General Principles of Metal Extraction

Submitted By : Ali Abbas Aslam

Roll No : Bsf1900252
Submitted to : Miss Abida
Class : BS Chemistry (Evening)
3rd Semester
University of Education, Township, Lahore
Extractive Metallurgy:
Extractive metallurgy is a branch of metallurgical engineering wherein process and methods of
extraction of metals from their natural mineral deposits are studied. The field is a materials science, covering
all aspects of the types of ore, washing, concentration, separation, chemical processes and extraction of pure
metal and their alloying to suit various applications, sometimes for direct use as a finished product, but more
often in a form that requires further working to achieve the given properties to suit the applications. The
field of ferrous and non-ferrous extractive metallurgy have specialties that are generically grouped into the
categories of mineral processing, hydrometallurgy, pyrometallurgy, and electrometallurgy based on the
process adopted to extract the metal. Several processes are used for extraction of same metal depending on
occurrence and chemical requirements.
It takes multiple steps to extract the "important" element from the ore:
1. First, the ore must be separated from unwanted rocks.
2. Then, the minerals need to be separated out of the ore
3. Since most minerals are not pure metals, further separation methods are required.
Most minerals are chemical compounds that contain metals and other elements.

General Principles/Processes:

1. Concentration:

After mining, large pieces of the ore feed are broken through crushing and/or grinding. This step creates
particles that are either mostly valuable or mostly waste. Concentrating the particles of value in a form
supporting separation enables the desired metal to be removed from waste products.

 Hydraulic Washing:
It is based on the difference in gravity of the particles of the gangue and the ore. So, it is considered
as a type of gravity separation. During this process, an upward stream of running water is used to wash the
powdered ore. The lighter gangue particles are washed leaving the heavier ore particles.  Hydraulic washing
is used for ores that have tin or lead, as they are heavier than the gangue.
 Hydraulic washing

 Magnetic Separation:

It is based on the principle of magnetic properties of the ore components. If either the ore particles or
the gangue is capable of being attracted in a magnetic field, magnetic separation can be used. Ore is kept in a
conveyer which passes through the magnetic roller.

Magnetic separation

 Froth floatation process:

This method is used to separate gangue from the sulphide ores. This process is used for sulphide ores
of Cu, Pb and Zn. Suspension of powdered ore is prepared using water. To this suspension, collectors and
froth stabilizers are added. Pine oils, fatty acids are used as collectors to enhance the non-wettability of the
mineral particles. Whereas froth stabilizers such as cresols, aniline, are added to stabilize the froth. A
rotating paddle agitates the mixture and draws air in it. This results in the formation of froth which carries
the mineral particles. The froth is light and is scanned off. It is then dried for recovery of the ore particles.
Sometimes depressants are used to separate the sulphide ores by adjusting the proportion of oil to water.
Such as, in case of an ore containing Zinc sulphide and lead sulphide. The depressant used is sodium
cyanide.
 Froth floatation process

Floatation stages are as follows:

 Roughing is the first stage of floatation. During this process, maximum amount of valuable material
is removed. Sometimes pre-floatation step is followed for before roughing. This is done to remove
contamination such as organic carbon.
 Cleaning is the next step for floatation. During this step, undesired material is removed. The product
of this step is known as cleaner concentrate.
 Scavenging is the last step of the floatation process. This is to recover those important materials
which are not recovered during roughing.

Chemicals of floatation process

 Collectors are anionic Sulphur ligands. For example, xanthate salts. Other collectors used are fatty
acids, fatty amines.

 Frothers are used to stabilize the froth. For example, pine oil, alcohols etc.

 Modifiers are used to optimize the separation process. pH modifiers include lime (CaO), Caustic

soda (NaOH), etc. Anionic modifiers include phosphates, silicates, and carbonates. Organic
modifiers include the thickeners dextrin, starch, glue, etc.

 Leaching:

It is used when ore is soluble in some solvent. It is explained based on following example-

 Leaching of alumina from bauxite. Bauxite is an ore of aluminium. It contains silicon dioxide, iron
oxides and titanium oxide. Concentrated solution of sodium hydroxide at a pressure of 473 – 523 K
and 35 – 36 bar is used for concentrating the ore. During this process, bauxite is leached out as
sodium aluminate, leaving other impurities:
 Al2O3(s) + 2NaOH(aq) + 3H2O(I) → 2Na[AI(OH)4](aq)

The carbon-dioxide is passed through it and hydrated bauxite is obtained.

2Na[Al(OH)4](aq) + CO2(g) → Al2O3.xH2O(s) + 2NaHCO3

Leaching of alumina from bauxite

2. Extraction of Metal from Concentrated Ore:

 Calcination and Roasting of the Ore

The concentrated ore is converted into metal oxide by calcination or roasting.

(A) Calcination:
Calcination involves heating of the concentrated ore in a limited supply of air so that it loses moisture,
water of hydration and gaseous volatile substances. The ore is heated to a temperature so that it does not
melt. Two examples of calcination are given below:
(i) Removal of water of hydration

Al2 O3 .2H2 O¾¾¾® Al2 O3 + 2H2O

(ii) Expulsion of CO2 from carbonate

ZnCO 3 ¾¾¾® ZnO + 2CO2

(B) Roasting:
Roasting is a process in which the concentrated ore is
heated in a free supply of air at a temperature insufficient to
melt it. The following changes take place during roasting:
(i) Drying of the ore.
(ii) Removal of the volatile impurities like arsenic, sulphur,
phosphorus and organic matter.

4As + 3O 2 ¾¾¾® 2As 2 O3 (g)

S + O 2 ¾¾¾® SO 2 (g)
(iii) Conversion of the sulphide ores
into oxides

2PbS + 3O2

¾¾¾® 2PbO + 2SO2

2ZnS + 3O 2

¾¾¾® 2ZnO + 2SO2

Calcination and roasting are

generally carried out in a reverberatory
furnace or in a multiple hearth
furnace.

 Reduction of
the Metal Oxides to Free Metal

This process is carried out after calcination or roasting of ores. In this process called smelting, the
oxide ores are converted into the metallic state by reduction.
(A) Smelting:
Smelting is a process in which the oxide ore in molten state is reduced by carbon or other reducing
agents to free metal.

(i) by using carbon as a reducing agent:

This method is used for the isolation of iron, tin and zinc metals from their respective oxides. The
oxide ores are strongly heated with charcoal or coke. Reduction occurs by the action of carbon and/or
carbon monoxide which is produced by the partial combustion of coke or charcoal.
 Fe2 O3 + 3C ¾¾¾® 2Fe + 3CO

Fe2 O3 + CO ¾¾¾® 2FeO + CO2

FeO + CO ¾¾¾® Fe + CO2

Although the ore has been concentrated in an earlier step, it is still contaminated with some gangue material
which is finally removed in the reduction process by the addition of flux during smelting.
“Flux is a chemical substance which combines with gangue at higher temperatures to form easily
fusible material called slag which is not soluble in the molten metal”. Flux are of two types:

 Basic Flux:

On heating, lime stone is converted into calcium oxide used as basic flux which combines with acidic impurities

like silica in metallurgy of iron and forms fusible calcium silicate ( CaSiO3 ).

CaCO 3 ¾¾¾® CaO + CO 2 (g)

(Limestone)

CaO + SiO 2 ¾¾¾® CaSiO3

(Basic flux)
(Acidic gangue) (Slag)

 Acidic flux:

SiO2 is used as acidic flux to remove basic impurity of FeO in metallurgy of Cu.

SiO 2 + FeO ¾¾¾® FeSiO3

(Basic gangue)
(Acidic flux) (Slag)

The fusible slag, such as calcium silicate formed during smelting floats over the molten metal and is
thus easily removed. Another advantage is that the slag provides a covering to the molten metal thus
preventing it from getting oxidized by air.
(ii) Other reducing agents:

Oxide ores which cannot be reduced by carbon or metals which show affinity to carbon by forming
metal carbides, are reduced by reducing agents like aluminium, sodium, magnesium or hydrogen.
Oxide like chromium oxide (Cr2 O3 ) or manganese oxide (Mn 3 O4 ) are reduced by aluminium
 powder is a highly exothermic reaction. This process is known as Goldschmidt's Alumino-thermite
reduction method.

Cr2 O3 + 2Al ¾¾¾® 2Cr + Al2 O3 + Heat

3Mn 3O 4 + 8Al ¾¾¾® 9Mn + 4Al2 O3 + Heat

Heat is generated in the process due to the formation of Al 2 O3 which is a highly exothermic reaction.

Titanium is obtained by the reduction of TiCl4 (produced by the action of carbon and chlorine on TiO2)
by Mg in an inert atmosphere of argon (Kroll process).

Heat
TiCl 4 + 2Mg ¾¾¾¾ ® Ti + 2MgCl 2

1103 K

(iii) Self-reduction:

This is applied to the sulphide ores of copper, mercury and lead. The ores are heated in air, a part of
these sulphide ores is changed into the oxide or sulphate which then reacts with the remaining part of
the sulphide ore to give the metal and sulphur dioxide. The reactions showing their extraction are given
below:

(1) 2Cu 2 S + 3O 2 ¾¾¾® 2Cu 2O + 2SO 2

Copper glance

2Cu 2 O + Cu 2S ¾¾¾® 6Cu + SO 2

Copper produced at this stage is called Blister copper. The evolution of sulphur dioxide produces blisters on the
surface of solidified copper metal.

(2) 2HgS + 3O 2 ¾¾¾® 2HgO + 2SO2

Cinnabar

2HgO + HgS ¾¾¾® 3Hg + SO2

(3) 2PbS + 3O 2 ¾¾¾® 2PbO + 2SO2

Galena

PbS + 2O 2 ¾¾¾® PbSO 4

PbS + 2PbO ¾¾¾® 3Pb + SO 2

 PbS + PbSO4 ¾¾¾® 2Pb + 2SO2

(B) Reduction of concentrated ores by other methods:

Some metals cannot be obtained from their ores by using common reducing agents such as C, CO, H2 etc. Other
methods of reduction are used for such cases.

(i) Reduction by precipitation:

Noble metals like silver and gold are extracted from their concentrated ores by dissolving metal ions in
the form of their soluble complexes. The metal ions are then regenerated by adding a suitable reagent.
For example, concentrated argentite ore

Ag 2S) is treated with a dilute solution of sodium cyanide (NaCN) to form a soluble complex :

Ag 2S + 4NaCN ¾¾¾® 2Na [Ag(CN)2 ] + Na2 S

This solution is decanted off and treated with zinc to precipitate silver,

2Na[Ag(CN) 2 ] + Zn ¾¾¾® Na 2 [Zn(CN)4 ] + 2Ag ¯

(ii) Electrolytic Reduction:

Active metals like sodium, potassium and aluminium etc., are extracted by the electrolysis of their
fused (molten) salts. For example, sodium is obtained by the electrolysis of fused sodium chloride
(Down's process). The reactions taking place in the electrolytic cell are:

+
Na ions move towards the cathode and Cl- ions move towards the anode. Following reactions take place at the
electrodes:
 + - ¾¾¾® Na
At the Cathode: Na + e (Reduction)
(Negative electrode) (metal)

At the Anode - ¾¾¾® Cl + e -

Cl

(Positive electrode) (Oxidation)

Cl + Cl ¾¾¾® Cl2

3. Refining of Metals
Except in the electrolytic reduction method, metals produced by any other method are generally impure. The
impurities may be in the form of (i) other metals (ii) unreduced oxide of the metal (iii) non-metals like
carbon, silicon, phosphorus, sulphur etc. and (iv) flux or slag. Crude metal may be refined by using one or
more of the following methods:

i. Liquation: Easily fusible metals like tin, lead etc. are refined by this process. In this method, the
impure metal is poured on the sloping hearth of a reverberatory furnace and heated slowly to a
temperature little above the melting point of the metal. The pure metal drains out leaving behind
infusible impurities.

Liquation

ii. Poling: Poling involves stirring the impure molten metal with green logs or bamboo. The
hydrocarbons contained in the pole reduce any metal oxide present as impurity. Copper and tin are
refined by this method.
 Poling

iii. Distillation: This method is used for the purification of metals which possess a low boiling point
such as mercury and zinc. In this process the impure metal is heated above its boiling point so that it can
form vapours. The impurities do not vaporize and hence they are separated. The vapours of the pure metal
are then condensed leaving the impurities
behind.

iv. Electrolytic Refining: A large number of metals like copper, silver, zinc, tin etc. are refined by
electrolysis. A block of impure metal is made the anode and a thin sheet of pure metal forms the
cathode of the electrolytic cell containing suitable metal salt solution which acts as an electrolyte. On
passing current, pure metal deposits at the cathode sheet while more electropositive impurities are
left in solution. Less electropositive metals do not
dissolve and fall away from the anode to settle below it
as anode mud.
 For example, in the electrolytic refining of crude copper (blister copper), a large piece of impure
copper is made anode and a thin piece of pure copper is made the cathode. An acidified solution of copper
sulphate is used as an electrolyte. On passing an electric current of low voltage through the solution copper
(II) ions obtained from copper sulphate solution go to the cathode where they are reduced to the free copper
metal and get deposited.

Cu 2+ + 2e - ¾¾¾® Cu (at cathode)

An equivalent amount of the metal from the anode dissolves into the electrolyte as Cu2+ ions

-
Cu ¾¾¾® Cu 2+ + 2e (at anode)

As the process goes on, anode becomes thinner while the cathode becomes thicker. The impurities like
silver, gold settle down at the bottom of the cell as 'anode mud'.