 (g) + CO (g) + CO2 (g).
• AlCl3, which is vapour at these temperatures, is separated from the
reaction products by condensation, at about 70oC, in a fluidized bed
containing AlCl3 particles.
• The solid AlCl3 particles thus formed are continuously fed into an
electrolytic cell containing a fused chloride electrolyte.
• This electrolyte, which is made up of 5 % AlCl3, 50 % NaCl
and 45 % LiCl, is maintained at 700oC.
• Upon electrolysis by a direct current, liquid aluminium is
formed at the cathode and gaseous chlorine liberated at the
anode. The chlorine produced is recycled in order to chlorinate
the fresh alumina.
• The cell in the ALCOA process has a novel design , i.e., it is
bipolar cell consisting of several bipolar electrodes, each bipolar
electrode behaves like a cathode at the top surface and like an
anode at the bottom surface.
• A continuous flow of electrolyte must be maintained across the
cell in order to prevent the molten aluminium produced upon
electrolysis from forming pools of the electrodes.

ALCOA bipolar cell

• An arrangement is made to collect this molten aluminium at the
bottom. Chlorine rises to the top, where it is collected.
• It is noted that one bipolar cell is equivalent to five conventional
monopolar cells in series. Also, the productivity and the cell voltage
of a bipolar cell are five times those of the conventional monopolar
cell.
• AlCOA has clamed operation at current densities up to 23,000 A/m2
with an electrode gap of less than 1.3 cm.
• In the ALCOA process, the chloride electrolyte has a much higher
conductivity, i.e., 4.0 mho cm-1 (electrical conductance) compared
with that of the conventional hall-heroult cell i.e., 2.8 mho cm-1.Also,
the distance between the electrodes is lower in the ALCOA cell.
• These two factors appreciably lower the energy wasted in the form of
heat that is produced due to the current flowing between the
electrodes.
 Production of Zinc
• Some of the important naturally occurring minerals of zinc are :
sphalerite (ZnS), zincite (ZnO), franklinite (ZnO (Fe, Mn)2O3),
calamine (Zn2(OH)2SiO3) and smithstone (ZnCO3). Of these
minerals, sphalerite is the commonest.
• Zinc ores are usually associated with several compounds mainly
sulphides of Pb, Cu and Cd.
• Zinc ores are often of a low grade. Differential flotation can,
however, be used to separate the sulphides of Pb, Cu and Zn from
a typical zinc ore. This produces a zinc concentrate containing as
much as 50 % Zn.
• Both pyrometallurgical and hydrometallurgical techniques are
currently being employed in the extraction of Zn. The former is
distinctly successful if the concentrate is of very high grade.
• Pyrometallurgical extraction of zinc:
• The zinc ore is crushed, concentrated by flotation, which contains about 55 % Zn
, is roasted at a temperature of about 800ºC.
• The resultant roasted oxide is first ground and agglomerated and then sintered at
1200ºC so as to provide a feed in the form of lumps for retort reduction.
• In the retort, the ZnO is reduced by carbon at about 1200ºC. The zinc which
distils off is collected in condensers. The reactions are:
ZnS + 1.5 O2 = ZnO + SO2 (roasting)
ZnO + CO = Zn (g) + CO2 (reduction)
C + CO2 = 2CO
• Partial pressure of CO in the retort gases has to be maintained at a high level in
order to prevent te oxidation of Zn to ZnO by CO2 .
• The zinc sulphide concentrate always contains some lead sulphide. In order to
eliminate this lead sulphide to a large extent during the initial stages of roasting,
i.e., by volatization, a hearth roaster is employed.
• The remaining lead sulphide is removed during sintering which is carried out at
rather high temperature.
• In order to prevent the distillation of any lead present in the zinc concentrate
along with the zinc and to obtain a high grade zinc, it becomes essential to ensure
that the feed for retort distillation has a low lead content.
• In most cases, roasting is carried out in a fluid bed roaster rather than in a
conventional hearth roaster because the former has certain advantages. For
instance, the roasting process in a fluid bed roaster is autogenous. Further, a fluid
bed roaster provides a good control over the temperature, ensures a rapid
roasting rate and generates SO2 which is suitable for acid production.
• A result of roasting is subsequently sintered in a Dwight-lloyd sintering machine
to provide lump feed for retort reduction and to eliminate residual S, Cd and Pb.

• Horizontal retort:
• It is usually made of fire clay and has a dia of 0.3 m and length of about 1.5 m
and thickness of 5-6 cm.
• The process is carried out by mixing the sintered ore with coal and shovelling
the same into the horizontal retort. A large number of retorts are placed in a
furnace chamber and heated by means of hot combustion gases.
• The carbon in the coal unites with the oxygen of the zinc oxide, metallic zinc
being liberated, which distils and is collected in the cool end of the retort
(condenser) from which it is periodically withdrawn into ladles for casting into
slabs.
• The CO gas burns to waste at the mouth of the condenser.
• The operation, both charging and emptying of the retorts and draining of the
condenser, is manual.
• Vertical retort:
• It is made of silicon carbide and has a rectangular shape 10-15m high,
2m long and 0.3 m wide. The retort is heated from outside and a number
of retorts separated by combustion chamber form a battery, in the same
way as in a coking plant.
• The retorts are charged with briquettes made of the following mixture,
after thorough grinding and mixing.
• Mixture: sinter- 52 %, bituminous coking coal- 26%, anthracite- 8%,
retained briquette fines- 10%, clay- 4% and little binders (sulphite lye).
• The briquettes are first coked at about 800ºC before being transferred to
the retorts.
• On being heated to 900ºC, the carbothermic reduction takes place, and
by the time the briquettes have reached the bottom of the retort virtually
all zinc is expelled, and the spent briquettes are discharged .
• Zinc vapours and gases move upwards through the vertical retort and
pass into the condenser where Zn condenses at a temperature of 525-
575ºC. Metal collects in the sump and is with drawn at intervals and cast
into slabs.
• Exhaust combustion gas is introduced under pressure at the bottom of
the retort in order to help the upward flow of gas and vapour through the
retort to the condenser.
• By means of a rotating impeller a shower of liquid zinc is formed, on which the
vapour condenses. The action of the impeller also helps to break down the films
of ZnO and to make the droplets combine. Also, to some extent, rapid cooling
helps to suppress reoxidation.
Flow chart of Zn production through Pyrometallurgy process
• Production of Zn through imperial smelting process (ISP route):
• In the ISP, ZnO is reduced by carbon to produce Zn. The reduction is carried
out in an imperial smelting blast furnace, in which, the Zn that is evolved in the
form of a vapour is condensed by using molten lead.
 Advantages of ISP:
• It is possible to simultaneously smelt low-grade complex mixed charges of Zn
and Pb ores and concentrates in order to recover both Zn and Pb.
• Since the overall thermal efficiency is higher, the recovery of Zn becomes less
expensive.
• A wide variety of furnace sizes are available, the trend being towards units with
larger capacities at lower operational costs.
• The furnace operation is fully automated.
• The mechanism is highly robust, i.e., it can withstand frequent shut-downs and
restarts.

• The smelting reactions that take place in the blast furnace are :
C + ½ O2 = CO (1)
C + O2 = CO2 (2)
CO2 + C = 2CO (3)
ZnO + CO = Zn + CO2 (4)
PbO + CO = Pb + CO2 (5)
• Besides the reaction of ZnO to Zn, PbO is reduced to Pb, Fe2O3 to
Fe, and certain sulpahtes to sulphides.
• Reaction (4) proceeds in the forward direction, but can be reversed
in some regions of the furnace. the amount of reduction per unit
carbon consumed is governed chiefly by the heat balance for the
unit operation.
• After the reduction has been completed, the molten slag and lead
are taken out of the furnace hearth at a temperature that is
approximately equal to the melting point of the slag, whereas the
gases generated emerge from the top of the furnace at a
temperature slightly higher than the equilibrium temperature for
reaction (4).
• Later the temperature is raised to 1000ºC by admitting air above
the top of the furnace charge in order to generate heat by the
combustion of CO. At this temperature, Zn could be collected with
out back reaction.
Imperial smelting Blast furnace
• The basic process during the smelting of zinc oxide is the combustion of
carbon in preheated metallurgical coke which produces gaseous carbon
monoxide. This monoxide affects the reduction of ZnO and PbO in a
sinter.
• Preheated coke (800ºC) and sinter are charged into the top of the ISP
furnace. the lead in the sinter, which is reduced to liquid metal, flows
down to the bottom of the furnace. in so doing, it collects Cu, Ag, and
Au together with other elements contained in the furnace charge (this
liquid lead is called lead bullion).
• The other products that is removed from the bottom of the furnace is
slag.
• This slag and the lead bullion are tapped together from the bottom of the
furnace and are separated by the difference in their density values.
• This bullion is usually cast into ingots which are subsequently refined by
conventional refining methods.
• The furnace gases generated during reduction, pass upwards through the
charge and are evenly divided between two condensers. These
condensers serve two purposes, i.e., they very rapidly cool the furnace
gases, resulting in the condensation of the Zn contained in these gases
and they help in dissolving the condensed Zn in molten lead.
Zn recovery system
• Each condenser consists of a bath of molten lead. Rotors capable of
generating an intense spray of lead droplets over the entire volume
of the condenser are immersed into the molten lead bath.
• When the furnace gases (containing Zn) pass through this spray,
they are cooled very rapidly. as a result , the Zn vapour present in
the furnace gases either goes directly into solution with the lead or
forms liquid Zn, which, in turn, immediately dissolves in the Pb.
• The Zn containing lead is constantly pumped out from the
condensers at a temperature of about 550ºC into water cooled
launder, where it is cooled to a temperature of about 440ºC.
• During cooling, the Pb becomes saturated with Zn, and any excess
Zn emerges from the Pb and floats in the form of stream on the
surface of Pb because the density of Zn is less than that of Pb.
• Zn is separated and collected in a holding tank where it is treated
with metallic sodium in order to remove arsenic. At this stage, the
metal is of a high grade and is ready for casting.
 Hydrometallurgical extraction of Zn
Electrolytic extraction:
• In the electrolytic process, the roasted Zn concentrate is leached with a
dilute H2SO4 solution to convert the Zn to ZnSO4 solution as free from
impurities as possible; then the deposition of the Zn from the solution by
electrolysis is carried out.
• Zn and other metals (Cu and Cd) which form soluble sulphates are
dissolved in H2SO4 . Compounds of insoluble metals such as Au, Fe, Pb
and Ag remain in the residue which is sent to a lead smelter for treatment
and recovery of values.
• In the solution containing soluble sulphate of Zn, Cu and Cd, Zn dust is
added to precipitate Cu and Cd which are electropositive to Zn.
• The solution is filtered to remove precipitates. The neutral solution of
zinc sulphate is electrolyzed in a tank containing tewnty five lead anodes
and twenty six cathodes of rolled sheet aluminium connected in parallel.
• The majority of plants use a current density of 25 to 35 A/sq.ft. of
cathode surface as being the most economical and satisfactory.
• The Zn, which has a high degree of purity, is deposited on Al cathodes, which is
periodically removed from the electrolyte and stripped.
• The stripped Zn is melted in a furnace and cast into ingots or pigs called slab zinc
or spelter.
• The process is cyclic: the electrolysis of Zn bearing solution regenerates H2SO4,
and this spent electrolyte is used for further leaching of Zn concentrate.
• Refining of Zn:
• Electrolytic Zn needs no refining.
• However, Zn obtained through other extraction methods contains impurities such
as Pb, Cd, Fe etc.
• Since, for the production of special Zn alloys, considerably high purity Zn is
required, impure Zn is refined by distillation.

Double distillation column for purification of Zn

• The two columns in the figure are built of superimposed trays of
silicon carbide. The lower half of the column is heated externally,
whereas the upper half is well insulated.
• The impure Zn obtained from the retort or Bf is fed in the middle
of the first column. During its flow through the lower part of the
column, Zn and Cd evaporate and the melt enriched in Pb (Zn-Pb
alloy) collects.
• The Zn and Cd vapor from the first column is condensed in the
condenser and passed on to the second column. The temperature
of the second column is somewhat lower than that of the first
column. Zn remains in the liquid state, whereas Cd evaporates and
is recovered in the Cd chamber by condensation of the over-
flowing vapour.
• Zn with a purity of about 99.99 % is withdrawn from the bottom
of the second column.
 Production of Lead
• In nature lead exists either in the form of sulphide or oxide. The common
minerals are galena (PbS), cerrusite (PbCO3) and anglesite (PbSO4). The
most common ores contain galena associated with ZnS, FeS, CuS,
PbCO3 and several precious metals.
• The lead sulphide along with precious metals, is first separated from the
other sulphides and is concentrated by differential flotation. The
concentration may contain 60-80 % Pb.
• The concentrate is roasted to the oxide which is subsequently reduced by
carbon to yield metallic lead. During roasting the temperature must be
carefully controlled because above 800ºC, PbS tends to fuse.
• Roasting is done in a Dwight-Lloyd sintering machine. This machine not
only eliminates sulphur to a large extent but also produces a sinter with
required properties, such as strength and porosity for the subsequent blast
furnace operation, during which , the sulphur content of the concentrate
is reduced from 16-18 % to 1-2%.
• The Dwight-Lloyd sintering machine operates at around 800ºC and
produces 200-1600 tons of sinter per day.
• The reactions that take place during roasting are:
PbS + 3/2 O2 = PbO + SO2
SiO2 + 2PbO = 2PbO.SiO2
2PbSO4 + SiO2 = 2PbO.SiO2 + 2SiO2
• The metal is ultimately produced by the carbon reduction of the sinter in
a lead blast furnace. Its total height is around 8m, top dia 3m and stack
height 5m.
• A cold blast of air is blown in through 15 tuyers around the bosh to
oxidize the carbon charged with the sinter which produces the required
heat.
• At the top of the furnace, either bag houses or electrostatic precipitators
are provided so as to recover the lead fumes from the outgoing gases.
• The blast furnace charge consist of sinter obtained from sinter machine,
coke (10%), limestone (5-10%), scrap iron (1%) and quartz.
• Limestone and quartz are added to the charge in order to obtain a slag
containing the gangue material. The normal composition of slag is SiO2-
18-35%, CaO- 10-20%, Pb- 2-4%.
• The scrap iron in the charge serves a number of useful purposes:
– First, it helps in reducing any residual PbS left unroasted in the
sintering machine.
– Secondly, it combines with SiO2 present in the charge to form
2FeO.SiO2, which lowers the melting point of slag, thus rendering it
more fluid at operating temperatures.
– Thirdly, it keeps the lead losses low.
• During the initial stages of smelting, lead enters the slag phase as lead
silicate, and major portion of this lead is recovered by adding iron.
PbSiO3 + Fe = FeSiO3 + Pb
Finally, it helps in reducing PbO:
PbO + Fe = FeO + Pb
• The smelting process produces four distinct layers of products:
(1) First layer- slag
(2) second layer – matte containing Cu and other elements
(3) third layer – Speiss (when As is present in the slag) FeAs4 + impurities
(4) fourth layer- lead ; also called base bullion.
Flow chart of smelting of lead ore through Blast
furnace route
• Treatment of base bullion:
• The lead rich layer produced in the blast furnace, namely, the base
bullion, is rich in several other valuable elements, each of these elements
is recovered during a series of steps.
• Drossing:
• The base bullion is first subjected to drossing at around 350ºC. (drossing
is a combination of liquation and oxidation and is usually carried out in a
reverberatory furnace).
• At this temperature, many metals get oxidized and are skimmed off.
Subsequently, the temperature is raised to 500-550ºC and sulphur is
added to eliminate Cu in the form of copper sulphide.

• Parkes process for desilverization of lead:

• In parkes process, a sufficient quantity of Zn is added to the molten
metal to bring about the desilverization of lead.
• This process is based on the fact that the mutual solubility of Zn and Pb
is low and that Ag dissolves more readily in Zn than in Pb. The Ag
absorbed by the Zn layer is subsequently recovered by distilling off the
Zn.
• Dezincing:
• In parkes process, some zinc inevitably dissolves in the lead and
vice versa. (Pb dissolves 0.6 % Zn and Zn dissolves 1.6 % Pb, both
metals being in the molten state).
• The Pb containing Zn is subjected to cupellation, where Zn is
removed by oxidation. Zn can be separated either by the application
of the vacuum or by preferential chlorination with chlorine.

• Debismuthizing:
• In the base bullion, if bismuth is present in a large quantity, it can
be separated by the addition of an alloy of calcium and magnesium
which forms an insoluble intermetallic compound with bismuth.
Flow chart of refining of lead bullion
• Electrolytic refining:
• Most attempts to refine the base bullion by electrolysis have proved
unsuccessful because there are not many water soluble salts of lead.
However, an electrolyte that proves successful is made up of H2SiF6
(Hexafluorosilicic acid).
• In the electrolytic cell, the cathode is made of pure Pb and the anode
is base bullion. Pb by itself can be selectively electrodeposited.
• During electrolysis, impurities such as bismuth, arsenic, antimony
and the precious metals collect at the bottom of the cell in the form
of anode slime.
• If the impurity content of the base bullion is very high, electrolytical
refining is preferable to conventional refining because the recovery
is more complete and easier.
 Production of lead in India
• At present, the sole producer of Pb in India is the Hindustan Zinc limited
(HZL). HZL operates two plants: one at Tundoo (Bihar) and the other at
visskhapatnam (Andhra pradesh). The former has a capacity of 8000 tons and
the latter has a capacity of 10,000 tons of lead per year.
• The smelters of the plant not only extract and refine lead from indigenous ores
but also yield a substantial quantity of Ag as a byproduct.
• In the tundoo plant, the procedure for lead production entails roasting and
sintering of the lead concentrate in pots. The exothermic reactions that take
place during roasting and sintering can render the process autogeneous,
provided the S content in the concentrate is between 8-10 %.
• The roasting section consists of several hemisphere cast iron sinter pots, each of
which has an inlet at the bottom through which air is blown in. suction is
created by hoods present above the pots which can be raised or lowered.
• The max temperature attained in the bed during operation is around 800ºC and
the time taken for roasting and sintering varies from 7-12 hrs.
• The product obtained is called primary sinter. This sinter is first cooled and then
crushed in two stages to a final size of -6mm.
• After crushing, the primary sinter is mixed with a suitable proportion of water
and charged back into the sinter pots where secondary roasting bring down the
S content to about 2 %. The product obtained is called secondary sintering.
• The secondary sinter has to be crushed to a size of 75-100 mm size before it
can be fed into the lead blast furnace.
• Since lead has low melting point, i.e., 327ºC, melting hardly poses any
problem. The slag, however, melts only at 1200ºC.
• When the bf is in operation, all the gases from the top are sucked in through
the cooling and settling chamber into a bag-house where a series of special
woolen bags collect the metallic dust.
• The flue pipes and the cooling chamber are cooled by water spray.
• The bf product is called hard lead because of the hardness imparted by
impurities such as copper antimony, zinc and silver.
• After these impurities have been removed, a soft metal with a purity of 99.99
% is obtained during subsequent refining.

• Lead refining:
• During lead refining, Cu is removed from the hard lead by a two-stage
drossing process in 30-ton kettles heated by oil burners and then again in 60-
ton kettles.
• The temperature of the refined lead after drossing is allowed to drop to about
340ºC and the rock sulphur is added on the basis of 1 Kg per ton of hard lead.
• After 2 hrs of stirring, the black powdery dross formed is skimmed
off. This dross contains about 80 % of the copper originally present
in the hard lead.
• Like Cu, antimony, too, is removed in stages. The main bulk is
removed after Cu drossing by raising the temperature of the kettle to
650ºC and blowing air under pressure for about 6 hrs.
• Some caustic soda is also added to precipitate a high antimony slag.
The remaining Sb is removed after desilverization and dezincing.
• Like Cu and Sb, silver, too, is removed in stages by the conventional
parkes process. In the first stage, Zn and low Zn layer from previous
charge are added and stirred.
• The fresh layer formed is taken out and mechanically pressed to
remove any entrained lead and to obtain a press crust which contain
Ag and Zn.
• In the second stage, some more Zn is added and the temperature is
allowed to drop gradually to the freezing point of Pb. As Zn
seperates, it removes with it Ag, Au and residual Cu.
• Dezincing or the removal of residual Zn from the Pb is
accomplished by blowing air for 3-4 hrs at 650ºC , when the Zn
dross is formed. The addition of caustic soda at this stage removes
the residual Sb.
• The approximate consumption of materials per ton of lead is as
follows: Zn- 16-17 kg, S- 1-1.2 kg and caustic soda 2-2.5 kg.
• A typical analysis of the products obtained during Pb refining is
given in below table.
 Production of Tin
• Cassiterite (SnO2) is by far the most important mineral of tin. It is found in
Bolivia, Malaysia and Indonesia. In India, no significant tin deposits have yet
been located.
• Naturally occurring cassiterite is usually associated with the gangue materials
and metallic sulphides such as galena, chalcopyrite, iron pyrite and sphalerite.
• The theoretical tin content of SnO2 is 78.6 %. In reality, however, ores may
contain as little as 1 % tin or even less.
• To upgrade these ores to about 65 % tin, the water gravity concentration
methods are employed. During such upgrading the gangue is removed, but since
the specific gravities of the other metal sulphides are almost the same as that of
cassiterite, they cannot be eliminated by ordinary gravity methods.
• Flotation methods have also not been successful so far in separating the tin
mineral from other minerals.
• Iron and tungsten bearing materials, if present with tin ores, are separated by
magnetic roasting and subsequent magnetic separation.
• Smelting of Tin concentrate- Reverberatory furnace smelting:
• If a tin concentrate contains iron sulphides, they are oxidized to the oxide before
or during smelting. From the free energy diagram for oxides, we can observe that
the Carbothermic reduction of SnO2 is feasible at moderate temperature. This
cause problems because the thermodynamic stabilities of SnO2, FeO and Fe3O4
are similar at 600ºC.
• However, at high temperatures FeO becomes more stable. In the temperature
range (1200-1300ºC) needed for smelting, i.e., obtaining a fluid slag of the
gangue, the difference in the stabilities of FeO and SnO2 is 20 Kcal.
• It should be noted that the free energy for SnO2 formation is almost equal to that
required for the oxidation of FeO to Fe2O3.
• The difference in stability between FeO and SnO2 is used as the basis for
selectively reducing SnO2 to Sn, while maintaining, to a large extent, iron in the
form of oxide in the slag.
• As the value of the differential stability is not high, it is not possible, in a single
smelting step to recover all the tin in the concentrate and transfer all the iron into
the slag.
• To overcome this difficulty and to attain a high degree of separation of tin from
iron, leading to a high level of tin recovery, the smelting of the tin concentrate is
done in three stages.
• In the first stage, high quality tin is obtained by partially reducing the tin
concentrate , by deliberately maintaining a high level of tin oxide in the slag,
any by retaining almost all the iron in the slag.
• This slag is subsequently reduced in two further stages; the first stage produces
tin containing 5 % iron and second stage tin containing 20% iron.
• The slag from the third stage has a very low tin content , and can be discarded.
The tin produced in the second and third stage is subjected to liquation refining
in order to eliminate iron.
• The tin oxide content in the first slag is deliberately kept high in order to obtain
tin with a very high degree of purity (99 %).
• This slag is subsequently smelted, additional flux (limestone), coal and iron
scrap being employed as the ingredients.
• Iron scrap facilitates the reduction of the tin oxide present in the slag. The
second slag, which contains a much smaller amount of tin than the first slag, is
also smelted to recover its tin content.
• The tin-iron alloys such as those produced in the second and third smelting
stages can be refined by liquation.
• When the tin-iron alloys are heated to a temperature higher than the melting
point of tin, the liquid tin flows out leaving behind iron-tin intermetallics.
• This metal, known as first-run metal, contains 99.9 % tin. As the temperature is
progressively increased, the iron content of the tin increases. This metal, known
as second-run metal, is reliquated.
• The dross left over after the final liquation is returned to the first smelting stage.
• Refining of Tin:
• There are two methods of refining of tin, namely, pyrometallurgical refining and
electrolytic refining.

• Pyrometallurgical refining of tin:

• It may be noted that the entire operation, which is carried out in a single container
(called kettle), takes about 40 hrs. The ultimate recovery of tin is more than 85 %.
• several common impurities form intermetallic compounds with each other or
with tin. Some of these are Ca3Sn, Sn3As2, FeAs, Fe2As, Cu3As, Cu2Sb, FeSb2
and FeSN2.
• Thus, if impure liquid tin is cooled to a temperature just above the melting point
of tin these intermetallic compounds, which have melting points higher than that
of tin, separate out and float as tiny crystals.
• Pulverized coal is added to facilitate liquation, i.e., the light, rising particles of
coal carry with them the crystallites of the intermetallic compounds to the
surface. Also, pulverized coal helps maintain reducing conditions in the tin bath
which aids intermetallic formation.
• Liquation, at 550ºC, in the presence of pulverized coal eliminates almost 99.8%
iron from the tin metal and yields a dry dross containing 25% tin.
• S is added to the liquid tin metal in order to remove Cu by the formation of
copper sulphide.
• As and Sb are eliminated in the form of intermetallic compounds, namely, AlAs
and AlSn by the addition of Al. these compounds have high melting point, i.e.,
1720ºC and 1070ºC, respectively, and are also insoluble in tin.
• The As and Sb skimmings have to be immediately treated for metallic recovery
as they react with atmospheric moisture to produce toxic arsenide and
antimonide.
• The reactions are
2AlAs + 6H2O = 2AsH3 + 2Al(OH)3
2AlSb + 6H2O = 2SbH3 + 2Al(OH)3
• NH4Cl is added with tin after Al treatment to remove surplus aluminum
according to the reaction
Al + 3NH4Cl = AlCl3 + 3NH3 + 3/2 H2
• Deleading of the tin by SnCl2 is based on the reaction
Pb + SnCl2 = PbCl2 + Sn -------------(1)

• Where Pb and Sn denote Pb and Sn in solution. The dross produced as a result

of reaction (1) contains both PbCl2 and some unreacted SnCl2. A lead-tin alloy is
recovered from this PbCl2- SnCl2 mixture by melting it in contact with Zn:
SnCl2 + PbCl2 + 2Zn = 2ZnCl2 + Pb-Sn.
• Tin metal, after deleading, is treated for bismuth removal by Ca and Mg addition.
• Ca and Mg together remove bismuth in the form of insoluble intermetallic
compounds, namely, Bi2Mg5, Bi2Ca3 and Bi3Ca. Any excess Ca or Mg is
removed by adding NH4Cl according to the reaction
2 NH4Cl + Ca(Mg) = 2NH3 + H2 + Ca(Mg)Cl2
• Electrolytic refining of Tin:
• Recent research has developed a viable process for the electrolytic refining of
tin. This process, which employs a mixture of sulphuric acid and phenol
sulphonic acid as the electrolyte, is feasible especially if the tin contains a large
amount of impurities such as Pb, Bi, Sb and As.
• The cell operates at room temperature at a cell voltage of 0.3 and a current
efficiency of 85 %.
• Anodes made of the impure metal, where as cathode is of pure metal sheets. If
the lead content of the anode is high, the slimes which fall from the anode are
excessive and have to be removed frequently.
• Further, other slimes sticking to the anode are scrubbed off with revolving
brushes so as to provide a smooth flow of electricity to ensure a high current
efficiency.
• The high purity tin obtained as a result of electrolysis typically analyzes Sn,
99.95; Sb, 0.02; As, 0.01; Bi, 0.01; Cd, 0.01; Cu, 0.001; Fe, 0.01; Pb, 0.02; (Ni +
CO), 0.01; S, 0.01 and Zn, 0.005