Principle of Extraction of Metals

OCCURRENCE OF METALS:

The earth's crust is the biggest source of metals. Some soluble salts of the metals are also found in sea-water.
Metals occur in nature sometimes free but mostly in combined state. The natural mode of occurrence of a metals is
largely dependent on its nature. Those metals which are least reactive and have little or no affinity for oxygen,
moisture and other chemical reagents occur in free or metallic or native state i.e., in uncombined state. Most of the
metals are reactive and hence are found in combined state i.e., as compounds.
The natural substances in which the metals or their compounds occur in the earth are called minerals. The mineral
has a definite composition. It may be a single compound or a complex mixture. The minerals from which the
metals can be conveniently and economically extracted are known as ores. All the ores are minerals but all
minerals cannot be ores. For example, both bauxite (Al2O3. 2H2O) and clay (Al2O3.2SiO2.2H2O) are minerals of
aluminium. It is bauxite which is used for extraction of aluminium and not clay. Thus, bauxite is an ore of aluminium.
Ores may be divided into four groups.

1. Native ores : These ores contain metals in free state, e.g., silver, gold, platinum, mercury, copper, etc. These are
found usually associated with rock or alluvial materials like clay, sand, etc. Sometimes lumps of pure metals are also
found. These are termed nuggets.

2. Oxidised ores : In these ores. Metals re present as their oxides or oxysalts such as carbonates, nitrates, sulphates,
phosphates, silicates, etc.
3. Halide ores : Metallic halides are very few in nature. Chlorides are most common.


2. METALLURGY:

The whole process of obtaining a pure metal from one of its ores is known as metallurgy.
In order to extract the metal from ores, several physical and chemical methods are used. The method used depends
upon the nature of the ore, the properties of the metal and the local conditions, Thus, it is not possible to have a
universal method for the extraction of all the metals from their ores. However, the metallurgy of a metal involves
three main operations:

1. Concentration or dressing of Ore,

2. Reduction of Ore

3. Purification or refining of Ore


1. Concentration or dressing of ores: Ores usually contain soil, sand, stones and other useless silicates. These
undesired impurities present in ores are called Gangue or Matrix.The removal of these impurities from the ores is
known as concentration. Before the ore is subjected to concentration, it is crushed into small pieces in gyratory
crushers. The crushed ore is then grinded with the help of rollers or in the stamp mill to powder form.


Physical Methods

The following physical methods are generally employed for the concentration of the ores depending upon the nature
of the ore.

1. Gravity separation : The separation is based on the difference in the specific gravities of the gangue particles and
the ore particles. The powdered ore is agitated with water or washed with a running stream of water. The heavy ore
particles settle down while the lighter particles of sand, clay, etc., are washed away. For this either Wilfley table is
used. It a wooden table having slanting floor on which long wooden strips called riffles are fixed.




The powdered ore is suspended in a stream of water. The heavier ore particles collect behind the riffles and the
gangue particles are carried away with the stream of water. Hydraulic classifier is shown in this. Powdered ore is
dropped from the top of classifier and strong stream of water is introduced from the bottom. The lighter gangue
particles are carried away by the water while the heavier ore particles settle down.
Generally, Oxide and carbonate ores are concentrated by this method. For example, tin ore (cassiterite) and iron
ore (haematite) are concentrated by gravity method.
Electromagnetic Separation


Electromagnetic Separation : When one component either the ore or impurity is magnetic in nature, this method
can be used for separation. A magnetic separator consisting a belt moving on two rollers is used. One of which is a
strong magnet. The powdered ore is dropped on the belt from one end (non-magnetic) and at the other end
(magnetic), the magnetic particles are attracted and fall nearer the roller while non-magnetic particles fall away from
the roller. Ferro-magnetic ores are concentrated by this method. For example, wolframite (FeWO4) - a magnetic ore,
is separated from the non-magnetic ore, cassiterite SnO2, by this method.





Froth floatation process : This method is used for the concentration of sulphide ores. The method is based on the
preferential wetting properties with the frothing agent and water. The powdered ore is added to water containing pine
oil (frothing agent) and sodium ethyl xanthate (collecting agent). A vigorous stream of air is now passed through,
which thoroughly agitates the mixture and disposes the oil into colloid sized particles. As a result of this, the sulphide
particles of the ore stick to the oil droplets and rise to the surface in the form of froth supported by air bubbles. Water
wets the gangue particles which sink to the bottom. With this method, it is possible to concentrate the dense ores
such as galena and zinc blende.




Leaching : It involves the treatment of the ore with a suitable reagent as to make it soluble while impurities remain
insoluble. The ore is recovered from the solution by suitable chemical method. For example, bauxite ore contains
ferric oxide, titanium oxide and silica as impurities. When the powdered ore is digested with an aqueous solution of
sodium hydroxide at about 150C under pressure, the alumina (Al
2
O
3
) dissolves forming soluble sodium
meaaluminate while ferric oxide (Fe2O
3
), TiO
2
and silica remain as insoluble part.

Chemical methods

1. Calcination : It involves heating of the ore below its fusion temperature in absence of air. This step expels organic
matter and moisture from the ores. It can remove moisture from hydrated oxides or carbon dioxide from carbonates.
Forexample


Al2O32H2O Al2O3 + 2H2O

2Fe2O33H2O 2Fe2O3 + 6H2O

CuCO3Cu(OH)2 2CuO + CO2 + H2O
Calcination makes the ore porous. The step is generally performed in reverberatory furnace.

2. Roasting : It is also heating of the ore either alone or with some other material usually in presence of air below its
fusion temperature. roasting is generally done in a reverberatory furnace or in a blast furnace. In roasting definite
chemical changes like oxidation, chlorination, etc., take place while in calcination these occurs only expulsion of
organic matter, water, carbon dioxide etc., i.e., it does not involve any major chemical change.

The roasting process may be any one of the following types :

1. Oxidising roasting : This is very common type of roasting in metallurgy and is carried out to remove sulphur and
arsenic in the form of their volatile oxides such as SO2 and As2O3respectively. The ores are simultaneously
converted into corresponding oxides. This type of roasting is generally applied in ores of lead, zinc, nickel, copper,
etc.
S + O2 SO2
4As + 3O2 2As2O3
2PbS + 3O2 2PbO + 2SO2
2CuS + 3O2 2Cu2O + 2SO2

Partial oxidising or sulphating roasting : This type of roasting is carried out at a temperature below the melting
point of the charge and air is admitted. Part of the sulphide ore is oxidised to sulphate and the rest is converted into
oxide. For example, the roasting of galena leads to the formation of a mixture of lead oxide and lead sulphate.

2PbS + 3O2 2PbO + 2SO2
PbS + 2O2 PbSO4
2. Chlorinating roasting : This type of roasting is done in the case of silver ore. The ore, argentite is mixed with
common salt and the mixture is heated in the presence of air. The final product is the chloride of the metal.

Ag2S + 2NaCl 2AgCl + Na2S
Al2O3 + 2NaOH 2NaAlO2 + H2O

Pure alumina is recovered from the filtrate

NaAlO2 + 2H2O Al(OH)3 + NaOH

2Al(OH)3 Al2O3 + 3H2O



Gold and silver are also extracted from their native ores by Leaching (Mac-Arthur Forrest cyanide process). Both
silver and gold particles dissolves in dilute solution of sodium cyanide in presence of oxygen of the air forming
complex cyanides

4Ag + 8NaCN + 2H2O + O2



4NaAg(CN)2 + 4NaOH

Sod. argento cyanide

4Au + 8NaCN + 2H2O + O2 4NaAu(CN)2 + 4NaOH


Ag or Au is recovered from the solution by the addition of electropositive metal like zinc.
2NaAg(CN)2 + Zn Na2Zn(CN)4 + 2Ag

2NaAu(CN)2 + Zn Na2Zn(CN)4+ 2Au



2. Second operationReduction to free metal

Some of the methods commonly used to get free metal the concentrated ore are given below :

(a) Smelting : This involves the reduction of the ore to the molten metal at a high temperature. For the extraction of
less electropositive metals such as Pb, Zn, Fe, Sn, etc., powerful reducing agents such as C, H
2
, CO, water gas, Na,
K, Mg, Al may be used. Some examples are given below :

PbO + C Pb + CO

WO3 + 3H2 W + 3H2O

CuO + CO Cu + CO2

TiCl4 + 2Mg Ti + 2MgCl2

Cr2O3 + 2Al 2Cr + Al2O3

Out of these carbon reduction and aluminium reduction are important processes.

(i) Carbon reduction process : It is generally called as smelting. The oxides of the less electropositive metals are
reduced by strongly heating them with coal or coke.
PbO + C Pb + CO

PbO + CO Pb + CO2


Similarly,
Fe2O3 + 3C 2Fe + 3CO

Fe2O3 + 3CO 2Fe + 3CO2


The ores, even after concentration, contain some gangue. To remove gangue, certain substances are mixed with
concentrated ore which combine with gangue to form fusible material which is not soluble in molten metal. The
substances used are called fluxes and the fusible material formed during reduction process is called slag. Slag is
usually lighter and floats on the surface of the molten metal.
An acidic flux (e.g., silica, borax, etc.) is the chemical substance which removes the basic impurities.

SiO2 + CaO


CaSiO3
Acidic flux

Basicimpurity

(Gangue)
Slag
The basic flux (e.g., limestone, magnesite, ferric oxide, etc.) is the chemical substance which removes the acidic
impurities.


MgCO3 + SiO2





MgSiO3 + CO2
Basic flux
Acidicimpurity

(Gangue)
Slag

(ii) Reduction by aluminium (Goldschmidt aluminothermic process) : This process is employed in the case of
those metals which have very high melting points and are to be extracted from their oxides. Their reduction with
carbon is not satisfactory. A mixture of concentrated oxide ore and aluminium powder, commonly called as thermite,
is taken in a steel crucible placed in a bed of sand. The reaction is started by the use of an ignition mixture containing
magnesium powder and barium peroxide.
Cr2O3 + 2Al 2Cr + Al2O3

3Mn3O4 + 8Al 9Mn + 4Al2O3
Large amount of heat energy is released during reduction, which fuses both the alumina and the metal.

(b) Self reduction process : This process is also called autoreduction process or air reduction process. The sulphide
ores of less electropositive metals like Hg, Pb, Cu, etc., are heated in air as to convert part of the ore into oxide or
sulphate which then reacts with the remaining sulphide ore to give the metal and sulphur dioxide. No external
reducing agent is used in this process.
2HgS + 3O2 2HgO + 2SO2 Extraction of Hg

2HgO + HgS 3Hg + SO2 from cinnabar ore

2PbS + 3O2 2PbO + 2SO2 Extraction of lead

2PbO + PbS 3Pb + SO2 from galena ore

Electrolytic reduction : The oxides of the highly electropositive metals like Na, K, Mg, Ca, Al, etc., cannot be
reduced easily with carbon at moderate temperatures. For reduction, a very high temperature is required at which the
metal may combine with carbon to form a carbide. These metals are thus extracted by the electrolysis of their oxides,
hydroxides or chlorides in fused state. Sometimes, a small amount of some other salt is added as to lower the fusion
temperature or to increase the conductivity or both. The metal is liberated at the cathode. Sodium is obtained by the
electrolysis of fused mixture of NaCl and CaCl2 (Down's process) or by electrolysis of fused sodium hydroxide
(Castner's process).


(d)Hydrometallurgy: This process is based on the fact that more electropositive metal can displace less
electropositive metal from its salt solution. The ore is treated with such chemical reagents which convert it into soluble
compound. By the addition of more electropositive metal to the filtrate, the metal present in the ore can be
precipitated. The following two examples illustrate this process.

(i) Extraction of copper : Malachite ore is first roasted.
CuCO3Cu(OH)2 2CuO + H2O + CO2
Copper oxide obtained is dissolved in sulphuric acid.
CuO + H2SO4 CuSO4 + H2O
(Soluble)
To the solution of copper sulphate, scrap iron is added which precipitates copper.

CuSO4 + Fe Cu + FeSO4
ppt. Soluble

(ii) Extraction of silver : The ore is dissolved in sodium cyanide solution.
Ag2S + 4NaCN 2NaAg(CN)2 + Na2S

By the addition of zinc turnings, Ag is precipitated

2NaAg(CN)2 + Zn Na2Zn(CN)4 + 2Ag
Soluble ppt.




(e) Amalgamation process : This method is used for the extraction of noble metals like gold, silver, etc., from the
native ores. The finely powdered ore is brought in contact with mercury which combines with the particles of the metal
present in the ore and form amalgam. The metal is recovered from the amalgam by subjecting it to distillation, where
the mercury distills over leaving behind the metal.


3. Third operation-Refining or purification : The metals obtained by the application of above reduction methods
from the concentrated ores are usually impure. These impure metals may be associated with small amounts of
(a) unchanged ore,
(b) other metals produced by the simultaneous reduction of their compounds originally present in the ore,
(c) non-metals like silicon, carbon, phosphorus, etc.
(d) residual slag, flux, etc.
The impure metal is thus subjected to some purifying processes known as refining in order to remove the undesired
impurities.
The following refining processes may be applied depending upon the nature of the metal under treatment and the
nature of the impurities.

(a) Liquation process : This process is based on the difference in fusibility of the metal and impurities. When the
impurities are less fusible than the metal itself, this process is employed. The metal melts and flows down leaving
behind the impurities on the hearth. This method is used to purify the metals like Bi, Sn, Pb, Hg, etc.

(b) Distillation : This process is used for those metals which are easily volatile. The impure metal is heated in a
retort and its vapours are separately condensed in a receiver. The non-volatile impurities are left-behind in the retort.
This is used for the purification of Zn, Cd, Hg, etc.

(c) Pyrometallurgical oxidation process : This process is used when the impurities have a greater affinity for
oxygen than the metal itself. This method is usually employed for refining the metals like Fe, Cu, Ag, etc. The
oxidation is done by various ways.
(i) Cupellation : The impure metal is heated in a cupel or oval shaped crucible made of bone ash or cement and a
blast of air is passed over the molten mass. The impurities get oxidised and removed with the blast of air. For
example the impurity of lead present in silver is removed by cupellation process.

(ii) Bessemerisation : The impure-metal is heated in a furnace and a blast of compressed air is blown through the
molten mass. The impurities get oxidised. For example, the molten pig iron is taken in a bassemer converter and
compressed air is passed which oxidises the impurities.

2Mn + O2 2MnO,
Si + O2 SiO2
2C + O2 2CO,
MnO + SiO2 MnSiO3
Slag



(iii) Poling : The impure metal containing oxides as impurity can be purified by this method. The molten impure metal
is stirred with green poles of wood. The green poles of wood release the hydrocarbon gases which reduce the oxide
impurities. This method is especially used in the purification of copper. (old method)
(d) Electrolytic refining of metals : Many of the metals such as copper, silver, gold, aluminium, lead, etc., are
purified by this method. This is perhaps the most important method. The impure metal is made anode while a thin
sheet of pure metal acts as a cathode. The electrolytic solution consists of generally an aqueous solution of a salt or
a complex of the metal. On passing the current, the pure metal is deposited on the cathode and equivalent amount of
the metal gets dissolved from the anode. Thus, the metal is transferred from anode to cathode through solution. The
soluble impurities pass into the solution while the insoluble one, especially less electropositive impurities collect
below the anode as anodic mud or anode sludge,. Some examples are given below :

(i) Purification of copper
Impure metalAnode; Thin sheets of copperCathode
ElectrolyteAn aqueous solution of copper sulphate containing H2SO4.

A current of 1.3 volt is used. Anodic mud contains Ag, Au, Pt, Pd, etc., and impurities like Fe, Zn, Ni, etc., pass into
the solution. 99.9% pure copper is obtained.

(ii) Purification of lead
Impure metalAnode; Thin sheets of pure leadCathode
ElectrolyteA solution of lead silico fluoride PbSiF6 containing 8 10% of H2<>/subSiF6

(e) Special methods

(i) Monds process : Nickel is purified by this method. Impure nickel is treated with carbon monoxide at 6080C
when volatile compound, nickel carbonyl, is formed. Nickel carbonyl decomposes at 180C to form pure nickel and
carbon monoxide which can again be used.

(ii) Van-Arkel process : This methods is generally applied for obtaining ultrapure metals. The impure metal is
converted into a volatile compound while the impurities are not affected. The volatile compound is then decomposed
electrically to get the pure metal.

Ti, Zr, Hf, Si, etc., have been refined by this method. The method is quite expensive.