Principles of Non Ferrous

Extraction Metallurgy
Date 14th Aug, 2014

Let us take case of Metallothermic

reduction of oxides and halides
TiCl4 (g) + 2Mg (l) = Ti (c) + 2MgCl2 (l)
Indicates above MP (650 deg C) of Mg

SiCl4(g) + 2Zn(g) = Si (c) + ZnCl2 (l)

Indicates above BP of Zn (907 deg C)

In above reaction vacuum will have adverse

effect on equilibrium???

High Pressure Process

This can be employed when net decrease in
volume of product is taking place
This means gaseous phase must get
consumed(reactant end) than generated
(product end)
High pressure process are not widely
employed for commercial extraction : the
reason is you require net decrease in volume
at product end during high pressure

High pressure process example

ZrO2(s) + 2 Ca(g) = Zr (s) + 2 CaO (s)
Ca has MP of 851 deg C and BP of 1482 deg C
From the above reaction, since equilibrim
partial pressure of Ca is quite high so high
pressure process become mandatory
This employed using stainless steel High
pressure vessel (BOMB) as a reduction
chamber

Extraction by smelting, metallothermic

reduction, solid state reduction
In all the three cases ore was in form of an
oxide

Similarly there is extraction of metal

from sulphide ores
Extraction of lead, zinc and copper

Reactive Metals
Metals like Ti, Zr, Li, Be, Ta, Nb, rare earth
metal
Reactive metals are produced via halide route
WHY HALIDE route??
Because they are more reactive towards
oxygen and if they reduced they again form
oxidesresidual oxygen in reactive metals
affects their mechanical properties

Ti extraction (KROLLs Process)

TiO2 (s) + C (s) + 2Cl2 (g) = TiCl4 (g) + CO2(g)
At 900 deg C
TiCl4 (g)+ 2 Mg (l) = Ti (s) + 2 MgCl2 (l)
At 900 deg C

Reactions
You have seen different types of chemical
reaction which are adopted in Pyrometallurgical
process
Reaction which are discussed till time are the
case of Heterogeneous reaction
Consider a reaction
[A] + [B2+] = [B] + [A2+]
Above reaction indicates that elements are
present in form of ions and neutral phase of
either [A] or [B]

Reactions
Let us take an example for metal oxide
MO + M = MO + M, can we say here that
exist an interface
Reaction does not occur in one go, reaction
consist of steps which is known as kinetic
steps

Reactions

[A]

[B2+]

Metal phase
Slag phase

For reaction [A] + [B2+] = [B] + [A2+]

(1) Transfer of [A] to the interface
(2) Transfer of [B2+] in the slag phase to the
interface
(3) Chemical reaction will take place at the
interphase (This will govern the chemical
reaction rates)
(4) Transfer of [B] from interface to metal phase
(5) Transfer of [A2+]from interface to slag phase

Reactions

The reaction which we are talking about is taking

place at interface
This also suggest that reaction is not homogeneous,
which normally takes place in bulk
Reaction 1,2, 4 and 5 are nothing but mass transfer
steps

Important
Rate of chemical reaction at the interface is
proportional to interfacial area

In homogeneous reaction, rate of chemical

reaction is proportional to volume

Interfacial reaction is different from

homogeneous reaction
The interfacial reaction consist of

Adsorption of reactants at the interface

Chemical reaction among the adsorbed
species

Desorption of products from the bulk
(reverse of adsorption)[Remember no
absorption or desorption occurs in
homogenous reaction]

To give you an idea what could be

happening at the interface

Adsorption at the interface is assumed to be few atomic

layer thick by the species

For your information

Adsorption are of two kinds
(a) Physical adsorption
(b) Chemical adsorption
Physical adsorption are weak and are physical
in nature
If adsorption is weak which means it may be
reversible

Physical adsorption vs Chemical

adsorption

Adsorption