Principles of Non Ferrous

Extraction Metallurgy
Date 20th Aug, 2014
Class test on 4th Sept (Thursday)

Questions
When to apply selective distillation?
What about high vapor pressure metals? Can
we apply selective distillation? If we can apply
than what challenges we have?
What about high vapor pressure metals?

Clue
Zinc and cadmium are two common materials
which are often avoided in high vacuum systems
due to their high vapor pressures.
The vapor pressures of most familiar metals are
well below 1 x 10-6 Torr at room temperature.
The vapor pressure of a material rises sharply
with temperature.
Two common elements which are solid at room
temperature but which also have relatively high
vapor pressures are sulfur and phosphorus.

Vapor pressure curves

Roasting
Temperature is an important factor in
determining the nature (Physical and
chemical) of product obtained
The desired product can be obtained by
knowing composition of gas used in Roasting
and equilibrium relationship in M-S-O system
The isothermal behavior of M-S-O system can
be represented by predominance area
diagram

Roasting
Predominance area diagram is at specified
temperature for solids which are in
equilibrium with gas having specified partial
pressure of oxygen and sulphur dioxide
Even in case of partial roasting this diagram is
helpful to determine product formed

Sulphide Roasting
MS2(c) = MS (c) + 1/2S2
S2(g) + O2(g) = SO2(g)
MS (c) + 3/2O2 =MO + SO2
Above reaction says that SO2 always forms as
soon as oxygen comes in contact with
sulphide ores

Ni-S-O system at 1000 K

Condense Phases: Ni,
NiO, Ni3S2, NiSO4
D
C

Gas Phases: SO2, O2

SO2(g)+ 1/2O2(g)= SO3(g)

Some SO3 may also form
due to above reaction

Say for condense system NiS and NiO

NiS (c) + 3/2 O2(g) = NiO + SO2(g)
K=pSO2/(pO2)3/2
log(K) = log pSO2 3/2logpO2

G= -RT ln(K), From here K can be calculated

D
C
B

What about BC

Ni3S2 (c)+ 7/2O2(g)=3NiO (c) + 2SO2(g)

K=pSO2/(pO2)7/2
log PSO2 = log K + 7/2logpO2
This line corresponds to line BC

D
C
B

Remember
there is
difference
between Line BC
and CD

Similarly for line AB

Ni(c) + O2 = NiO(c)
K=1/(pO2)1/2
Log K=-1/2 log pO2
This equation indicates that Ni(c) + O2 =
NiO(c) reaction exist at fixed value of pO2
Equilibrium is independent of pSO2
D
C
B
A

Why Predominance Area

It is are where both pO2 and pSO2 can be varied
i.e 2 degree of freedom
Along the vertical line only parameter can be
varied: only one degree of freedom
Along point: non variant
D
C
B
A

Roasting Practice in Industry

In order to practice roasting we have to
answer

( a) the required physical condition

(b) the required chemical composition of the
roasted product

Physical condition
If roasted product will be used in blast furnace
than product has to be coarse and cellular
For Retort F/c or reverberatory f/c, product
has to be fine
For leaching, product should be porous,
the formation of insoluble compound must be
avoided

Chemical composition
This is ore specific
In some cases you want to remove sulphur
before next operation (For zinc and lead
roasting entile sulphur is removed)
Or in some cases sulphur are desirable (In
copper sulphur is intentionally retained for
next operation)
From chemical composition point of view the most desirable roasting
process is one which is Commercially more satisfactory